(METH)acrylate compound, method for synthesizing the same, and use thereof

Abstract

To provide a novel (meth)acrylate compound, a method for synthesizing the (meth)acrylate compound, and a resin composition including the (meth)acrylate compound and a resin component; and to provide a cured product obtained by curing the resin composition and an adhesive obtained using the resin composition.SOLUTION: A (meth)acrylate compound is represented by chemical formula (I). (R1 and R2 are identical or different to denote a glycidyl group or a group represented by formula (1), R3 denotes a hydrogen atom or a methyl group, and n denotes an integer of 1 to 3.) (R3 and n are as defined above.)SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a novel (meth)acrylate compound, a method for synthesizing the compound, and use of the compound. [Background technology]

[0002] Acrylic resins obtained by polymerizing (curing) (meth)acrylate compounds having an acryloyl group (-COCH=CH2) or a methacryloyl group (-COC(CH3)=CH2) have excellent light resistance (weather resistance), and are therefore widely used as materials for items exposed to light, such as light-emitting elements and devices such as displays. In order to impart heat resistance and desired mechanical properties to acrylic resins, various (meth)acrylate compounds (polyfunctional monomers or polyfunctional prepolymers) have been proposed and adopted.

[0003] As a polyfunctional monomer, an isocyanurate-type (meth)acrylate compound represented by chemical formula (VI) is known (see Patent Document 1). However, since this (meth)acrylate compound has a rigid molecular structure derived from the isocyanuric acid skeleton of the core portion, it exhibits the property of small volumetric shrinkage upon curing, but its adhesiveness (adhesion) to metals and other types of resins, flexibility, and heat resistance are still not sufficient.

[0004] [ka] (In the formula, R represents a hydrogen atom or a methyl group.) [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 52-128387 Summary of the Invention [Problem to be solved by the invention]

[0006] An object of the present invention is to provide a novel (meth)acrylate compound, a method for synthesizing the compound, and a resin composition containing the compound. Another object of the present invention is to provide a cured product obtained by curing the resin composition, and an adhesive containing the resin composition as a component. [Means for solving the problem]

[0007] As a result of extensive research to solve the above problems, the present inventors have discovered that one or more -CH2CH2CH2SCH2(CH2) n OCOCR 3 Isocyanuric acid compounds having a ═CH group (wherein R 3 represents a hydrogen atom or a methyl group, and n represents an integer of 1 to 3.) the present inventors have recognized that the above-mentioned object can be achieved by the above-mentioned method, and have thus completed the present invention. That is, the first invention is a (meth)acrylate compound represented by chemical formula (I).

[0008] [ka] (In the formula, R 1 or R 2 are the same or different and represent a glycidyl group or a group represented by formula (1). 3 represents a hydrogen atom or a methyl group, and n represents an integer of 1 to 3.

[0009] [ka] (In the formula, R 3 and n is the same as above.

[0010] The second invention is a method for synthesizing the (meth)acrylate compound of the first invention, characterized by reacting an isocyanuric acid compound represented by chemical formula (II) with a thiol compound represented by chemical formula (III), and then reacting the resulting mixture with a (meth)acryloyl halide represented by chemical formula (IV) or a (meth)acrylic anhydride represented by chemical formula (V).

[0011] [ka] (In the formula, R 4 or R 5 are the same or different and represent a glycidyl group or an allyl group.

[0012] [ka] (wherein n is the same as defined above).

[0013] [ka] (In the formula, R 3 is the same as above. X represents a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

[0014] [ka] (In the formula, R 3 are the same or different and represent a hydrogen atom or a methyl group.

