Curable resin composition, adhesive composition, cured product, semiconductor device, and electronic component

Abstract

The present invention addresses the problem of providing: a curable resin composition which can be applied with a narrow line width (for example, 1,000 μm or less) and a high coating height; an adhesive composition; a cured product of the same; a semiconductor device which comprises the cured product; and an electronic component.　Provided are: a curable resin composition which contains (A) a polymerizable compound, (B) a polymerization initiator, (C) an inorganic thixotropy-imparting agent, and (D) a modified polydimethylsiloxane, wherein the content of (C) the inorganic thixotropy-imparting agent is 10-70 parts by mass with respect to 100 parts by mass of the curable resin composition, and the content of (D) the modified polydimethylsiloxane is 0.01-15 parts by mass with respect to 100 parts by mass of (C) the inorganic thixotropy-imparting agent; an adhesive composition; a cured product of the same; a semiconductor device which comprises the cured product; and an electronic component.

Description

Curable resin composition, adhesive composition, cured product, semiconductor device and electronic component

[0001] The present invention relates to a curable resin composition, an adhesive composition, a cured product thereof, and a semiconductor device and an electronic component each including the cured product.

[0002] Currently, adhesives, sealants, etc. containing curable resin compositions are often used for assembling and mounting components used in semiconductor devices or electronic components in order to maintain reliability, etc. Various types of curable resin compositions have been developed depending on the application location and use of the adhesive or sealant (for example, Patent Documents 1 to 3).

[0003] In particular, adhesives used in assembling and aligning optical components require a high degree of fixing precision because they are used to align, fix, and join the light path (optical axis) with high precision.

[0004] Republished Patent Publication No. 2017 / 094584 JP 2021-147584 A JP 2017-101112 A

[0005] A technology called active alignment is used to achieve high-precision bonding in optical module assembly. To increase precision, the active alignment method involves capturing a test pattern using an image sensor such as a CCD (charge-coupled device) or CMOS (complementary metal-oxide semiconductor), aligning the optical axis to ensure there is no blurring in any area of ​​the image, and then bonding using a high-precision adhesive for alignment.

[0006] In recent years, optical modules have been required to be increasingly smaller and more highly integrated, and it is expected that the application area of ​​the alignment adhesive used in the active alignment method will become increasingly narrow. Therefore, the adhesive must be capable of application with a narrow line width (e.g., 1000 μm or less). At the same time, to enable high-precision alignment even in a narrow application area, the adhesive must be able to be applied to a desired height without sagging when applied with a narrow line width.

[0007] Therefore, an object of the present invention is to provide a curable resin composition, an adhesive composition, a cured product thereof, and a semiconductor device and an electronic component each including the cured product, which can be applied to a thin line width (for example, 1000 μm or less) while maintaining a coating height.

[0008] Specific means for solving the above problems are as follows. The present invention encompasses a curable resin composition, an adhesive composition, a cured product, and a semiconductor device or electronic component according to the following embodiments. [1] A curable resin composition comprising: (A) a polymerizable compound; (B) a polymerization initiator; (C) an inorganic thixotropy-imparting agent; and (D) a modified polydimethylsiloxane, wherein the content of the (C) inorganic thixotropy-imparting agent is 10 to 70 parts by mass per 100 parts by mass of the curable resin composition; and the content of the (D) modified polydimethylsiloxane is 0.01 to 15 parts by mass per 100 parts by mass of the (C) inorganic thixotropy-imparting agent. [2] The curable resin composition according to [1] above, wherein the (A) polymerizable compound comprises a (meth)acrylate compound. [3] The curable resin composition according to [1] above, wherein the (A) polymerizable compound comprises an epoxy compound. [4] The curable resin composition according to [1] above, wherein the polymerizable compound (A) comprises a (meth)acrylate compound and an epoxy compound. [5] The curable resin composition according to any one of [1] to [4] above, wherein the inorganic thixotropy-imparting agent (C) comprises inorganic fine particles. [6] The curable resin composition according to any one of [1] to [5] above, wherein the inorganic thixotropy-imparting agent (C) comprises silica fine particles. [7] The curable resin composition according to any one of [1] to [6] above, wherein the modified polydimethylsiloxane (D) is modified with at least one modifying group selected from the group consisting of C3 to C20 alkyl, aralkyl, alcohol, phenol, polyether, aryl, amino, epoxy, and carboxyl. [8] The curable resin composition according to any one of [1] to [7] above, wherein the modified polydimethylsiloxane (D) has a hydroxyl group, a phenyl group, or a combination thereof. [9] The curable resin composition according to any one of the items [1], [2], and [4] to [8], wherein the (A) polymerizable compound contains a (meth)acrylate compound, and when the curable resin composition is applied in one layer with a line width W in the range of 100 to 500 μm, the ratio (H1 / W1) of the height H1 of one layer of the curable resin composition to the line width W1 of one layer of the curable resin composition is 0.82 or more.

[10] The curable resin composition according to any one of claims [1], [2], and [4] to [9], wherein the polymerizable compound (A) comprises a (meth)acrylate compound, and when the curable resin composition is applied in two layers with a line width W in the range of 100 to 500 μm, the ratio (H2 / W1) of the height H2 of the second layer of the curable resin composition to the line width W1 of the first layer of the curable resin composition is 1.49 or more.

[11] The curable resin composition according to any one of claims [1] and [3] to [8], wherein the polymerizable compound (A) comprises an epoxy compound, and when the curable resin composition is applied in one layer with a line width W in the range of 100 to 500 μm, the ratio (H1 / W1) of the height H1 of the first layer of the curable resin composition to the line width W1 of the first layer of the curable resin composition is 0.78 or more.

[12] The curable resin composition according to any one of [1], [3] to [8], and

[11] , wherein the (A) polymerizable compound comprises an epoxy compound, and when the curable resin composition is applied in two layers with a line width W in the range of 100 to 500 μm, the ratio (H2 / W1) of the height H2 of the second layer of the curable resin composition to the line width W1 of the first layer of the curable resin composition is 1.40 or more.

[13] The curable resin composition according to any one of [1] to

[12] , which is to be applied in a line width in the range of 50 to 1000 μm.

[14] The curable resin composition according to any one of [1] to

[13] , which is to be applied in two or more layers.

[15] The curable resin composition according to any one of [1] to

[14] , which is an adhesive composition.

[16] The curable resin composition according to any one of [1] to

[15] , which is used in a component alignment step in a manufacturing method of a semiconductor device or electronic component.

[17] A cured product obtained by curing the curable resin composition according to any one of [1] to

[16] above.

[18] A semiconductor device or electronic component comprising the cured product according to

[17] above.

[0009] According to an aspect of the present invention, there are provided a curable resin composition, an adhesive composition, a cured product thereof, and a semiconductor device and an electronic component including the cured product, which can be applied to a thin line width (for example, 1000 μm or less) while maintaining a coating height.

[0010] In this specification, following the convention in the field of synthetic resins, the term "resin," which usually refers to a polymer (particularly a synthetic polymer), may be used to refer to a component constituting a curable resin composition before curing, even if the component is not a polymer, for example, a prepolymer compound before curing. In this specification, "(meth)acryloyl group" refers to both a methacryloyl group and an acryloyl group. Furthermore, "(meth)acrylate compound" refers to both an acrylate compound and a methacrylate compound. Furthermore, in this specification, "curable resin composition" may be simply referred to as "resin composition."

[0011] [Curable Resin Composition] A curable resin composition according to one embodiment of the present invention comprises: (A) a polymerizable compound; (B) a polymerization initiator; (C) an inorganic thixotropy-imparting agent; and (D) a modified polydimethylsiloxane, wherein the content of the inorganic thixotropy-imparting agent (C) is 10 to 70 parts by mass per 100 parts by mass of the curable resin composition; and the content of the modified polydimethylsiloxane (D) is 0.01 to 15 parts by mass per 100 parts by mass of the inorganic thixotropy-imparting agent (C). According to this embodiment, a curable resin composition is provided that can be applied to produce a thin line width (e.g., 1000 μm or less) while maintaining a coating height.

[0012] (A) Polymerizable Compound The curable resin composition of this embodiment contains (A) a polymerizable compound (hereinafter also referred to as "component (A)"). The (A) polymerizable compound has a reactive group for curing and imparts curability to the resin composition. In this embodiment, the (A) polymerizable compound can be appropriately selected from a radical polymerizable compound, a cation polymerizable compound, an anion polymerizable compound, or any combination thereof.

[0013] Examples of the radical polymerizable compound include, but are not limited to, compounds having an unsaturated double bond such as (meth)acrylate compounds, maleimide compounds, (meth)acrylamide compounds, cyanoacrylate compounds, vinyl ether compounds, styrene compounds, and methylene malonates (2-methylene-1,3-dicarbonyl compounds and derivatives thereof), or mixtures of compounds having an unsaturated double bond and thiol compounds (mixtures capable of ene-thiol reaction).

[0014] In this specification, the (meth)acrylate compound refers to a compound having at least one (meth)acryloyl group in the molecule, and includes a monofunctional (meth)acrylate compound having one (meth)acryloyl group and a polyfunctional (meth)acrylate compound having two or more (meth)acryloyl groups. Examples of the monofunctional (meth)acrylate compound include: Ethyl (meth)acrylate, trifluoroethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, isoamyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, isobornyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, phenoxyethyl (meth)acrylate, benzyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, butoxydiethylene glycol (meth)acrylate Esters of monohydric alcohols and (meth)acrylic acid such as acrylate, methoxydipropylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, 2-ethylhexyldiethylene glycol (meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate, and 3-phenoxybenzyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, octyl acrylate, nonyl acrylate, isononyl acrylate, 3,3,5-trimethylcyclohexyl acrylate, cyclic trimethylolpropane formal acrylate, and 1-naphthalenemethyl (meth)acrylate.1-Ethylcyclohexyl (meth)acrylate, 1-methylcyclohexyl (meth)acrylate, 1-ethylcyclopentyl (meth)acrylate, 1-methylcyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentanyl (meth)acrylate, nonylphenoxy polyethylene glycol (meth)acrylate, tetrahydrodicyclopentadienyl (meth)acrylate, 2-(o-phenylphenoxy)ethyl (meth)acrylate, isobornyl Cyclohexyl (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, 1-adamantyl (meth)acrylate, 3-hydroxy-1-adamantyl (meth)acrylate, 2-methyl-2-adamantanyl (meth)acrylate, 2-ethyl-2-adamantanyl (meth)acrylate, 2-isopropyladamantan-2-yl (meth)acrylate, 3-hydroxy-1-adamantyl (meth)acrylate, (adamantan-1-yloxy)methyl (meth)acrylate, 2-isopropyladamantan-2-yl (meth)acrylate, Isopropyl-2-adamantyl (meth)acrylate, 1-methyl-1-ethyl-1-adamantylmethanol (meth)acrylate, 1,1-diethyl-1-adamantylmethanol (meth)acrylate, 2-cyclohexylpropan-2-yl (meth)acrylate, 1-isopropylcyclohexyl (meth)acrylate, 1-methylcyclohexyl (meth)acrylate, 1-ethylcyclopentyl (meth)acrylate, 1-methylcyclohexyl (meth)acrylate, tetrahydropyranyl (meth)acrylate, tetrahydro-2-furan Examples of the acrylic acid ester include mono(meth)acrylates of polyhydric alcohols or esters of monohydric alcohols and (meth)acrylic acid, such as 5-oxotetrahydrofuranyl(meth)acrylate, 2-oxotetrahydrofuran-3-yl(meth)acrylate, (5-oxotetrahydrofuran-2-yl)methyl(meth)acrylate, (2-oxo-1,3-dioxolan-4-yl)methyl(meth)acrylate, N-acryloyloxyethylhexahydrophthalimide, α-acryloyl-ω-methoxypoly(oxyethylene), and 1-ethoxyethyl(meth)acrylate.The polyfunctional (meth)acrylate compound is not limited to these. These may be used alone or in combination of two or more. Examples of the polyfunctional (meth)acrylate compound include di(meth)acrylate of tris(2-hydroxyethyl)isocyanurate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, or an oligomer thereof; pentaerythritol tri(meth)acrylate, or an oligomer thereof; poly(meth)acrylate of dipentaerythritol; tris(acryloxyethyl)isocyanurate; caprolactone-modified tris((meth)acryloxyethyl)isocyanurate; poly(meth)acrylate of alkyl-modified dipentaerythritol; poly(meth)acrylate of caprolactone-modified dipentaerythritol; ethoxylated bisphenol A di(meth)acrylate; Examples of the (meth)acrylate include, but are not limited to, dihydrocyclopentadiethyl (meth)acrylate, polyester (meth)acrylate, dimethylol-tricyclodecane di(meth)acrylate, ditrimethylolpropane poly(meth)acrylate, polyurethane having two or more (meth)acryloyl groups in one molecule, polyester having two or more (meth)acryloyl groups in one molecule, phenoxyethyl (meth)acrylate, isobornyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate, epoxy resin half (meth)acrylate, and (meth)acrylate having an allyloxymethyl group (see JP 2024-009452 A). The (meth)acrylate compound may be any one of the above-mentioned (meth)acrylate compounds, or two or more may be used in combination. Commercially available (meth)acrylate compounds include, for example, polyester acrylate (product name: EBECRYL810) manufactured by Daicel-Allnex Corporation, ditrimethylolpropane tetraacrylate (product name: EBECRYL140) manufactured by Daicel-Allnex Corporation, polyester acrylate (product name: M7100) manufactured by Toagosei Co., Ltd., and dimethylol-tricyclodecane diacrylate (product name: Light Acrylate DCP-A) manufactured by Kyoeisha Chemical Co., Ltd.Examples include, but are not limited to, neopentyl glycol modified trimethylolpropane diacrylate (product name: Kayarad R-604) manufactured by Nippon Kayaku Co., Ltd.