[0015] A third invention is a resin composition characterized by containing the (meth)acrylate compound of the first invention. A fourth invention relates to a cured product obtained by curing the resin composition of the third invention. A fifth invention is an adhesive containing the resin composition of the third invention as a component. [Effects of the Invention]

[0016] The (meth)acrylate compound of the present invention has one or more -CH2CH2CH2SCH2(CH2) n OCOCR 3 Because it contains a =CH2 group, its use as a raw material or modifier (crosslinking agent) for photocurable and thermosetting resins is expected to produce polymers (cured products) with lower crosslinking density than those produced using conventional (meth)acrylate compounds, i.e., cured products with excellent flexibility, adhesion, heat resistance, moisture resistance, etc. In addition, because it contains an isocyanuric acid skeleton, it is expected to produce cured products with excellent transparency and weather resistance. [Brief explanation of the drawings]

[0017] [Figure 1] 1 is an IR spectrum chart of the pale yellow liquid obtained in Example 1. [Figure 2] 1 is an IR spectrum chart of the pale yellow liquid obtained in Example 2. DETAILED DESCRIPTION OF THE INVENTION

[0018] The present invention will be described in detail below. In the present invention and the description thereof, the names of acrylic resins, acrylic compounds, acrylate compounds, etc. may be generally used, for example, "acryloyl" and "methacryloyl" may be collectively referred to as "(meth)acryloyl", "acrylic" and "methacrylic" may be collectively referred to as "(meth)acrylic", and "acrylate" and "methacrylate" may be collectively referred to as "(meth)acrylate". Furthermore, even if the name of a substance is not followed by "compound" or "class," not limited to acrylic compounds, it may be expressed as a general name in the same way as when "compound" or "class" is added, as is customary.

[0019] 1. (Meth)acrylate compounds The present invention relates to a (meth)acrylate compound represented by chemical formula (I) (hereinafter, sometimes referred to as "the compound of the present invention"). Examples of the compound of the present invention include compounds represented by chemical formulas (I-1) to (I-10).

[0020] [ka]

[0021] [ka]

[0022] In the compounds of the present invention, preferred substituents are as follows. R 1 is preferably a glycidyl group or a group represented by formula (1), and more preferably a glycidyl group. R 2 is preferably a glycidyl group or a group represented by formula (1). R 3 are preferably the same and are a hydrogen atom or a methyl group. n is preferably an integer of 1 to 3, and more preferably an integer of 1 to 2.

[0023] [ka] (In the formula, R 3 and n is the same as above.

[0024] 2.Synthesis method The compound of the present invention can be synthesized by reacting an isocyanuric acid compound represented by chemical formula (II) with a thiol compound represented by chemical formula (III) (first step), and then reacting the resulting compound with a (meth)acryloyl halide represented by chemical formula (IV) or a (meth)acrylic anhydride represented by chemical formula (V) (second step). For example, the reaction scheme (A) shows an example in which the compound of the present invention is synthesized by reacting an isocyanuric acid compound represented by chemical formula (II) with a thiol compound represented by chemical formula (III) and then reacting the resulting compound with a (meth)acryloyl halide represented by chemical formula (IV).

[0025] [ka] (In the formula, R 1 ~R 5 , X and n are the same as above. 6 or R 7 are the same or different and represent a glycidyl group or a group represented by formula (2).

[0026] [ka] (wherein n is the same as defined above).

[0027] [1st step] The first step is a step of reacting an isocyanuric acid compound represented by chemical formula (II) with a thiol compound represented by chemical formula (III).

[0028] The isocyanuric acid compound represented by the chemical formula (II) includes the isocyanuric acid compounds represented by the chemical formulas (II-1) to (II-3).

[0029] [ka]

[0030] These isocyanuric acid compounds can be purchased as commercially available reagents or can be synthesized in accordance with the methods described in, for example, JP-A No. 2015-502919 and JP-A No. 2016-216399.

[0031] The thiol compound represented by the chemical formula (III) includes the thiol compounds represented by the chemical formulas (III-1) to (III-3). These thiol compounds can be purchased as commercially available reagents.

[0032] [ka]

[0033] The amount of the thiol compound represented by the chemical formula (III) used (charged amount) is preferably 1 to 2 equivalents relative to the allyl group in the isocyanuric acid compound represented by the chemical formula (II).

[0034] In the first step, a radical initiator (i) may be used to promote the reaction, and a reaction solvent (ii) may be used to facilitate the reaction.