[0015] Maleimide compounds include monofunctional maleimide compounds having one maleimide group and polyfunctional maleimide compounds having two or more maleimide groups, and maleimide compounds having two maleimide groups in particular are sometimes called bismaleimide compounds.

[0016] 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-maleimidophenyl)methane, m-phenylene bismaleimide (N,N'-1,3-phenylene bismaleimide), 1,6-bismaleimidehexane, 1,2-bismaleimideethane (N,N'-ethyl Examples of the dimaleimide include, but are not limited to, N,N'-(1,2-phenylene)bismaleimide, N,N-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, N,N'-(sulfonyldi-p-phenylene)dimaleimide, N,N'-[3,3'-(1,3-phenylenedioxy)diphenyl]bismaleimide, N,N'-[4,4'-(1,3-phenylenedioxy)diphenyl]bismaleimide, and 4,4'-dimaleimide phenyl ether. These may be used alone or in combination of two or more.

[0017] Another example of a maleimide compound is a bismaleimide having a hydrocarbon group derived from a dimer acid. Such bismaleimides are described, for example, in JP 2015-193725 A. Commercially available bismaleimides having a hydrocarbon group derived from a dimer acid include, but are not limited to, products under the trade names "BMI-689," "BMI-1500," and "BMI-1700," which are liquid at 25°C, and "BMI-3000," which is solid at 25°C (all manufactured by Designer Molecules Inc.). These compounds may be used alone or in combination of two or more.

[0018] Examples of monofunctional maleimide compounds include, but are not limited to, monofunctional aliphatic maleimide compounds such as N-n-butylmaleimide, N-hexylmaleimide, 2-maleimidoethyl-ethyl carbonate, 2-maleimidoethyl-propyl carbonate, and N-ethyl-(2-maleimidoethyl)carbamate; alicyclic monofunctional maleimide compounds such as N-cyclohexylmaleimide; N-arylmaleimides such as N-phenylmaleimide; and N-aralkylmaleimides such as N-benzylmaleimide. The aliphatic maleimides and alicyclic maleimides may have a substituent, and examples of the substituent include a phenyl group, a benzyl group, and a hydroxy group. The N-arylmaleimides and N-aralkylmaleimides may have a substituent, and examples of the substituent include, but are not limited to, an alkyl group, a nitro group, a hydroxy group, an alkoxy group, a carboxyl group, and a halogeno group. These compounds may be used alone or in combination of two or more. Commercially available monofunctional maleimides include, for example, Imilex （Ｒ） -C, Imilex （Ｒ） -P (both manufactured by Nippon Shokubai Co., Ltd.), O-CPMI (manufactured by Daiwa Kasei Kogyo Co., Ltd.), etc., but are not limited to these.

[0019] The (meth)acrylamide compound has an acrylamide group (H ２ C=CHCONH-) or methacrylamide group ((H ２ C=C(CH ３)CONH-) Examples of the (meth)acrylamide compound include, but are not limited to, N,N'-methylenebis(meth)acrylamide, N,N'-ethylenebis(meth)acrylamide, 1,2-di(meth)acrylamide ethylene glycol, and the like.

[0020] The cyanoacrylate compound is H ２ Known groups represented by the formula C═C(CN)—COOR can be used. In this formula, R is an ester residue such as an alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group, or aryl group. The number of carbon atoms in the ester residue is not particularly limited, but typically, those having 1 to 8 carbon atoms can be used. Ester residues consisting of substituted hydrocarbon groups such as alkoxyalkyl groups and trialkylsilylalkyl groups can also be used. Examples of cyanoacrylate compounds include alkyl and cycloalkyl cyanoacrylates such as methyl cyanoacrylate, ethyl cyanoacrylate, propyl cyanoacrylate, butyl cyanoacrylate, and cyclohexyl cyanoacrylate; alkenyl and cycloalkenyl cyanoacrylates such as allyl cyanoacrylate, methallyl cyanoacrylate, and cyclohexenyl cyanoacrylate; alkynyl cyanoacrylates such as propanegyl cyanoacrylate; aryl cyanoacrylates such as phenyl cyanoacrylate and toluyl cyanoacrylate; methoxyethyl cyanoacrylate, ethoxyethyl cyanoacrylate, and furfuryl cyanoacrylate containing heteroatoms; trimethylsilylmethyl cyanoacrylate, trimethylsilylethyl cyanoacrylate, trimethylsilylpropyl cyanoacrylate, and dimethylvinylsilylmethyl cyanoacrylate containing silicon; but are not limited thereto.These compounds may be used alone or in combination of two or more.

[0021] The vinyl ether compound has a vinyl ether group (H ２C═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, dodecyl vinyl ether, cyclohexyl vinyl ether, 1,4-butanediol divinyl ether, nonanediol divinyl ether, cyclohexanediol divinyl ether, and cyclohexanedimethanol divinyl ether. These compounds may be used alone or in combination of two or more.

[0022] Styrene compounds contain a styrene group (H ２ C=CH-C ６ H ５ -). Examples of the styrene compound include styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 4-t-butylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 2,4,6-trimethylstyrene, 2-ethyl-4-benzylstyrene, 4-(phenylbutyl)styrene, N,N-diethyl-4-aminoethylstyrene, and 4-methoxystyrene, but are not limited to these. These may be used alone or in combination of two or more.

[0023] Methylene malonates are malonates having at least one methylene group in the molecule, including monofunctional methylene malonates having one methylene group and polyfunctional methylene malonates having two or more methylene groups. The methylene malonates preferably have a molecular weight of 220 or more. There are no particular limitations on the type of methylene malonate that can be used, and various disclosed methylene malonates can be used, including compounds described in WO 2018 / 212330 A1 and the like. Methylene malonates may be used alone or in combination of two or more.

[0024] The thiol compound in the mixture of the compound having an unsaturated double bond and the thiol compound is a compound containing at least one thiol group, and the thiol group is capable of undergoing a radical addition reaction (ene-thiol reaction) with the unsaturated double bond of the compound having an unsaturated double bond. Examples of the thiol compound include monofunctional thiol compounds having one thiol group and polyfunctional thiol compounds having two or more thiol groups. In one embodiment, the thiol compound includes a bifunctional thiol compound. In one embodiment, the thiol compound includes a trifunctional or higher functional thiol compound. In one embodiment, the thiol compound includes a trifunctional and / or tetrafunctional thiol compound. In one embodiment, the thiol compound includes a combination of a bifunctional thiol compound and a trifunctional or higher functional thiol compound. In one embodiment, the thiol compound includes a combination of a bifunctional thiol compound and a trifunctional and / or tetrafunctional thiol compound. In one embodiment, the thiol compound includes a combination of a monofunctional thiol compound and a polyfunctional thiol compound. Thiol compounds can also be divided into thiol compounds having a hydrolyzable partial structure such as an ester bond in the molecule (i.e., hydrolyzable) and thiol compounds not having such a partial structure (i.e., non-hydrolyzable). Examples of hydrolyzable thiol compounds include trimethylolpropane tris(3-mercaptopropionate) (manufactured by SC Organic Chemical Co., Ltd.: TMMP), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate (manufactured by SC Organic Chemical Co., Ltd.: TEMPIC), pentaerythritol tetrakis(3-mercaptopropionate) (manufactured by SC Organic Chemical Co., Ltd.: PEMP), tetraethylene glycol bis(3-mercaptopropionate) (manufactured by SC Organic Chemical Co., Ltd.: EGMP-4), dipentaerythritol hexakis(3-mercaptopropionate) (manufactured by SC Organic Chemical Co., Ltd.: DPMP), pentaerythritol tetrakis(3-mercaptobutyrate) (manufactured by Resonac Co., Ltd.: KarenzMT (registered trademark) PE1), 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,Examples of non-hydrolyzable polyfunctional thiol compounds include, but are not limited to, 1,3,4,6-tetrakis(2-mercaptoethyl)glycoluril (manufactured by Shikoku Chemical Industry Co., Ltd.: TS-G), 1,3,4,6-tetrakis(3-mercaptopropyl)glycoluril (manufactured by Shikoku Chemical Industry Co., Ltd.: C3 TS-G), 1,3,4,6-tetrakis(mercaptomethyl)glycoluril, 1,3,4,6-tetrakis(mercaptomethyl)-3a-methylglycoluril, 1,3,4,6-tetrakis(2-mercaptoethyl)-3a-methylglycoluril, 1,3,4,6-tetrakis(3-mercaptopropyl)-3a-methylglycoluril, 1,3,4,6-tetrakis(mercaptomethyl)-3a,6a-dimethyl glycoluril, 1,3,4,6-tetrakis(2-mercaptoethyl)-3a,6a-dimethylglycoluril, 1,3,4,6-tetrakis(3-mercaptopropyl)-3a,6a-dimethylglycoluril, 1,3,4,6-tetrakis(mercaptomethyl)-3a,6a-diphenylglycoluril, 1,3,4,6-tetrakis(2-mercaptoethyl)-3a,6a-diphenylglycoluril, 1,3,4 ,6-tetrakis(3-mercaptopropyl)-3a,6a-diphenylglycoluril, tris(3-mercaptopropyl)isocyanurate, 1,3,5-tris[3-(2-mercaptoethylsulfanyl)propyl]isocyanurate, 1,3,5-tris[2-(3-mercaptopropoxy)ethyl]isocyanurate, pentaerythritol trippropanethiol (manufactured by SC Organic Chemical Co., Ltd.: PEPT), 3-[2, 3-bis(3-sulfanylpropoxy)propoxy]propane-1-thiol, 1,2,3-tris(3-mercaptopropoxy)propane, 1,3-bis(3-mercaptopropoxy)propane, 1,3-bis(3-mercaptopropoxy)propanol or a derivative thereof, 3-[2,2-bis[(3-mercaptopropoxy)methyl]butoxy]-1-propanethiol, pentaerythritol tetrapropanethiol, 1,2,3-tris(mercaptomethylthio)propane, 1,2,3-tris(2-mercaptoethylthio)propane, 1,2,3-tris(3-mercaptopropylthio)propane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, tetrakis(mercapto methylthiomethyl)methane, tetrakis(2-mercaptoethylthiomethyl)methane, tetrakis(3-mercaptopropylthiomethyl)methane, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 1,1,5,5-tetrakis(mercaptomethylthio)-3-thiapentane, 1,1,6,6-tetrakis(mercaptomethylthio)-3,4-dithiahexane, 2,2-bis(mercaptomethylthio)ethanethiol, 3-mercaptomethylthio-1,7-dimercapto-2, 6-dithiaheptane, 3,6-bis(mercaptomethylthio)-1,9-dimercapto-2,5,8-trithianonane, 3-mercaptomethylthio-1,6-dimercapto-2,5-dithiahexane, 1,1,9,9-tetrakis(mercaptomethylthio)-5-(3,3-bis(mercaptomethylthio)-1-thiapropyl)3,7-dithianonane, tris(2,2-bis(mercaptomethylthio)ethyl)methane, tris(4,4-bis(mercaptomethylthio)-2-thiabutyl)methane, tetrakis(2,2-bis(mercaptomethylthio)ethyl ) methane, tetrakis(4,4-bis(mercaptomethylthio)-2-thiabutyl)methane, 3,5,9,11-tetrakis(mercaptomethylthio)-1,13-dimercapto-2,6,8,12-tetrathiatridecane, 3,5,9,11,15,17-hexakis(mercaptomethylthio)-1,19-dimercapto-2,6,8,12,14,18-hexathianonadecane, 9-(2,2-bis(mercaptomethylthio)ethyl)-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-tetrathiaundecane, 3,4,8,9,13,14-hexakis(mercaptomethylthio)-1,16-dimercapto-2,5,7,10,12,15-hexathiahexadecane, 8-[bis(mercaptomethylthio)methyl]-3,4,12,13-tetrakis(mercaptomethylthio)-1,15-dimercapto-2,5,7,9,11,14-hexathiapentadecane, 4,6-bis[3,5-bis(methyl 1,1-bis[4-(6-mercaptomethylthio)-1,3-dithianylthio]-1,3-bis(mercaptomethylthio)propane, 1-[4-(6-mercaptomethylthio)-1,3-dithianylthio]-3-[2,2-bis(mercaptomethylthio)ethyl]-7,9-bis(mercaptomethylthio) 2,4,6,10-tetrathiaundecane, 3-[2-(1,3-dithietanyl)]methyl-7,9-bis(mercaptomethylthio)-1,11-dimercapto-2,4,6,10-tetrathiaundecane, 9-[2-(1,3-dithietanyl)]methyl-3,5,13,15-tetrakis(mercaptomethylthio)-1,17-dimercapto-2,6,8,10,12,16-hexathiaheptadecane, 3-[2-(1,3-dithietanyl)]methyl-7,9,13,15-tetrakis(mercaptomethylthio)-1,17-dimercapto-2,4, 6,10,12,16-hexathiaheptadecane, 4,6-bis[4-(6-mercaptomethylthio)-1,3-dithianylthio]-6-[4-(6-mercaptomethylthio)-1,3-dithianylthio]-1,3-dithiane, 4-[3,4,8,9-tetrakis(mercaptomethylthio)-11-mercapto-2,5,7,10-tetrathiaundecyl]-5-mercaptomethylthio-1,3-dithiolane, 4,5-bis[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]-1,3-dithiolane, 4-[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]-5-mercaptomethylthio-1,3-dithiolane, 4-[3-bis(mercaptomethylthio)methyl-5,6-bis(mercaptomethylthio)-8-mercapto-2,4,7-trithiaoctyl]-5-mercaptomethylthio-1,3-dithiolane, 2-{bis[3,4-bis(mercaptomethylthio)-6- mercapto-2,5-dithiahexylthio]methyl}-1,3-dithietane, 2-[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]mercaptomethylthiomethyl-1,3-dithietane, 2-[3,4,8,9-tetrakis(mercaptomethylthio)-11-mercapto-2,5,7,10-tetrathiaundecylthio]mercaptomethylthiomethyl-1, 3-Dithietane, 2-[3-bis(mercaptomethylthio)methyl-5,6-bis(mercaptomethylthio)-8-mercapto-2,4,7-trithiaoctyl]mercaptomethylthiomethyl-1,3-dithietane, 4-{1-[2-(1,3-dithietanyl)]-3-mercapto-2-thiapropylthio}-5-[1,2-bis(mercaptomethylthio)-4-mercapto-3-thiabutylthio] Examples of suitable thiol compounds include, but are not limited to, various bifunctional thiol compounds disclosed in WO 2019 / 082962, such as 2,2'-[cyclohexylidenebis(thio-2,1-ethanediylthio)]bis[ethanethiol] and 4,4'-[(1,3-phenylene)bis(oxy)]bis[1-butanethiol], as well as dimers, trimers, and tetramers of the above thiol compounds. Furthermore, these thiol compounds may contain their derivatives and / or their monofunctional and / or bifunctional compounds as impurities or by-products in the synthesis. These compounds may be used alone or in combination of two or more.

[0025] The radical polymerizable compounds may be used alone or in combination of two or more.

[0026] The cationically polymerizable compound is a compound having one or more cationically polymerizable groups in the molecule. Examples of the cationically polymerizable compound include, but are not limited to, compounds having an epoxy group, compounds having an oxetanyl group, compounds having a vinyl ether group, compounds having other cationically polymerizable groups, and compounds having any combination of these cationically polymerizable groups.

[0027] In this specification, a compound having an epoxy group refers to a compound having at least one epoxy group in the molecule, and is also referred to as an epoxy compound. Examples include monofunctional epoxy compounds having one epoxy group and polyfunctional epoxy compounds having two or more epoxy groups. In one embodiment, the epoxy compound preferably contains at least a polyfunctional epoxy compound, and may contain a combination of a polyfunctional epoxy compound and a monofunctional epoxy compound. Epoxy compounds can be broadly classified into epoxy compounds having an aromatic ring skeleton, aliphatic epoxy compounds, and alicyclic epoxy compounds depending on the type of skeleton.

[0028] In this specification, a compound having an oxetanyl group is a compound having at least one oxetane ring (e.g., a 3-oxetanyl group) in the molecule, and is also referred to as an oxetane compound. In one embodiment, the oxetane compound preferably has 1 to 6 oxetanyl groups in the molecule, and more preferably has 1 to 2 oxetanyl groups in the molecule.

[0029] In this specification, a compound having a vinyl ether group is a compound having at least one vinyl ether group in the molecule.

[0030] Specific examples of the cationic polymerizable compound include glycidyl ethers of tetra(hydrophenyl)alkanes, glycidyl ethers of tetrahydroxybenzophenone, epoxidized polyvinylphenol, p-tert-butylphenyl glycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, n-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, 1,2-epoxytetradecane, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate, 6-methyl-3,4-eth ... 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, bis(3,4-epoxycyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexanecarboxylate, methylenebis(3,4-epoxycyclohexane), propanediol Pan-2,2-diyl-bis(3,4-epoxycyclohexane), 2,2-bis(3,4-epoxycyclohexyl)propane, dicyclopentadiene diepoxide, ethylene bis(3,4-epoxycyclohexanecarboxylate), limonene dioxide (1,2:8,9-diepoxylimonene), (3,3',4,4'-diepoxy)bicyclohexyl, dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1-epoxyethyl-3,4-epoxycyclohexane, 1,2-epoxy-2-epoxyethylcyclohexane, 1,2-epoxy-4-vinylcyclohexane, α-pinene oxide, 1,2-bis(3,4-epoxycyclohexane-1-yl)ethane, 1,2-epoxy-1,2-bis(3,4-epoxycyclohexane-1-yl)ethane, bis(3,4-epoxycyclohexylmethyl)ether, siloxane compounds having a cycloalkene oxide structure, 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol, epoxidized polybutadiene, compounds in which some or all of the double bonds of styrene-butadiene copolymers have been epoxidized, polyalkylene oxide-modified bisphenol A-type epoxy, lauryl alcohol polyethylene glycol glycidyl ether, diglycidyl ether of alicyclic diol, diglycidyl ether of polyalkylene oxide adduct of alicyclic diol, bis[1-ethyl( 3-oxetanyl)]methyl ether (also known as (3-ethyl-3{[(3-ethyloxetan-3-yl)methoxy]methyl}oxetane)), xylylene bisoxetane, 4,4'-bis[3-ethyl-(3-oxetanyl)methoxymethyl]biphenyl, 1,4-bis(3-ethyl-3-oxetanylmethoxy)methylbenzene, (bis[(3-ethyl-3-oxetanyl)methyl]isophthalate), 3-ethyl-3-hydroxymethyloxetane oxetane, 2-ethylhexyloxetane, (3-ethyloxetan-3-yl)methyl methacrylate, 3-ethyl-3-[(2-ethylhexyloxy)methyl]oxetane, 3-ethyl-3-(4-hydroxybutyl)oxymethyloxetane, 3-ethyl-3-phenoxymethyloxetane, oxetanyl silsesquioxetane, 3-ethyl-3{[(3-ethyloxetan-3-yl)methoxy]methyl}oxetane, phenol novolac oxetane, 1,Examples of vinyl vinyl ether include, but are not limited to, 4-butanediol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, normal propyl vinyl ether, isopropyl vinyl ether, normal butyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether, 2-(2-vinyloxyethoxy)ethyl acrylate, 2-(2-vinyloxyethoxy)ethyl methacrylate, 1,4-cyclohexanedimethanol monovinyl ether, and 1,4-cyclohexanedimethanol divinyl ether.

[0031] Commercially available cationically polymerizable compounds include EPICLON (registered trademark) 850, 850-S, EXA-850CRP, and EXA-8067 manufactured by DIC Corporation; AER9000 manufactured by Asahi Kasei Corporation; EP-4000S, EP-4003S, EP-4005, EP-4010S, EP-4088S, and EP-4088L manufactured by ADEKA Corporation; Rikaresin BEO-60E manufactured by New Japan Chemical Co., Ltd.; EX-171 manufactured by Nagase ChemteX Corporation; EPICLON (registered trademark) 830-S and EXA manufactured by DIC Corporation. -830LVP, EXA-835LV; EPICLON (registered trademark) HP-4032D, HP-720H manufactured by DIC Corporation; EPICLON (registered trademark) N-740, N-770 manufactured by DIC Corporation; EPICLON (registered trademark) N-660, N-670, N-655-EXP-S manufactured by DIC Corporation; ADEKA GLYCIROL (registered trademark) ED-509E, ED-509S manufactured by ADEKA Corporation; OPP-G manufactured by Sanko Co., Ltd.; Epolite 100MF manufactured by Kyoeisha Chemical Co., Ltd.; jER manufactured by Mitsubishi Chemical Corporation YX7400N; jER YX8000 manufactured by Mitsubishi Chemical Corporation; CELLOXIDE (registered trademark) 2021P manufactured by Daicel Corporation; CELLOXIDE (registered trademark) 8010 manufactured by Daicel Corporation; EHPE3150 manufactured by Daicel Corporation; EPOLEAD PB manufactured by Daicel Corporation; EPOFRIEND manufactured by Daicel Corporation; HiREM-1 and HiREM-2 manufactured by Shikoku Chemicals Corporation; OXT-191 manufactured by Toagosei Co., Ltd.; OXT-221 manufactured by Toagosei Co., Ltd.; PHOX manufactured by Toagosei Co., Ltd., and the like, but are not limited to these.

[0032] The cationically polymerizable compounds may be used alone or in combination of two or more.

[0033] Examples of anionically polymerizable compounds include the compounds having an epoxy group listed as examples of the cationic polymerizable compounds, and their curing agents, such as thiol-based curing agents, phenol-based curing agents, acid anhydride-based curing agents, and amine-based curing agents. Furthermore, methylene malonates listed as examples of the radically polymerizable compounds are also listed as anionically polymerizable compounds. Furthermore, (meth)acrylate compounds listed as examples of the radically polymerizable compounds are also listed as anionically polymerizable compounds when used in combination with a thiol compound. These compounds may be used alone or in combination of two or more.

[0034] As the thiol-based curing agent, the above-mentioned thiol compounds can be used.

[0035] Examples of phenolic curing agents refer to monomers, oligomers, and polymers in general that have a phenolic hydroxyl group, and include, but are not limited to, phenol novolac resins and alkylated or allylated products thereof, cresol novolac resins, phenol aralkyl (including phenylene and biphenylene skeletons) resins, naphthol aralkyl resins, triphenolmethane resins, and dicyclopentadiene-type phenolic resins.

[0036] Examples of acid anhydride curing agents include, but are not limited to, alkylated tetrahydrophthalic anhydrides such as methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, and methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhimic anhydride, alkenyl-substituted succinic anhydride, methylnadic anhydride, and glutaric anhydride.

[0037] Examples of the amine-based curing agent include, but are not limited to, aliphatic polyamines such as triethylenetetraamine, tetraethylenepentamine, m-xylenediamine, trimethylhexamethylenediamine, and 2-methylpentamethylenediamine; alicyclic polyamines such as isophoronediamine, 1,3-bisaminomethylcyclohexane, bis(4-aminocyclohexyl)methane, norbornenediamine, and 1,2-diaminocyclohexane; piperazine-type polyamines such as N-aminoethylpiperazine and 1,4-bis(2-amino-2-methylpropyl)piperazine; and aromatic polyamines such as diethyltoluenediamine, dimethylthiotoluenediamine, 4,4'-diamino-3,3'-diethyldiphenylmethane, bis(methylthio)toluenediamine, diaminodiphenylmethane, m-phenylenediamine, diaminodiphenylsulfone, diethyltoluenediamine, trimethylenebis(4-aminobenzoate), and polytetramethyleneoxide-di-p-aminobenzoate. Commercially available products include Epicure-W and Epicure-Z (Yuka Shell Epoxy Co., Ltd., trade names), jER Cure (registered trademark)-W and jER Cure (registered trademark)-Z (Mitsubishi Chemical Corporation, trade names), Kayahard A-A, Kayahard A-B, and Kayahard A-S (Nippon Kayaku Co., Ltd., trade names), Thothamine HM-205 (Nippon Steel Sumikin Chemical Co., Ltd., trade names), Adeka Hardener EH-101 (ADEKA Corporation, trade names), Epomic Q-640 and Epomic Q-643 (Mitsui Chemicals, Inc., trade names), DETDA80 (Lonza, trade names), and Thothamine HM-205 (Nippon Steel Sumikin Chemical Co., Ltd., trade names), but are not limited to these.

[0038] The polymerizable compound (A) may be any one of a radically polymerizable compound, a cationically polymerizable compound, and an anionically polymerizable compound, or any combination thereof.

[0039] In one embodiment, the polymerizable compound (A) includes a (meth)acrylate compound. In one embodiment, the polymerizable compound (A) includes an epoxy compound. In one embodiment, the polymerizable compound (A) includes a (meth)acrylate compound and an epoxy compound.