[0035] Examples of the radical initiator (i) include 2,2'-azobis(isobutyronitrile), t-hexylperoxyisopropyl monocarbonate, t-hexylperoxy 2-ethylhexanoate, 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate, t-butylperoxypivalate, t-hexylperoxypivalate, t-butylperoxyneodecanoate, t-hexylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1,1-bis(t-hexylperoxy)cyclohexane, benzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, lauroyl peroxide, 2,2'-azobis(2-methylbutyronitrile), and dimethyl 2,2'-azobis(2-methylpropionate).

[0036] The amount (charge amount) of the radical initiator (i) used is preferably an appropriate ratio in the range of 0.001 to 0.1 times the amount (charge amount) of the isocyanuric acid compound represented by the chemical formula (II).

[0037] The reaction solvent (ii) is not particularly limited as long as it does not inhibit the reaction, and examples thereof include water, methanol, ethanol, propanol, 2-propanol, butanol, ethyl acetate, propyl acetate, butyl acetate, tetrahydrofuran, dioxane, acetonitrile, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoric triamide, etc. These may also be used in combination as the reaction solvent (ii).

[0038] In the reaction of the first step, the reaction temperature is preferably set in the range of 55 to 70° C. The reaction time is appropriately set depending on the set reaction temperature, but is preferably set in the range of 1 to 24 hours.

[0039] After completion of the reaction of the first step, the precursor compound of the compound of the present invention can be isolated from the resulting reaction liquid (reaction mixture) by, for example, concentrating the reaction liquid by distilling off the reaction solvent or by solvent extraction. If necessary, the product can be further purified by washing with water or the like, treatment with activated carbon, silica gel chromatography, recrystallization, or the like. The precursor compound of the compound of the present invention may be subjected to the above-mentioned concentration, extraction, purification, etc. before being subjected to the second step, or the reaction solution obtained after the completion of the reaction of the first step may be subjected to the second step as it is.

[0040] [Second process] The second step is a step of synthesizing the compound of the present invention by reacting the precursor compound of the compound of the present invention obtained in the first step with a (meth)acryloyl halide represented by chemical formula (IV) or a (meth)acrylic anhydride represented by chemical formula (V).

[0041] Examples of the (meth)acryloyl halide represented by chemical formula (IV) include acryloyl fluoride, acryloyl chloride, acryloyl bromide, and acryloyl iodide (all of which are acryloyl halides), and methacryloyl fluoride, methacryloyl chloride, methacryloyl bromide, and methacryloyl iodide (all of which are methacryloyl halides). These (meth)acryloyl halides can be purchased as commercially available reagents and used, or can be synthesized in accordance with the methods described in, for example, Journal of the Chemical Society, Chemical Communications, 1979, 24, 1180-1181, Russian Journal of Organic Chemistry, 2003, 12, 1702-1705, and Spectrochimica Acta, Part A: Molecular and Biomolecular Spectroscopy, 2018, 189, 66-79.

[0042] Examples of the (meth)acrylic anhydride represented by the chemical formula (V) include acrylic anhydride, methacrylic anhydride, and mixed acrylic and methacrylic anhydride. Acrylic acid-methacrylic acid mixed anhydride is synthesized as a mixture of acrylic acid anhydride and methacrylic acid anhydride by reacting acrylic acid and methacrylic acid with acetic anhydride, for example, according to the method described in Japanese Patent Laid-Open No. 62-158237. The acrylic acid-methacrylic acid mixed anhydride can then be isolated from this mixture by an appropriate separation means.

[0043] The amount of (meth)acryloyl halide represented by chemical formula (IV) or (meth)acrylic anhydride represented by chemical formula (V) used (charged amount) is preferably 1 to 2 equivalents relative to the hydroxy group in the precursor compound of the compound of the present invention.

[0044] In the second step, a base (iii) may be used to remove an acid by-product generated during the reaction, and a polymerization inhibitor (iv) may be used to suppress side reactions. A reaction solvent (v) may also be used to facilitate the reaction.