[0040] In one embodiment, the (A) polymerizable compound includes an epoxy compound and a curing agent therefor. When the (A) polymerizable compound includes an epoxy compound and a curing agent therefor, the ratio of the number of epoxy group equivalents of the epoxy compound to the number of functional group equivalents of the curing agent ([number of epoxy group equivalents of the epoxy compound] / [number of functional group equivalents of the curing agent]) is preferably 0.1 to 1,000, more preferably 0.1 to 100, and even more preferably 0.2 to 10. In one embodiment, the (A) polymerizable compound includes a (meth)acrylate compound and a thiol compound. When the polymerizable compound (A) contains a (meth)acrylate compound and a thiol compound, the ratio of the number of (meth)acryloyl group equivalents of the (meth)acrylate compound to the number of thiol group equivalents of the thiol compound ([number of (meth)acryloyl group equivalents of the (meth)acrylate compound] / [number of thiol group equivalents of the thiol compound]) is preferably 0.1 to 1,000, more preferably 0.1 to 100, and even more preferably 0.2 to 10.

[0041] From the viewpoint of the adhesive strength of the curable resin composition, the content of the (A) polymerizable compound is preferably 10 to 95 mass %, and more preferably 20 to 90 mass %, relative to the total mass of the curable resin composition.

[0042] (B) Polymerization Initiator The curable resin composition of this embodiment contains (B) a polymerization initiator (hereinafter also referred to as "component (B)"). In this embodiment, the (B) polymerization initiator includes (B1) a photopolymerization initiator, (B2) a thermal polymerization initiator, or a combination thereof.

[0043] (B1) Photopolymerization Initiator A photopolymerization initiator is a reactant that absorbs light to generate active species such as radicals, cations, anions, etc., and causes the polymerization of a polymerizable compound to proceed. The photopolymerization initiator can be appropriately selected from photoradical polymerization initiators, photocationic polymerization initiators, photoanionic polymerization initiators, or any combination thereof, depending on the type of polymerizable compound (A).

[0044] The photoradical polymerization initiator absorbs light to generate radicals as active species, thereby promoting the polymerization of the radical polymerizable compound. Examples of the photoradical polymerization initiator include, but are not limited to, alkylphenone compounds, acylphosphine oxide compounds, oxime ester compounds, and compounds having a photosensitive moiety and a peroxide structure.

[0045] Examples of alkylphenone compounds include benzyl dimethyl ketals such as 2,2-dimethoxy-1,2-diphenylethan-1-one (commercially available as Omnirad 651 from IGM Resins B.V.); α-aminoalkylphenones such as 2-methyl-2-morpholino(4-thiomethylphenyl)propan-1-one (commercially available as Omnirad 907 from IGM Resins B.V.); α-hydroxyalkylphenones such as 1-hydroxy-cyclohexyl-phenyl-ketone (commercially available as Omnirad 184 from IGM Resins B.V.); 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one (commercially available as Omnirad 184 from IGM Resins B.V.); 379EG), 2-benzyl-2-(dimethylamino)-4'-morpholinobutyrophenone (commercially available as Omnirad 369 manufactured by IGM Resins BV), etc., but are not limited to these. These may be used alone or in combination of two or more.

[0046] Examples of the acylphosphine oxide compound include, but are not limited to, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (commercially available as Omnirad TPO H manufactured by IGM Resins B.V.) and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (commercially available as Omnirad 819 manufactured by IGM Resins B.V.). These compounds may be used alone or in combination of two or more.

[0047] Examples of oxime ester compounds include, but are not limited to, 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)] (trade name: Irgacure OXE-01, manufactured by BASF), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (trade name: Irgacure OXE-02, manufactured by BASF), methanone, ethanone, 1-[9-ethyl-6-(1,3-dioxolane, 4-(2-methoxyphenoxy)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (trade name: ADEKA OPT-N-1919, manufactured by ADEKA Corporation). These compounds may be used alone or in combination of two or more.

[0048] Examples of compounds having a photosensitive moiety and a peroxide structure or commercially available products thereof include 3,3′,4,4′-tetrakis(tert-butylperoxycarbonyl)benzophenone (BTTB), Perdual TA, and Perdual TX (all manufactured by NOF Corporation), but are not limited to these.

[0049] In addition to the above-mentioned photoradical polymerization initiators, examples of the photoradical polymerization initiator include 2-hydroxy-2-methyl-1-phenylpropan-1-one, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl)ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin phenyl ether, and benzyl dimethyl Examples of the benzoxanthone include, but are not limited to, ketals, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3'-dimethyl-4-methoxybenzophenone, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, methylphenyl glyoxylate, benzyl, camphorquinone, etc. These may be used alone or in combination of two or more.

[0050] The photoradical polymerization initiators may be used alone or in combination of two or more.

[0051] When the curable resin composition contains a photoradical polymerization initiator, the content of the photoradical polymerization initiator in the curable resin composition is preferably 0.1 to 10 parts by mass, and more preferably 0.2 to 8 parts by mass, relative to 100 parts by mass of the polymerizable compound (A), from the viewpoint of photoirradiation reactivity.

[0052] The cationic photopolymerization initiator absorbs light to generate a cation (acid) as an active species, thereby promoting polymerization of the cationic polymerizable compound. The cationic photopolymerization initiator is not particularly limited, and may be, for example, various compounds described in JP-A-2022-080366. A preferred cationic photopolymerization initiator is BF ４ － , SbF ６ -, AsF ６ － , B(C ６ F ５ ) ４ － , Ga(C ６ F ５ ) ４ － , C(CF ３ SO ２ ) ３ － , [P(R １ ) ａ F ６－ａ ] － , [C(R １ SO ２ ) ３ ] － , or [N(R １ SO ２ ) ２ ] － (In the formula, R １ are each independently an alkyl group in which at least a portion of the hydrogen atoms is substituted with a fluorine atom, a is an integer of 0 to 5, and when a is an integer of 2 or more, a plurality of R １ may be the same or different.) as a counter anion, and an iodonium cation, a sulfonium cation, an ammonium cation, a phosphonium cation, or the like as a cation moiety.

[0053] Examples of iodonium cations include iodonium ions such as diphenyliodonium, di-p-tolyliodonium, bis(4-dodecylphenyl)iodonium, bis(4-methoxyphenyl)iodonium, (4-octyloxyphenyl)phenyliodonium, bis(4-decyloxy)phenyliodonium, 4-(2-hydroxytetradecyloxy)phenylphenyliodonium, 4-isopropylphenyl(p-tolyl)iodonium, and 4-isobutylphenyl(p-tolyl)iodonium.

[0054] Examples of sulfonium ions include triphenylsulfonium, tri-p-tolylsulfonium, tri-o-tolylsulfonium, tris(4-methoxyphenyl)sulfonium, 1-naphthyldiphenylsulfonium, 2-naphthyldiphenylsulfonium, tris(4-fluorophenyl)sulfonium, tri-1-naphthylsulfonium, tri-2-naphthylsulfonium, tris(4-hydroxyphenyl)sulfonium, 4-(phenylthio)phenyldiphenylsulfonium, 4-(p-tolylthio)phenyldi-p-tolylsulfonium, 4-(4-methoxyphenylthio)phenylbis(4-methoxyphenyl)sulfonium, 4-(phenylthio)phenylbis(4-fluorophenyl)sulfonium, phenyl)sulfonium, 4-(phenylthio)phenylbis(4-methoxyphenyl)sulfonium, 4-(phenylthio)phenyldi-p-tolylsulfonium, [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium, [4-(2-thioxanthonylthio)phenyl]diphenylsulfonium, bis[4-(diphenylsulfonio)phenyl]sulfide, bis[4-{bis[4-(2-hydroxyethoxy)phenyl]sulfonio}phenyl]sulfide, bis{4-[bis(4-fluorophenyl)sulfonio]phenyl}sulfide, bis{4-[bis(4-methylphenyl)sulfonio]phenyl}sulfide, bis{4-[bis(4-methoxyphenyl)sulfonio] phenyl} sulfide, 4-(4-benzoyl-2-chlorophenylthio)phenylbis(4-fluorophenyl)sulfonium, 4-(4-benzoyl-2-chlorophenylthio)phenyldiphenylsulfonium, 4-(4-benzoylphenylthio)phenylbis(4-fluorophenyl)sulfonium, 4-(4-benzoylphenylthio)phenyldiphenylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-yldi-p-tolylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-yldi-p-tolylsulfonium,10-Dihydroanthracen-2-yldiphenylsulfonium, 2-[(di-p-tolyl)sulfonio]thioxanthone, 2-[(diphenyl)sulfonio]thioxanthone, 4-(9-oxo-9H-thioxanthen-2-yl)thiophenyl-9-oxo-9H-thioxanthen-2-ylphenylsulfonium, 4-[4-(4-t-butylbenzoyl)phenylthio]phenyldi-p-tolylsulfonium, 4-[4-(4-t-butylbenzoyl)phenylthio]phenyl triarylsulfoniums such as 4-[4-(benzoylphenylthio)]phenyldi-p-tolylsulfonium, 4-[4-(benzoylphenylthio)]phenyldiphenylsulfonium, 5-(4-methoxyphenyl)thiaanthrenenium, 5-phenylthiaanthrenenium, 5-tolylthiaanthrenenium, 5-(4-ethoxyphenyl)thiaanthrenenium, and 5-(2,4,6-trimethylphenyl)thiaanthrenenium.

[0055] Examples of ammonium cations include pyrrolidiniums such as N,N-dimethylpyrrolidinium, N-ethyl-N-methylpyrrolidinium, and N,N-diethylpyrrolidinium; imidazoliniums such as N,N'-dimethylimidazolinium, N,N'-diethylimidazolinium, N-ethyl-N'-methylimidazolinium, 1,3,4-trimethylimidazolinium, and 1,2,3,4-tetramethylimidazolinium; tetrahydropyrimidiniums such as N,N'-dimethyltetrahydropyrimidinium; and morpholiniums such as N,N'-dimethylmorpholinium. pyridinium such as N-methylpyridinium, N-benzylpyridinium, and N-phenacylpyridinium; imidazolium such as N,N'-dimethylimidazolium; quinolium such as N-methylquinolium, N-benzylquinolium, and N-phenacylquinolium; isoquinolium such as N-methylisoquinolium; thiazonium such as benzylbenzothiazonium and phenacylbenzothiazonium; and acridium such as benzylacridium and phenacylacridium.

[0056] Examples of the phosphonium cation include tetraarylphosphoniums such as tetraphenylphosphonium, tetra-p-tolylphosphonium, tetrakis(2-methoxyphenyl)phosphonium, tetrakis(3-methoxyphenyl)phosphonium, and tetrakis(4-methoxyphenyl)phosphonium; triarylphosphoniums such as triphenylbenzylphosphonium, triphenylphenacylphosphonium, triphenylmethylphosphonium, and triphenylbutylphosphonium; and tetraalkylphosphoniums such as triethylbenzylphosphonium, tributylbenzylphosphonium, tetraethylphosphonium, tetrabutylphosphonium, tetrahexylphosphonium, triethylphenacylphosphonium, and tributylphenacylphosphonium.

[0057] Specific examples of the iodonium salt-based photocationic polymerization initiator include arsenate-based iodonium salt photocationic polymerization initiators such as diphenyliodonium hexafluoroarsenate, di(4-chlorophenyl)iodonium hexafluoroarsenate, di(4-bromophenyl)iodonium hexafluoroarsenate, and phenyl(4-methoxyphenyl)iodonium hexafluoroarsenate; 4-methylphenyl-4-(1-methylethyl)phenyliodonium hexafluorophosphate, 4-methylphenyl-4-(1-methylethyl)phenyliodonium tri(pentafluoroethyl)trifluorophosphate (e.g., IK-1 manufactured by San-Apro Co., Ltd.), 4-methylphenyl-4-(2-methylpropyl)phenyliodonium hexafluorophosphate (e.g., IRGACURE (registered trademark) 250 manufactured by BASF), and bis(C １０～１４cationic photopolymerization initiators which are phosphate-based iodonium salts such as 4-methylphenyl-4-(1-methylethyl)phenyliodonium hexafluorophosphate (for example, WPI-113 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.); cationic photopolymerization initiators which are antimonate-based iodonium salts such as 4-methylphenyl-4-(1-methylethyl)phenyliodonium hexafluoroantimonate (for example, WPI-116 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.); photo / thermal cationic polymerization initiators which are gallate-based iodonium salts such as IK-1FG (manufactured by San-Apro Co., Ltd.); 4-methylphenyl-4-(1-methylethyl)phenyliodonium tetrakis(pentafluorophenyl)borate, 4-isopropyl-4'-methyldiphenyliodonium tetrakis(pentafluorophenyl)borate (for example, BLUESIL (registered trademark) PI manufactured by ELKEM SILICONES, Inc.); Examples of suitable photo-cationic polymerization initiators include, but are not limited to, borate-based iodonium salts such as 2074 and the like.

[0058] Specific examples of the sulfonium salt-based cationic photopolymerization initiator include, but are not limited to, borate-based sulfonium salt photocationic polymerization initiators (for example, San-Apro Ltd. product names: CPI-110B, CPI-310B, CPI-410B, etc., and IGM Resins B.V. product name: Omnirad 290, etc.), phosphate-based sulfonium salt photocationic polymerization initiators (San-Apro Ltd. product names: CPI-210S, VC-1S, CPI-410S, etc.), and gallate-based sulfonium salt photocationic polymerization initiators (San-Apro Ltd. product names: CPI-310FG, VC-1FG, etc.).

[0059] The cationic photopolymerization initiators may be used alone or in combination of two or more.

[0060] When the curable resin composition contains a cationic photopolymerization initiator, the content of the cationic photopolymerization initiator in the curable resin composition is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, and even more preferably 1 to 15 parts by mass, relative to 100 parts by mass of the polymerizable compound (A).

[0061] An anionic photopolymerization initiator absorbs light to generate an anion (base) as an active species, thereby promoting polymerization of an anionic polymerizable compound. Examples of an anionic photopolymerization initiator include, but are not limited to, various compounds that generate a base such as an amine, amidine, guanidine, phosphazene, or carbene.Specific examples of the photoanionic polymerization initiator include 2-benzyl-2-(dimethylamino)-1-[4-(morpholino)phenyl]-1-butanone, 2-(dimethylamino)-2-(4-methylbenzyl)-1-(4-morpholinophenyl)butan-1-one, 2-nitrobenzyl 4-hydroxypiperidine-1-carboxylate, 4,5-dimethoxy-2-nitrobenzyl 2,6-dimethylpiperidine-1-carboxylate, 1-(9,10-dioxo-9,10-dihydroanthracen-2-yl)ethyl cyclohexylcarbamate, 1-(9,10-dioxo-9,10-dihydroanthracen-2-yl)ethyl 1H-imidazole-1-carboxylate, 3,4,6,7,8,9-hexahydro-2H-pyrimido[1,2-a]pyrimidine- 1-ium 2-(3-benzoylphenyl)propanoate, diaminomethaniminium 2-(3-benzoylphenyl)propanoate, (Z)-N-(((bis(dimethylamino)methylene)amino)(isopropylamino)methylene)propan-2-aminium 2-(3-benzoylphenyl)propanoate, 1,2-dicyclohexyl-4,4,5,5-tetramethylbiguanidinium n-butyltriphenylborate, (Z)-{[bis(dimethylamino)methylidene]amino}-N-cyclohexyl(cyclohexylamino)methaniminium tetrakis(3-fluorophenyl)borate, 1,2-diisopropyl-3-[bis(dimethylamino)methylene]guanidinium 2-(3-benzoylphenyl)propionate, 9-anthrylmethyl Examples of the diastereoisopropyl methyl ester include, but are not limited to, N,N-diethylcarbamate, (E)-1-piperidino-3-(2-hydroxyphenyl)-2-propen-1-one, 2-nitrophenylmethyl 4-methacryloyloxypiperidine-1-carboxylate, tetramethylguanidium tetrakis(3-fluorophenyl)borate, tetramethylguanidium tetrakis(4-fluorophenyl)borate, salts containing protonated DBU and tetrakis(3-fluorophenyl)borate anions, and salts containing benzylated DBU and tetrakis(3-fluorophenyl)borate anions. These may be used alone or in combination of two or more.The photoanionic polymerization initiators may be used alone or in combination of two or more.

[0062] When the curable resin composition contains a photoanionic polymerization initiator, the content of the photoanionic polymerization initiator in the curable resin composition is preferably 0.5 to 15 parts by mass, and more preferably 1 to 10 parts by mass, relative to 100 parts by mass of the polymerizable compound (A).

[0063] (B2) Thermal Polymerization Initiator The (B2) thermal polymerization initiator is a compound that generates an active species such as a radical, an anion, or a cation by heat, and examples thereof include a thermal radical polymerization initiator, a thermal anionic polymerization initiator, and a thermal cationic polymerization initiator depending on the type of the active species. The thermal polymerization initiator can be appropriately selected from a thermal radical polymerization initiator, a thermal cationic polymerization initiator, a thermal anionic polymerization initiator, or any combination thereof depending on the type of the polymerizable compound (A).

[0064] The thermal radical initiator generates an active species radical by cleavage at a predetermined temperature, thereby promoting the polymerization of the radically polymerizable compound. When used in a cationic polymerization system, the thermal radical initiator generates an active species radical by cleavage at a predetermined temperature, which reductively decomposes the cationic polymerization initiator and promotes the generation of a cation (acid) from the cationic polymerization initiator. Examples of thermal radical polymerization initiators include methyl ethyl ketone peroxide, methylcyclohexanone peroxide, methylacetoacetate peroxide, acetylacetone peroxide, 1,1-bis(t-butylperoxy)3,3,5-trimethylcyclohexane, 1,1-bis(t-hexylperoxy)cyclohexane, 1,1-bis(t-hexylperoxy)3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, 2,2-bis(4,4-di-t-butylperoxycyclohexyl)propane, 1,1-bis(t-butylperoxy)cyclododecane, n-butyl 4,4-bis(t-butylperoxy)cyclohexane ... ) valerate, 2,2-bis(t-butylperoxy)butane, 1,1-bis(t-butylperoxy)-2-methylcyclohexane, t-butyl hydroperoxide, p-menthane hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, t-hexyl hydroperoxide, dicumyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, α,α'-bis(t-butylperoxy)diisopropylbenzene, t-butylcumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyne-3, isobutyryl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, cinnamic acid peroxide, m-toluoyl peroxide, benzoyl peroxide, diisopropyl peroxydicarbonate, bis(4-t-butylcyclohexyl) peroxydicarbonate, di-3-methoxybutyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, di(3-methyl-3-methoxybutyl) peroxydicarbonate, Di(4-t-butylcyclohexyl)peroxydicarbonate, α,α'-bis(neodecanoylperoxy)diisopropylbenzene, cumyl peroxyneodecanoate, 1,1,3,3-tetramethylbutyl peroxyneodecanoate, 1-cyclohexyl-1-methylethyl peroxyneodecanoate, t-hexyl peroxyneodecanoate, t-butyl peroxyneodecanoate, t-hexyl peroxypivalate, t-butyl peroxypivalate, 2,5-dimethyl-2,5-bis(2-ethylhexanoate) t-butylperoxy)hexane, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, t-butylperoxymaleic acid, t-butylperoxylaurate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxyisopropyl monocarbonate Examples of peroxybenzoates include, but are not limited to, t-butylperoxy-2-ethylhexyl monocarbonate, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, t-butylperoxyacetate, t-hexylperoxybenzoate, t-butylperoxy-m-toluoylbenzoate, t-butylperoxybenzoate, bis(t-butylperoxy)isophthalate, t-butylperoxyallyl monocarbonate, and 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone. These may be used alone or in combination of two or more.

[0065] Examples of thermal anionic polymerization initiators include, but are not limited to, amines such as 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, triethylamine, triethylenediamine, 2-(dimethylaminomethyl)phenol, 1,8-diaza-bicyclo[5,4,0]undecene-7, tris(dimethylaminomethyl)phenol, and benzyldimethylamine, and phosphines such as triphenylphosphine, tributylphosphine, and trioctylphosphine. These may be used alone or in combination of two or more.

[0066] In addition to the above examples, examples of thermal anionic polymerization initiators include "thermal latent curing catalysts," which are basic catalysts that are inactive at room temperature but are activated by heating to function as a polymerization catalyst. Examples of thermal latent curing catalysts include amine compounds that are solid at room temperature; amine adduct-based thermal latent curing catalysts such as reaction products of amine compounds and epoxy compounds (amine-epoxy adducts) and reaction products of amine compounds and isocyanate compounds or urea compounds (urea adducts); microcapsule-type thermal latent curing catalysts; and solid-dispersion-type thermal latent curing catalysts such as inclusion-type thermal latent curing catalysts. Amine compounds include aliphatic amines, aromatic amines, and heterocyclic amines.

[0067] Examples of amine compounds that are solid at room temperature include dicyandiamide, 2-heptadecylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-undecylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4-benzyl-5-hydroxymethylimidazole, 2,4-diamino-6-(2-methyl-1-imidazolyl-(1))-ethyl-S-triazine, 2,4-diamino-6-(2'-methylimidazolyl-(1)')-ethyl-S-triazine, and 2,4-diamino-6-(2'-methylimidazolyl-(1)')-ethyl-S-triazine. Examples of the alkyl acrylate include, but are not limited to, triazine-isocyanuric acid adduct, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole-trimellitate, 1-cyanoethyl-2-phenylimidazole-trimellitate, N-(2-methylimidazolyl-1-ethyl)-urea, and N,N'-(2-methylimidazolyl-(1)-ethyl)-adiboyldiamide.

[0068] The amine compound used as one of the raw materials for producing the amine adduct-based thermal latent curing catalyst may be any compound as long as it has one or more active hydrogen atoms in the molecule capable of addition reacting with an epoxy group or an isocyanate group, and at least one functional group selected from a primary amino group, a secondary amino group, and a tertiary amino group in the molecule. Examples of such amine compounds include, in addition to the above-mentioned amine compounds that are solid at room temperature, aliphatic amines such as diethylenetriamine, triethylenetetramine, n-propylamine, 2-hydroxyethylaminopropylamine, cyclohexylamine, and 4,4'-diamino-dicyclohexylmethane; aromatic amine compounds such as 4,4'-diaminodiphenylmethane and 2-methylaniline; and nitrogen-containing heterocyclic amine compounds such as 2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazoline, 2,4-dimethylimidazoline, piperidine, and piperazine. However, the present invention is not limited to these.

[0069] Among these, compounds having a tertiary amino group in the molecule and imidazole derivatives are particularly useful as raw materials that provide thermally latent curing catalysts with excellent curing acceleration capabilities.Examples of such compounds include amine compounds such as dimethylaminopropylamine, diethylaminopropylamine, di-n-propylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine, and N-methylpiperazine, as well as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and 2-phenyl-4,5-dihydroxymethylimidazole. imidazole compounds such as phenyl-4-methylimidazole and 1-(2-aminoethyl)-2-methylimidazole; 2-dimethylaminoethanol, 1-methyl-2-dimethylaminoethanol, 1-phenoxymethyl-2-dimethylaminoethanol, 2-diethylaminoethanol, 1-butoxymethyl-2-dimethylaminoethanol, 1-(2-hydroxy-3-phenoxypropyl)-2-methylimidazole, 1-(2-hydroxy-3-phenoxypropyl)-2-ethyl-4-methylimidazole, 1-(2-hydroxy 1-(2-hydroxy-3-butoxypropyl)-2-methylimidazole, 1-(2-hydroxy-3-butoxypropyl)-2-ethyl-4-methylimidazole, 1-(2-hydroxy-3-phenoxypropyl)-2-phenylimidazoline, 1-(2-hydroxy-3-butoxypropyl)-2-methylimidazoline, 2-(dimethylaminomethyl)phenol, 2,4,6-tris(dimethylaminomethyl)phenol, N-β-hydroxyethylmorpholine, 2-dimethylaminoethanethiol, 2-mercaptopyridine, benzimidazole, 2 Examples of the tertiary amino acid include, but are not limited to, alcohols, phenols, thiols, carboxylic acids, and hydrazides having a tertiary amino group or an imidazole skeleton in the molecule, such as N,N-mercaptobenzimidazole, 2-mercaptobenzothiazole, 4-mercaptopyridine, N,N-dimethylaminobenzoic acid, N,N-dimethylglycine, nicotinic acid, isonicotinic acid, picolinic acid, N,N-dimethylglycine hydrazide, N,N-dimethylpropionic acid hydrazide, nicotinic acid hydrazide, and isonicotinic acid hydrazide.

[0070] Examples of epoxy compounds used as one of the raw materials for producing the amine-epoxy adduct thermal latent curing catalyst include, but are not limited to, polyglycidyl ethers obtained by reacting epichlorohydrin with polyhydric phenols such as bisphenol A, bisphenol F, catechol, and resorcinol, or polyhydric alcohols such as glycerin and polyethylene glycol; glycidyl ether esters obtained by reacting epichlorohydrin with hydroxycarboxylic acids such as p-hydroxybenzoic acid and β-hydroxynaphthoic acid; polyglycidyl esters obtained by reacting epichlorohydrin with polycarboxylic acids such as phthalic acid and terephthalic acid; glycidyl amine compounds obtained by reacting epichlorohydrin with 4,4'-diaminodiphenylmethane or m-aminophenol; and polyfunctional epoxy compounds such as epoxidized phenol novolac resins, epoxidized cresol novolac resins, and epoxidized polyolefins; and monofunctional epoxy compounds such as butyl glycidyl ether, phenyl glycidyl ether, various phenylphenol glycidyl ethers, and glycidyl methacrylate.