[0045] Examples of the base (iii) include trimethylamine, triethylamine, diisopropylethylamine, diazabicyclononene, diazabicycloundecene, pyridine, imidazole, lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium hydrogencarbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, cesium hydrogencarbonate, trilithium phosphate, trisodium phosphate, tripotassium phosphate, tricesium phosphate, dilithium hydrogenphosphate, disodium hydrogenphosphate, dipotassium hydrogenphosphate, discesium hydrogenphosphate, lithium dihydrogenphosphate, sodium dihydrogenphosphate, potassium dihydrogenphosphate, cesium dihydrogenphosphate, lithium acetate, sodium acetate, potassium acetate, cesium acetate, etc. These may be used in combination as the base (iii).

[0046] The amount of base (iii) used (charged amount) is preferably 1 to 2 equivalents relative to the hydroxy group in the precursor compound of the compound of the present invention.

[0047] Examples of the polymerization inhibitor (iv) include hydroquinone, 4-methoxyphenol, 4-methoxy-1-naphthol, 4-tert-butylcatechol, 3,5-di-tert-butyl-4-hydroxytoluene, 2,5-di-tert-butylhydroquinone, phenothiazine, copper chloride, copper sulfate, copper dibutyldithiocarbamate, etc. These may also be used in combination as the polymerization inhibitor (iv).

[0048] The amount of polymerization inhibitor (iv) used (charged amount) is preferably an appropriate ratio in the range of 0.0001 to 0.002 times the amount of the precursor compound of the compound of the present invention used (charged amount).

[0049] The reaction solvent (v) is not particularly limited as long as it does not inhibit the reaction, and examples thereof include solvents such as tetrahydrofuran, dioxane, ethyl acetate, acetonitrile, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoric triamide, water, etc. These may also be used in combination as the reaction solvent (v).

[0050] In the reaction of the second step, the reaction temperature is preferably set in the range of 0 to 40° C. The reaction time is appropriately set depending on the set reaction temperature, but is preferably set in the range of 1 to 24 hours.

[0051] After completion of the reaction in the second step, the target compound of the present invention can be isolated from the resulting reaction solution (reaction mixture) by, for example, concentrating the reaction solution by distilling off the reaction solvent or by solvent extraction. If necessary, the product can be further purified by washing with water or the like, treatment with activated carbon, silica gel chromatography, recrystallization, or the like.

[0052] In this synthesis method, a compound (compound represented by chemical formula (VII)) in which a sulfur atom is bonded to the carbon atom at the 2-position of the allyl group of the isocyanuric acid compound represented by chemical formula (II) may be obtained (see reaction scheme (B)).

[0053] [ka] (In the formula, R 3 ~R 5 , X and n are the same as above. 8 or R 9 are the same or different and represent a glycidyl group, a group represented by formula (2) or a group represented by formula (3). 10 or R 11 are the same or different and represent a glycidyl group, a group represented by formula (1) or a group represented by formula (4).

[0054] [ka] (wherein n is the same as defined above).

[0055] [ka] (In the formula, R 3 and n is the same as above.

[0056] Examples of the compound represented by chemical formula (VII) include compounds represented by chemical formulas (VII-1) to (VII-14). These compounds may be contained in the resin composition of the present invention.

[0057] [ka]

[0058] [ka]

[0059] [ka]

[0060] 3.Resin composition The resin composition of the present invention contains the compound of the present invention as an essential component, and may contain one or more types of the compound of the present invention. The content of the compound of the present invention in the resin composition of the present invention is preferably 0.001 to 99% by weight. In the present invention, the term "resin composition" refers to the state of a mixture before curing.

[0061] A cured product is obtained by polymerizing the compound of the present invention, but by allowing a curable compound other than the compound of the present invention (hereinafter simply referred to as the "curable compound") to coexist during this polymerization, a cured product can be obtained in which the compound of the present invention and the curable compound are copolymerized. The curable compound includes both a polymerizable monomer and a polymerizable oligomer (semi-cured product) having a structure in which a polymerizable monomer is polymerized.

[0062] Examples of the curable compound include an epoxy compound (a) (referring to an epoxy resin before curing) and an ene compound (b) having a carbon-carbon double bond (hereinafter, sometimes simply referred to as "ene compound (b)"). Hereinafter, the resin composition of the present invention will be described as a "first resin composition" containing the compound of the present invention and an epoxy compound (a), and a "second resin composition" containing the compound of the present invention and an ene compound (b).