[0071] Examples of the isocyanate compound used as one of the raw materials for producing the amine-urea adduct thermal latent curing catalyst include monofunctional isocyanate compounds such as n-butyl isocyanate, isopropyl isocyanate, phenyl isocyanate, and benzyl isocyanate; polyfunctional isocyanate compounds such as hexamethylene diisocyanate, toluylene diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, xylylene diisocyanate, paraphenylene diisocyanate, 1,3,6-hexamethylene triisocyanate, and bicycloheptane triisocyanate; and terminal isocyanate group-containing compounds obtained by reacting these polyfunctional isocyanate compounds with active hydrogen compounds. Examples of such a terminal isocyanate group-containing compound include, but are not limited to, an addition compound having a terminal isocyanate group obtained by reacting toluylene diisocyanate with trimethylolpropane, and an addition compound having a terminal isocyanate group obtained by reacting toluylene diisocyanate with pentaerythritol.

[0072] Examples of urea compounds used as one of the raw materials for producing the amine-urea adduct thermal latent curing catalyst include, but are not limited to, urea and thiourea.

[0073] Amine adduct thermally latent curing catalysts are, for example, a combination of the two components (a) an amine compound and an epoxy compound, (b) a combination of the two components and an active hydrogen compound, or (c) a combination of two or three components (an amine compound and an isocyanate compound and / or a urea compound). These can be easily prepared by mixing the components, reacting them at a temperature between room temperature and 200°C, cooling them to solidify them, and then pulverizing them, or by reacting them in a solvent such as methyl ethyl ketone, dioxane, or tetrahydrofuran, removing the solvent, and then pulverizing the solid content.

[0074] A microcapsule-type thermally latent curing catalyst is a curing catalyst having a core made of an amine compound or an amine adduct compound obtained by reacting an amine compound with an epoxy compound, an isocyanate compound, or a urea compound, and coated with a shell made of a synthetic resin or an inorganic oxide. Examples of the amine compound include the amine compounds described above. Because the amine compound exhibits favorable latency, it is preferable that the amine compound be an imidazole derivative. Examples of imidazole derivatives include 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, and 2-phenyl-4-methyl-5-hydroxymethylimidazole. Examples of synthetic resins that form the shell include phenolic resins, melamine resins, epoxy resins, urethane resins, and urea resins, and these resins can also be used in combination. Examples of inorganic oxides that form the shell include silica, alumina, titania, and magnesia.

[0075] Representative examples of commercially available thermal latent curing catalysts include, but are not limited to, the following: Amine-epoxy adduct curing catalysts include "Amicure PN-23" (product name of Ajinomoto Fine-Techno Co., Ltd.), "Amicure PN-40" (product name of Ajinomoto Fine-Techno Co., Ltd.), "Amicure PN-50" (product name of Ajinomoto Fine-Techno Co., Ltd.), "Hardener X-3661S" (product name of ACR Co., Ltd.), "Hardener X-3670S" (product name of ACR Co., Ltd.), "Novacure HX-3742" (product name of Asahi Kasei Corporation), and "Novacure Examples of the hydroxybenzoates include, but are not limited to, "Novacure HX-3721" (product name of Asahi Kasei Corporation), "Novacure HXA9322HP" (product name of Asahi Kasei Corporation), "Novacure HXA3922HP" (product name of Asahi Kasei Corporation), "Novacure HXA3932HP" (product name of Asahi Kasei Corporation), "Novacure HXA5945HP" (product name of Asahi Kasei Corporation), "Novacure HXA5911HP" (product name of Asahi Kasei Corporation), and "Novacure HXA9382HP" (product name of Asahi Kasei Corporation). Examples of the amine-urea adduct curing catalyst include, but are not limited to, "Fujicure FXE-1000" (product name of T&K TOKA Corporation), "Fujicure FXR1020" (product name of T&K TOKA Corporation), "Fujicure FXR-1030" (product name of T&K TOKA Corporation), "Fujicure FXR1121" (product name of T&K TOKA Corporation), "Fujicure FXR1081" (product name of T&K TOKA Corporation), "Fujicure 1061" (product name of T&K TOKA Corporation), "Fujicure 1171" (product name of T&K TOKA Corporation), and "Fujicure 2015" (product name of T&K TOKA Corporation).

[0076] An inclusion-type thermally latent curing catalyst is a curing catalyst having a structure in which guest molecules such as amine compounds are confined at the molecular level in crystalline spaces formed by host molecules. An example of a commercially available inclusion-type thermally latent curing catalyst is "NISSOCURE TIC-188" (product name of Nippon Soda Co., Ltd.).

[0077] The thermal latent curing catalysts as the thermal anionic polymerization initiator may be used alone or in combination of two or more.

[0078] The thermal cationic polymerization initiator is a compound that generates an acid (cation) as an active species by heat, and can promote the polymerization of a cationic polymerizable compound. Examples of the thermal cationic polymerization initiator include BF ４ － , SbF ６ -, AsF ６ － , B(C ６ F ５ ) ４ － , Ga(C ６ F ５ ) ４ － , C(CF ３ SO ２ ) ３ － , [P(R １ ) ａ F ６－ａ ] － , [C(R １ SO ２ ) ３ ] － , or [N(R １ SO ２ ) ２ ] － (In the formula, R １ are each independently an alkyl group in which at least a portion of the hydrogen atoms is substituted with a fluorine atom, a is an integer of 0 to 5, and when a is an integer of 2 or more, a plurality of R １may be the same or different.) as a counter anion, and an iodonium cation, a sulfonium cation, an ammonium cation, a phosphonium cation, or the like as a cation moiety. Examples of the thermal cationic polymerization initiator include dimethylphenyl(4-methoxybenzyl)ammonium tetrakis(pentafluorophenyl)borate, which is a borate-based quaternary ammonium salt (e.g., product name: CXC-1821 manufactured by King Industries, Inc.), 4-isopropyl-4'-methyldiphenyliodonium tetrakis(pentafluorophenyl)borate, which is a borate-based iodonium salt (e.g., product name: BLUESIL (registered trademark) PI 2074 manufactured by ELKEM SILICONES), 4-methylphenyl-4-(1-methylethyl)phenyliodonium tri(pentafluoroethyl)trifluorophosphate (e.g., product name: IK-1 manufactured by San-Apro Co., Ltd.), a thermal cationic polymerization initiator represented by the following formula, which is a phosphate-based sulfonium salt (e.g., product name: TA-100 manufactured by San-Apro Co., Ltd.), A photo / thermal cationic polymerization initiator which is a gallate-based iodonium salt represented by the following formula (for example, product name: IK-1FG manufactured by San-Apro Co., Ltd.; see JP 2022-080366 A). A thermal cationic polymerization initiator which is a gallate-based sulfonium salt represented by the following formula (for example, product name: TA-100FG manufactured by San-Apro Co., Ltd.; see WO2018 / 020974). These include, but are not limited to:

[0079] When the curable resin composition contains the thermal polymerization initiator (B2), the content of the thermal polymerization initiator (B2) in the curable resin composition is preferably 0.5 to 30 mass%, more preferably 0.5 to 25 mass%, and even more preferably 0.5 to 20 mass%, relative to the total mass of the resin composition.

[0080] (C) Inorganic Thixotropy-Imparting Agent The curable resin composition of this embodiment contains (C) an inorganic thixotropy-imparting agent (hereinafter also referred to as "component (C)"). The (C) inorganic thixotropy-imparting agent imparts thixotropy to the curable resin composition and increases the fluidity of the curable resin composition when shear is applied to the curable resin composition. From the viewpoint of thixotropy and applicability to a dispensing method, in this embodiment, the content of the (C) inorganic thixotropy-imparting agent is 10 to 70 parts by mass, preferably 12 to 68 parts by mass, and more preferably 15 to 65 parts by mass, relative to 100 parts by mass of the curable resin composition.

[0081] Examples of (C) inorganic thixotropy-imparting agents include, but are not limited to, silica such as colloidal silica, hydrophobic silica, fine silica, and nanosilica, and inorganic fine particles such as calcium carbonate, bentonite, acetylene black, and ketjen black. Among these, silica fine particles and calcium carbonate fine particles are preferred, and silica fine particles are more preferred. Silica fine particles may be used in combination with other inorganic fine particles. The average particle size of the particulate inorganic thixotropy-imparting agent is preferably 5 to 750 nm, and more preferably 10 to 600 nm. In this specification, the average particle size of the inorganic fine particles can be measured using a dynamic light scattering Nanotrac particle size analyzer.

[0082] (C) Examples of commercially available inorganic thixotropy-imparting agents include, but are not limited to, hydrophobic fumed silica manufactured by CABOT Corporation (product name: CAB-O-SIL (registered trademark) TS720, average particle size: 12 nm), hydrophobic fumed silica manufactured by Nippon Aerosil (product name: R805, average particle size: 20 nm), hydrophilic fumed silica manufactured by Nippon Aerosil (product name: 200, average particle size: 12 nm), amorphous silica manufactured by Nippon Shokubai (product name: Seahoster KE-P10, average particle size: 100 nm), and calcium carbonate manufactured by Ube Material Industries (product name: CS3NA, average particle size: <0.5 μm, and product name: CS4NA, average particle size: <0.5 μm).

[0083] The inorganic thixotropy-imparting agents (C) may be used alone or in combination of two or more.

[0084] (D) Modified Polydimethylsiloxane The curable resin composition of this embodiment contains (D) a modified polydimethylsiloxane (hereinafter also referred to as "component (D)"). More specifically, the modified polydimethylsiloxane is a compound represented by the formula: Here, "an organic substituent has been introduced into the side chain of the polydimethylsiloxane main chain" means that some of the methyl groups in the polydimethylsiloxane main chain have been substituted with organic substituents. "an organic substituent has been introduced into the end of the polydimethylsiloxane main chain" means that some of the methyl groups in the polydimethylsiloxane main chain have been substituted with organic substituents. ３ ) ３ ) is substituted with an organic substituent. The position of the modifying group in the modified polydimethylsiloxane may be a side chain, a terminal (one terminal or both terminals), or both a side chain and a terminal. Modified polydimethylsiloxanes also include polydimethylsiloxanes with a gemini structure. The degree of polymerization of the modified polydimethylsiloxane (the number of dimethylsiloxane repeating units) is not particularly limited and is, for example, 3 or more, preferably 5 or more.

[0085] In this embodiment, the content of the (D) modified polydimethylsiloxane is 0.01 to 15 parts by mass, preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the (C) inorganic thixotropy-imparting agent.

[0086] In recent years, optical modules have been required to be increasingly smaller and more highly integrated, and it is expected that the application area of ​​alignment adhesives used in active alignment techniques will become increasingly narrow. Therefore, adhesives are required to be able to be applied in narrow line widths (e.g., 1000 μm or less) using a dispensing method. At the same time, to enable high-precision alignment even in narrow application areas, adhesives are required to be able to achieve a high application height without sagging when applied in narrow line widths. The present inventors have discovered that by using a curable resin composition containing (A) a polymerizable compound and (B) a polymerization initiator in combination with (C) an inorganic thixotropic agent and (D) a modified polydimethylsiloxane in specific amounts, a curable resin composition can be obtained that can be applied in narrow line widths (e.g., 1000 μm or less) while achieving a high application height. The mechanism of this action is not limited to the following: (1) by including a specific amount of (C) inorganic thixotropy-imparting agent, when shear is applied for discharge by a dispensing method, the fluidity of the curable resin composition increases, and smooth discharge from a nozzle or the like becomes possible; (2) once discharged from a nozzle or the like and released from the shear applied when discharging the curable resin composition, the (C) inorganic thixotropy-imparting agent aggregates due to its interaction, and the shape of the curable resin composition is maintained; (3) the inorganic thixotropy-imparting agent (C) and the modified polydimethylsiloxane (D) are mixed together, and the curable resin composition is then allowed to stand for a certain period of time. (D) modified polydimethylsiloxane promotes and maintains aggregation of the inorganic thixotropy-imparting agent (C) when released from shear during extrusion of the curable resin composition, thereby improving the shape retention of a curable resin composition with a narrow line width; and (4) compared with unmodified polydimethylsiloxane, (D) modified polydimethylsiloxane has good miscibility with the polymerizable compound (A), and can be dispersed in the curable resin composition when shear is applied to the curable resin composition.

[0087] In one embodiment, the modified polydimethylsiloxane (D) is modified with at least one modifying group selected from the group consisting of C3 to C20 alkyl, aralkyl, alcohol, phenol, polyether, aryl, amino, epoxy, and carboxyl.

[0088] In one embodiment, the (D) modified polydimethylsiloxane has hydroxyl groups, phenyl groups, or a combination thereof. The presence of hydroxyl groups and / or phenyl groups in the (D) modified polydimethylsiloxane is thought to generate OH interactions (hydrogen bonds) and / or OH / π interactions with the surface of the (C) inorganic thixotropy-imparting agent, further improving the effect of promoting and maintaining aggregation between the (C) inorganic thixotropy-imparting agents.

[0089] The curable resin composition of this embodiment may contain optional components other than the above components (A) to (D), such as those described below, if desired.