[0063] (First resin composition) The first resin composition of the present invention is a resin composition containing the compound of the present invention and an epoxy compound (a). That is, the first resin composition contains the compound of the present invention and the epoxy compound (a), and may optionally contain a curing agent (c), a curing accelerator (d), a photopolymerization initiator (e), a thermal polymerization initiator (f), a stabilizer (g), triphenylsilanol (h), talc (j), a filler (k), calcium carbonate (l), a reactive diluent (m), an additive (modifier) ​​(n), and the like.

[0064] The epoxy compound (a) can be any compound having an epoxy group (glycidyl group) in the molecule without any particular limitation. For example, diepoxy resins such as polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane diglycidyl ether, polytetramethylene ether glycol diglycidyl ether, glycerin diglycidyl ether, cyclohexane diglycidyl ether, and dicyclopentadiene diglycidyl ether; Triepoxy resins such as trimethylolpropane triglycidyl ether and glycerin triglycidyl ether; Polyglycidyl ethers obtained by reacting epichlorohydrin with polyhydric phenols such as bisphenol A, bisphenol F, bisphenol AD, catechol, and resorcinol, or polyhydric alcohols such as glycerin and polyethylene glycol (for example, bisphenol A epoxy resins and bisphenol F epoxy resins); Glycidyl ether esters obtained by reacting hydroxycarboxylic acids such as p-hydroxybenzoic acid and β-hydroxynaphthoic acid with epichlorohydrin; Polyglycidyl esters obtained by reacting polycarboxylic acids such as phthalic acid and terephthalic acid with epichlorohydrin; Glycidyl glycoluril compounds having two or more epoxy groups in the molecule, such as 1,3,4,6-tetraglycidyl glycoluril; Cycloaliphatic epoxy resins such as 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, vinyl(3,4-cyclohexene) dioxide, and 2-(3,4-epoxycyclohexyl)-5,1-spiro-(3,4-epoxycyclohexyl)-m-dioxane; dicyclopentadiene-type diglycidyl ethers such as dicyclopentadiene dimethanol diglycidyl ether; cyclohexane-type diglycidyl ethers such as 1,4-cyclohexanedimethanol diglycidyl ether; Glycidylamine-type epoxy resins such as tetraglycidylbis(aminomethyl)cyclohexane; Liquid epoxy resins containing a naphthalene skeleton, such as 1,6-bis(glycidyloxy)naphthalene; Epoxy resins having a silicone skeleton, such as 1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldisiloxane; nitrogen-containing cyclic epoxy resins such as triglycidyl isocyanurate and hydantoin-type epoxy resins (e.g., 1,3-diglycidyl-5-methyl-5-ethylhydantoin); In addition, we also offer epoxy phenol novolac resins (phenol novolac type epoxy resins), epoxy cresol novolac resins, epoxy polyolefins, cyclic aliphatic epoxy resins, urethane modified epoxy resins, and more. Examples include epoxy-modified organopolysiloxane compounds obtained by a hydrosilylation addition reaction between an organic compound having a carbon-carbon double bond and a glycidyl group and a silicon compound having a SiH group (for example, the epoxy-modified organopolysiloxane compounds disclosed in JP-A-2004-99751 and JP-A-2006-282988), and these may be used in combination.

[0065] The content of the epoxy compound (a) in the first resin composition of the present invention is preferably 0.1 to 70% by weight, more preferably 1 to 60% by weight, and even more preferably 20 to 50% by weight, based on the entire first resin composition (total amount).

[0066] The content of the compound of the present invention in the first resin composition of the present invention is preferably 0.1 to 70% by weight, more preferably 1 to 60% by weight, and even more preferably 20 to 50% by weight, based on the entire first resin composition (total amount).

[0067] The first resin composition of the present invention may contain a curing agent (c). Examples of the curing agent (c) include: Thiol compounds; Compounds containing a phenolic hydroxyl group; acid anhydride; organic phosphine compounds such as triphenylphosphine, diphenylnaphthylphosphine, and diphenylethylphosphine; Aromatic phosphonium salts; Aromatic diazonium salts; Aromatic iodonium salts; Aromatic selenium salts and the like are included.