[0090] Coupling Agent The curable resin composition of this embodiment may contain a coupling agent, if desired, to the extent that the effect of this embodiment is not impaired. The coupling agent has two or more different functional groups in the molecule, one of which is a functional group that chemically bonds with an inorganic material, and the other is a functional group that chemically bonds with an organic material. By including a coupling agent in the resin composition, the adhesive strength of the resin composition to an adherend such as a substrate is improved.

[0091] Examples of coupling agents include, but are not limited to, silane coupling agents, aluminum coupling agents, titanium coupling agents, etc., depending on the type of functional group that chemically bonds with the inorganic material.

[0092] Examples of coupling agents include, but are not limited to, various coupling agents such as epoxy, amino, vinyl, methacrylic, acrylic, and mercapto coupling agents depending on the type of functional group that chemically bonds with the organic material. Among these, epoxy coupling agents containing an epoxy group are preferred from the viewpoint of moisture resistance reliability.

[0093] The coupling agents may be used alone or in combination of two or more.

[0094] When a coupling agent is added, the amount of the coupling agent added is preferably 0.01 to 10 parts by weight, and more preferably 0.1 to 5 parts by weight, per 100 parts by weight of the total amount of the resin composition, from the viewpoint of improving adhesive strength.

[0095] Photosensitizer The resin composition of this embodiment may contain a photosensitizer, if desired, within a range that does not impair the effects of this embodiment. The photosensitizer absorbs light energy and transmits it to the photopolymerization initiator, thereby increasing the sensitivity of the photopolymerization initiator to light. Examples of photosensitizers include thioxanthone derivatives, carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, azo and diazo compounds, halogen compounds, and photoreducible dyes, with thioxanthone derivatives being preferred.

[0096] Specific examples of thioxanthone derivatives include isopropylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and thioxanthone ammonium salt, with 2,4-diethylthioxanthone being preferred.

[0097] Other examples of photosensitizers include 9-fluorenone, anthrone, dibenzosuberone, fluorene, 2-bromofluorene, 9-bromofluorene, 9,9-dimethylfluorene, 2-fluorofluorene, 2-iodofluorene, 2-fluorenamine, 9-fluorenol, 2,7-dibromofluorene, 9-aminofluorene hydrochloride, 2,7-diaminofluorene, 9,9'-spirobi[9H-fluorene], 2-fluorenecarboxaldehyde, 9-fluorenylmethanol, 2-acetylfluorene, benzophenone, diethoxyacetophenone, 2- Examples of suitable hydroxy-2-methyl-1-phenylpropan-1-one include, but are not limited to, hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-methyl-2-morpholino(4-thiomethylphenyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone oligomer, nitro compounds, and dyes.

[0098] The photosensitizer may be used alone or in combination of two or more. When the resin composition contains a photosensitizer, the content of the photosensitizer is preferably 0.1 to 20 parts by weight, and more preferably 1 to 15 parts by weight, relative to 100 parts by weight of the photopolymerization initiator.

[0099] Other Additives If desired, the resin composition of this embodiment may further contain other additives, such as pigments, conductive fillers, stabilizers, ion trapping agents, leveling agents, antioxidants, antifoaming agents, viscosity modifiers, flame retardants, colorants, plasticizers, etc., within the scope of the present embodiment. The type and amount of each additive are as per usual.

[0100] From the viewpoint of preventing a reduction in curing strength and adhesion and preventing outgassing and bleeding, the resin composition of this embodiment is substantially free of liquid components such as water, solvents, ionic liquids, etc. (excluding the liquid components (A) to (D)). For example, the content of liquid components relative to the total weight of the resin composition is preferably 3 wt % or less, and more preferably 1 wt % or less. Examples of the solvent include organic solvents commonly used in the field of curable compositions, such as hydrocarbons (benzene, toluene, xylene, cyclohexane, etc.), aprotic polar solvents (N,N-dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, etc.), nitriles (acetonitrile, etc.), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), esters (ethyl acetate, butyl acetate, butyrolactone, propylene carbonate, etc.), ethers (cyclopentyl methyl ether, diethyl ether, tetrahydrofuran, dimethoxyethane, etc.), alcohols (methanol, ethanol, propanol, butanol, etc.), terpenes (turpentine, terpineol, isobornyl acetate, etc.), and halogenated solvents (dichloromethane, chloroform, etc.).

[0101] The method for producing the resin composition of this embodiment is not particularly limited. For example, the resin composition of this embodiment can be obtained by simultaneously or separately introducing components (A) to (D), and other optional components as needed, into an appropriate mixer, and stirring and mixing while melting by heating if necessary to form a homogeneous composition. The mixer is not particularly limited, but examples that can be used include a Raikai mixer, a Henschel mixer, a three-roll mill, a ball mill, a planetary mixer, and a bead mill equipped with a stirrer and a heater. These devices may also be used in appropriate combinations.

[0102] The resin composition of this embodiment can be a one-component resin composition contained in a single container, or a two-component (or multi-component) resin composition divided into two or more containers, depending on the intended use. When a two-component (or multi-component) resin composition is used, the components (A) to (D) and other optional components as needed can be selected in the same manner as for a one-component resin composition. Furthermore, when a two-component (or multi-component) resin composition is used, the components (A) to (D) and other optional components as needed can be divided into two or multiple components in any manner without particular limitation. When divided into two or multiple components in any manner, each component may contain one or more components selected from the components (A) to (D) and other optional components as needed. The components (A) to (D) may be contained in a single component, or a component may contain only the components (A) to (D) and / or other optional components as needed. For example, when separating into liquid A and liquid B, the separation may be as follows: liquid A: component (A), liquid B: component (B) and component (C) and component (D), or liquid A: component (A) and component (C), liquid B: component (B) and component (D), or liquid A: component (A) and component (D), or liquid B: component (B) and component (C), or liquid A: component (B), liquid B: component (A) and component (C) and component (D), or liquid A: component (A), component (B) and component (D), or liquid B: component (A), component (C) and component (D). When components (A) to (D) are contained in liquid A and other components are contained in liquid B, only liquid A, or a combination of liquid A and liquid B, can be considered the resin composition of this embodiment. On the other hand, when components (A) to (D) are contained in separate liquids, the respective liquids can be combined to form the resin composition of this embodiment. Examples of the case where the components (A) to (D) are contained in separate liquids include a resin composition in which the components (A) to (D) are separated into two or more containers, specifically a kit composed of multiple liquids containing any of the components (A) to (D).

[0103] The resin composition thus obtained is photocurable when the (B) polymerization initiator contains the (B1) photopolymerization initiator, is thermocurable when the (B) polymerization initiator contains the (B2) thermal polymerization initiator, and is photo- and thermocurable when the (B) polymerization initiator contains the (B1) photopolymerization initiator and the (B2) thermal polymerization initiator.

[0104] When photocuring the resin composition, the light to be irradiated is, for example, ultraviolet (UV) light. In this specification, ultraviolet light refers to light having a wavelength in the range of 200 nm to 410 nm. The resin composition of this embodiment can be cured by irradiation with any of wavelengths of, for example, 365 nm, 385 nm, or 405 nm. The irradiation dose of the light to be irradiated is 50 mJ / cm. ２ ~2000mJ / cm ２ It is preferable that:

[0105] When the resin composition is thermally cured, the resin composition can be cured, for example, by heat treatment at 40 to 200°C for 0.1 to 300 minutes. At a temperature of 100°C, the resin composition preferably cures within 5 hours, more preferably within 3 hours, and even more preferably within 1 hour. When the resin composition of this embodiment is used to manufacture semiconductor devices or electronic components that contain components that deteriorate under high temperature conditions, the composition is preferably thermally cured at a temperature of 40 to 90°C for 30 to 120 minutes. For example, when the resin composition is used in an optical sensor module, the curing temperature is preferably 40 to 90°C, more preferably 60 to 90°C.

[0106] When the resin composition of this embodiment contains (B1) a photopolymerization initiator and (B2) a thermal polymerization initiator, the resin composition can be further cured with heat, for example, after being cured with light (UV) or during light irradiation.

[0107] The method for applying the resin composition is not particularly limited, and for example, the resin composition can be applied to a desired portion of a component such as a substrate by a known printing method, dispensing method, or coating method. Printing methods include, but are not limited to, inkjet printing, screen printing, lithographic printing, carton printing, metal printing, offset printing, gravure printing, and flexographic printing. Dispensing methods include, but are not limited to, methods using a jet dispenser, air dispenser, volumetric dispenser, screw dispenser, tubing dispenser, and the like. Coating methods include, but are not limited to, dip coating, spray coating, bar coater coating, gravure coating, reverse gravure coating, and spin coater coating. The curable resin composition of this embodiment is suitable for dispensing methods for application in thin line widths (e.g., 1000 μm or less). In particular, it is suitable for application to a line width preferably within the range of 50 to 1000 μm, more preferably within the range of 50 to 800 μm, and even more preferably within the range of 100 to 500 μm.

[0108] Furthermore, since the curable resin composition of this embodiment has high shape retention after being discharged by a dispensing method, even when two or more layers are applied in layers, the curable resin composition does not sag and a higher application height can be achieved. When two or more layers are applied in layers, it is not necessary to perform a curing treatment for each applied layer before applying the next layer, and the second and subsequent layers can be applied on top of the first layer immediately after applying it.

[0109] The curable resin composition of this embodiment has high shape retention, making it possible to form a coating having a high aspect ratio (height / width). In one embodiment, when the curable resin composition is applied in a single layer with a line width W in the range of 100 to 500 μm, the ratio (H1 / W1) of the height H1 of one curable resin composition layer to the line width W1 of one curable resin composition layer is 0.78 or more, preferably 0.80 or more, and more preferably 0.82 or more. In one embodiment, when the curable resin composition is applied in two layers with a line width W in the range of 100 to 500 μm, the ratio (H2 / W1) of the height H2 of the second curable resin composition layer (the sum of the first and second layers) to the line width W1 of the first curable resin composition layer is 1.40 or more, preferably 1.45 or more, and more preferably 1.50 or more. In one embodiment, when the (A) polymerizable compound includes a (meth)acrylate compound, when the curable resin composition is applied in one layer with a line width W in the range of 100 to 500 μm, the ratio (H1 / W1) of the height H1 of the curable resin composition to the line width W1 of the curable resin composition layer is 0.82 or more, preferably 0.88 or more. In one embodiment, when the (A) polymerizable compound includes a (meth)acrylate compound, when the curable resin composition is applied in two layers with a line width W in the range of 100 to 500 μm, the ratio (H2 / W1) of the height H2 of the second curable resin composition to the line width W1 of the first curable resin composition layer is 1.49 or more, preferably 1.60 or more. In one embodiment, when the (A) polymerizable compound includes an epoxy compound, when the curable resin composition is applied in one layer with a line width W in the range of 100 to 500 μm, the ratio (H1 / W1) of the height H1 of one layer of the curable resin composition to the line width W1 of one layer of the curable resin composition is 0.78 or more, preferably 0.80 or more, and more preferably 0.82 or more.In one embodiment, when the (A) polymerizable compound includes an epoxy compound, and the curable resin composition is applied in two layers with a line width W in the range of 100 to 500 μm, the ratio (H2 / W1) of the height H2 of the second layer of curable resin composition (the total of the first and second layers) to the line width W1 of the first layer of curable resin composition is 1.40 or more, preferably 1.45 or more, and more preferably 1.50 or more. However, it should be noted that the aspect ratio of the applied curable resin composition may vary depending on the type of adherend to which it is applied. Application may be performed, for example, at room temperature (20°C ± 5°C).

[0110] The curable resin composition of this embodiment can be used as an adhesive composition. The adhesive composition enables good fixing, bonding, or protection of general-purpose plastics (e.g., PE, PS, PP, etc.), engineering plastics (e.g., LCP (liquid crystal polymer), polyamide, polycarbonate, etc.), ceramics (e.g., alumina, aluminum nitride, beryllium oxide, etc.), and metals (e.g., copper, nickel, etc.), and can be used to fix, bond, or protect components constituting a semiconductor device or electronic component. Examples of semiconductor devices include, but are not limited to, HDDs, semiconductor elements, optical sensor modules such as image sensor modules and time-of-flight sensor modules, other semiconductor modules, and integrated circuits.

[0111] In one embodiment, the curable resin composition of this embodiment is used in a component alignment step in a manufacturing method for a semiconductor device or electronic component. An example of an alignment step is an active alignment step. A technique called active alignment is used to achieve high-precision bonding in optical module assembly. To improve accuracy, the active alignment method involves capturing a test pattern using an image sensor such as a CCD (charge-coupled device) or CMOS (complementary metal-oxide semiconductor), aligning the optical axis, and ensuring that there is no blurring in any area of ​​the image. Then, bonding is performed using a high-precision adhesive for alignment. The curable resin composition of this embodiment can be applied with a narrow line width (e.g., 1000 μm or less) while maintaining a desired coating height, making it suitable for use in a component alignment step in a manufacturing method for a semiconductor device or electronic component.

[0112] [Cured Product of Resin Composition] A cured product according to one embodiment of the present invention is a cured product obtained by curing the resin composition according to the above embodiment.

[0113] [Semiconductor Device, Electronic Component] A semiconductor device or electronic component according to one embodiment of the present invention includes the cured product according to the above embodiment. Here, the term "semiconductor device" refers to any device that can function by utilizing semiconductor properties, and includes electronic components, semiconductor circuits, modules incorporating these, electronic devices, etc. Examples of semiconductor devices or electronic components include, but are not limited to, HDDs, semiconductor elements, optical sensor modules such as image sensor modules and time-of-flight (TOF) sensor modules, other semiconductor modules, and integrated circuits.

[0114] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. In the following examples, parts and % represent parts by mass and % by mass unless otherwise specified.

[0115] [Production of Curable Resin Composition] Resin compositions were prepared by mixing predetermined amounts of each component using a three-roll mill according to the formulations shown in Tables 1 and 2. In Tables 1 and 2, the amount of each component is expressed in mass %. The components used in the examples and comparative examples are as follows.

[0116] (A) Polymerizable Compound (Component (A)) (A-1): Polyester acrylate (product name: M7100, manufactured by Toagosei Co., Ltd., (meth)acryloyl group equivalent: 152 g / eq) (A-2): Dimethylol-tricyclodecane diacrylate (product name: Light Acrylate DCP-A, manufactured by Kyoeisha Chemical Co., Ltd., (meth)acryloyl group equivalent: 152 g / eq) (A-3): 2-(o-phenylphenoxy)ethyl acrylate (product name: HRD-01, manufactured by Nisshoku Techno Fine Chemical Co., Ltd., (meth)acryloyl group equivalent: 268 g / eq) (A-4): 1,3,4,6-tetrakis(3-mercaptopropyl)glycoluril (product name: C3 TS-G, manufactured by Shikoku Chemicals Corporation, thiol equivalent: 110 g / eq) (A-5): hydrogenated bisphenol A diglycidyl ether (product name: jER YX8000, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 205 g / eq) (A-6): special epoxy resin (product name: AER9000, manufactured by Asahi Kasei Corporation, polyether type epoxy, epoxy equivalent: 380 g / eq) (A-7): 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (product name: CELLOXIDE (registered trademark) 2021P, manufactured by Daicel Corporation, alicyclic epoxy, epoxy equivalent: 130 g / eq) (A-8): 3-ethyl-3{[(3-ethyloxetan-3-yl)methoxy]methyl}oxetane (product name: OXT-221, manufactured by Toagosei Co., Ltd., oxetane equivalent: 107 g / eq)

[0117] (B) Polymerization initiator (component (B)) (B1-1): 1-hydroxy-cyclohexyl-phenyl-ketone (product name: Omnirad 184, manufactured by IGM Resins B.V., photoradical polymerization initiator) (B1-2): 4-isopropyl-4'-methyldiphenyliodonium tetrakis(pentafluorophenyl)borate (product name: BLUESIL (registered trademark) PI 2074, manufactured by ELKEM SILICONES, photocationic polymerization initiator) (B2-1): amine-epoxy adduct latent curing catalyst (product name: Novacure HXA9322HP, manufactured by Asahi Kasei Corporation, thermal anionic polymerization initiator) (B2-2): dicetyl peroxydicarbonate (product name: Perkadox 24L, manufactured by Kayaku Nouryon Co., Ltd., thermal radical polymerization initiator)

[0118] (C) Inorganic thixotropic agent (component (C)) (C-1): calcium carbonate particles (product name: CS3NA, manufactured by Ube Material Industries, Ltd., average particle size: <0.5 μm) (C-2): surface-treated silica (product name: SE5200SEE, manufactured by Admatechs Co., Ltd., average particle size: 2 μm) (C-3): polydimethylsiloxane surface-treated fumed silica (product name: CAB-O-SIL (registered trademark) TS-720, manufactured by Cabot Corporation, average particle size: 12 nm) (C-4): hydrophobic fumed silica (product name: R805, manufactured by Nippon Aerosil, average particle size: 20 nm) (C-5): hydrophilic fumed silica (product name: AEROSIL (R) 200, manufactured by Nippon Aerosil, average particle size: 12 nm)

[0119] (D) Modified polydimethylsiloxane (ingredient (D)) (D-1): Polyether-modified polydimethylsiloxane (product name: KF-6013, manufactured by Shin-Etsu Chemical Co., Ltd., PEG-9 dimethicone, having hydroxyl groups) (D-2): Polyether-modified polydimethylsiloxane (product name: KF-6043, manufactured by Shin-Etsu Chemical Co., Ltd., PEG-10 dimethicone, having hydroxyl groups) (D-3): Polyether-modified polydimethylsiloxane (product name: BYK-378, manufactured by BYK Japan KK) (D-4): Phenyl-modified polydimethylsiloxane (product name: KF-53, manufactured by Shin-Etsu Chemical Co., Ltd., diphenyl dimethicone, having phenyl groups) (D-5): C8 alkyl-modified polydimethylsiloxane (product name: KF-4418, manufactured by Shin-Etsu Chemical Co., Ltd., caprylyl methicone) (D-6): Polyether-modified polydimethylsiloxane (product name: KF-6011, manufactured by Shin-Etsu Chemical Co., Ltd., PEG-11 methyl ether dimethicone) (D-7): Polyether-modified polydimethylsiloxane (product name: BYK-333, manufactured by BYK Japan Co., Ltd.)

[0120] (E) Other optional components (E-1): 2,4-diethylthioxanthone (DETX) (photosensitizer)

[0121] The obtained samples of the examples and comparative examples were subjected to the following measurements.

[0122] [Measurement of the aspect ratio (height / width) of dispensed lines] (1) The test was conducted at room temperature (20°C ± 5°C). Using a fully automatic multipurpose dispenser FAD2500 (registered trademark) manufactured by Musashi Engineering Co., Ltd., three single-layer lines of the resin compositions of the Examples and Comparative Examples, each 250 to 300 μm wide and 30 mm long, were dispensed onto each of an LCP substrate and an alumina substrate to prepare test specimens. After allowing the test specimens to stand for approximately 30 seconds, the test specimens were irradiated with ultraviolet light of a wavelength of 365 nm and an irradiation intensity of 500 mW / cm using a single-wavelength UV LED light source (OmniCure (registered trademark) AC475, manufactured by Excelitas Technologies) at a position 4 cm above the light source. ２ The cumulative light intensity is 2000 mJ / cm ２The resin composition was photocured by continuous irradiation until the line width and height of the cured product of one layer of the resin composition reached a value (measured using an ultraviolet integrating actinometer UIT-250 and a photodetector UVD-S365 (manufactured by Ushio Inc.)). Thereafter, using a microscope (STM6-F21-3 manufactured by Olympus Corporation), the line width and height of one layer of the cured product of the resin composition were measured at three points per line. The average line width W1 and height H1 were used to calculate the ratio (H1 / W1) of the line width W1 of one layer of the curable resin composition to the height H1 of one layer of the curable resin composition (aspect ratio of one layer). The results are shown in Tables 1 and 2. (2) The test was conducted at room temperature (20°C ± 5°C). Three first-layer lines of the resin compositions of the Examples and Comparative Examples, each having a line width of 250 to 300 μm and a length of 30 mm, were dispensed onto each of the LCP substrate and the alumina substrate using a fully automatic multipurpose dispensing machine FAD2500 (registered trademark) manufactured by Musashi Engineering Co., Ltd. Immediately thereafter, a second-layer line was dispensed on top of the first-layer line under the same conditions to prepare a test specimen. After leaving the test specimen stationary for approximately 30 seconds, a single-wavelength UV LED light source (OmniCure (registered trademark) AC475, manufactured by Excelitas Technologies) was used to irradiate the test specimen with ultraviolet light having a wavelength of 365 nm and an irradiation intensity of 500 mW / cm at a position 4 cm above the light source from the top surface of the test specimen. ２ The cumulative light intensity is 2000 mJ / cm ２ The resin composition was photocured by continuous irradiation until the line width of the first layer of the resin composition and the height of the two layers, the first and second layers of the resin composition combined, reached a value of 1 / 2 (measured using an ultraviolet integrating actinometer UIT-250 and a photodetector UVD-S365 (manufactured by Ushio Inc.)). Thereafter, using a microscope (STM6-F21-3 manufactured by Olympus Corporation), the line width of the first layer of the resin composition and the height of the two layers, the first and second layers of the resin composition combined, were measured at three points per line. The average line width W1 and height H2 were used to calculate the ratio (H2 / W1) of the height H2 of the second layer of the curable resin composition to the line width W1 of the first layer of the curable resin composition (aspect ratio of the two layers). The results are shown in Tables 1 and 2.

[0123]

[0124]

[0125] The resin compositions of Examples 1 to 18, which satisfied the configuration of the present invention, were capable of dispense application with a narrow line width of 250 to 300 μm, while achieving a higher aspect ratio (height / width) than the resin compositions of the comparative examples. Furthermore, in the case of two-layer application, the second layer could be applied on top of the first layer immediately after the first layer was applied, and even in the case of overlapping applications with narrow line widths, it was possible to achieve a high application height without the resin composition dripping.

[0126] All publications, patent applications, and technical standards mentioned in this specification are herein incorporated by reference to the same extent as if each individual publication, patent application, or technical standard was specifically and individually indicated to be incorporated by reference.

Claims

1. A curable resin composition comprising: (A) a polymerizable compound; (B) a polymerization initiator; (C) an inorganic thixotropy-imparting agent; and (D) a modified polydimethylsiloxane, wherein the content of the (C) inorganic thixotropy-imparting agent is 10 to 70 parts by mass per 100 parts by mass of the curable resin composition; and the content of the (D) modified polydimethylsiloxane is 0.01 to 15 parts by mass per 100 parts by mass of the (C) inorganic thixotropy-imparting agent.

2. The curable resin composition according to claim 1, wherein the polymerizable compound (A) comprises a (meth)acrylate compound.

3. The curable resin composition according to claim 1, wherein the polymerizable compound (A) comprises an epoxy compound.

4. The curable resin composition according to claim 1, wherein the polymerizable compound (A) comprises a (meth)acrylate compound and an epoxy compound.

5. A curable resin composition according to any one of claims 1 to 4, wherein (C) the inorganic thixotropy-imparting agent comprises inorganic fine particles.

6. A curable resin composition according to any one of claims 1 to 5, wherein (C) the inorganic thixotropy-imparting agent comprises silica fine particles.

7. A curable resin composition according to any one of claims 1 to 6, wherein (D) the modified polydimethylsiloxane is modified with at least one modifying group selected from the group consisting of C3 to C20 alkyl, aralkyl, alcohol, phenol, polyether, aryl, amino, epoxy, and carboxyl.

8. A curable resin composition according to any one of claims 1 to 7, wherein (D) the modified polydimethylsiloxane has a hydroxyl group, a phenyl group, or a combination thereof.

9. The curable resin composition according to any one of claims 1, 2, and 4 to 8, wherein (A) the polymerizable compound comprises a (meth)acrylate compound, and when the curable resin composition is applied in one layer with a line width W in the range of 100 to 500 μm, the ratio (H1 / W1) of the height H1 of one layer of the curable resin composition to the line width W1 of one layer of the curable resin composition is 0.82 or greater.

10. The curable resin composition according to any one of claims 1, 2, and 4 to 9, wherein (A) the polymerizable compound comprises a (meth)acrylate compound, and when the curable resin composition is applied in two layers with a line width W in the range of 100 to 500 μm, the ratio (H2 / W1) of the height H2 of the second layer of the curable resin composition to the line width W1 of the first layer of the curable resin composition is 1.49 or greater.

11. The curable resin composition according to any one of claims 1, 3 to 8, wherein (A) the polymerizable compound comprises an epoxy compound, and when the curable resin composition is applied in one layer with a line width W in the range of 100 to 500 μm, the ratio (H1 / W1) of the height H1 of one layer of the curable resin composition to the line width W1 of one layer of the curable resin composition is 0.78 or more.

12. The curable resin composition according to any one of claims 1, 3 to 8, and 11, wherein (A) the polymerizable compound comprises an epoxy compound; and when the curable resin composition is applied in two layers with a line width W in the range of 100 to 500 μm, the ratio (H2 / W1) of the height H2 of the second layer of the curable resin composition to the line width W1 of the first layer of the curable resin composition is 1.40 or more.

13. The curable resin composition according to any one of claims 1 to 12, which is to be applied in a line width within the range of 50 to 1000 μm.

14. The curable resin composition according to any one of claims 1 to 13, which is to be applied in two or more layers.

15. The curable resin composition according to any one of claims 1 to 14, which is an adhesive composition.

16. The curable resin composition according to any one of claims 1 to 15, which is used in a component alignment step in a method for manufacturing a semiconductor device or electronic component.

17. A cured product obtained by curing the curable resin composition according to any one of claims 1 to 16.

18. A semiconductor device or electronic component comprising the cured product according to claim 17.

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