[0068] Examples of thiol compounds include: Aliphatic thiol compounds such as ethanedithiol, propanedithiol, hexamethylenedithiol, decamethylenedithiol, tolylene-2,4-dithiol, 2,2-bis(mercaptomethyl)-1,3-propanedithiol, 2-(mercaptomethyl)-2-methyl-1,3-propanedithiol, and 2-ethyl-2-(mercaptomethyl)-1,3-propanedithiol; Aromatic thiol compounds such as benzenedithiol, toluenedithiol, and xylenedithiol (p-xylenedithiol); Cyclic sulfide compounds such as 1,4-dithiane ring-containing polythiol compounds represented by chemical formula (VIII); mercaptoalkyl sulfide compounds such as 3-thiapentane-1,5-dithiol and 4-mercaptomethyl-3,6-dithia-1,8-octanedithiol; mercaptopropionic acid esters such as pentaerythritol tetrakis(3-mercaptopropionate); Epoxy resin terminal mercapto compound; 3,6-dioxa-1,8-octanedithiol, a mercaptoalkyl ether disulfide compound represented by chemical formula (IX), 2,2′-[[2,2-bis[(2-mercaptoethoxy)methyl]-1,3-propanediyl]bis(oxy)]bisethanethiol, 3,3′-[[2,2-bis[(3-mercaptopropoxy)methyl]-1,3-propanediyl]bis(oxy)]bis-1-propanethiol, 3-[2,2-bis[(3-mercaptopropoxy)methyl]butoxy]-1-propanethiol, 3-(3-mercaptopropoxy)-2,2-bis[(3-mercaptopropoxy)methyl]-1-propanol, mercaptoalkyl ether compounds such as 2,2-bis[(3-mercaptopropoxy)methyl]-1-butanol; 1,3,4,6-tetrakis(2-mercaptoethyl)glycoluril, 1,3,4,6-tetrakis(3-mercaptopropyl)glycoluril, etc. These thiol compounds may be used alone or in combination of two or more.

[0069] [ka] (In the formula, p represents an integer of 1 to 5.)

[0070] [ka] (In the formula, q represents an integer of 1 to 20.)

[0071] Examples of compounds having a phenolic hydroxyl group include: Examples include bisphenol A, bisphenol F, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol S, tetrachlorobisphenol A, tetrabromobisphenol A, dihydroxynaphthalene, phenol novolac, cresol novolac, bisphenol A novolac, brominated phenol novolac, and resorcinol.

[0072] Examples of acid anhydrides include: Examples of the anhydride include methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, trimellitic anhydride, nadic anhydride, himic anhydride, methylnadic anhydride, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride, bicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride, and methylnorbornane-2,3-dicarboxylic acid.

[0073] The content of the curing agent (c) in the first resin composition of the present invention is preferably 10 to 300 parts by weight, more preferably 50 to 200 parts by weight, based on 100 parts by weight of the epoxy compound (a).

[0074] The first resin composition of the present invention may contain a curing accelerator (d). Examples of the curing accelerator (d) include: (d-1) Amines; (d-2) reaction products of epoxy compounds and amines; (d-3) Examples include reaction products of a compound having one or more isocyanate groups in the molecule and a compound having at least one of a primary amino group and a secondary amino group in the molecule, and these may be used in combination.

[0075] The (d-1) amines may be any amines having at least one amino group selected from a primary amino group, a secondary amino group, and a tertiary amino group in the molecule. (d-1) Examples of amines include: aliphatic amines such as diethylenetriamine, triethylenetetramine, n-propylamine, 2-hydroxyethylaminopropylamine, cyclohexylamine, 4,4'-diaminodicyclohexylmethane, and dimethylbenzylamine; Aromatic amines such as 4,4'-diaminodiphenylmethane and o-methylaniline; Examples thereof include nitrogen-containing heterocyclic compounds such as 2-ethyl-4-methylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazoline, 2,4-dimethylimidazoline, piperidine, and piperazine.

[0076] The content of the curing accelerator (d) (particularly, (d-1) amines) in the first resin composition of the present invention is preferably 0.1 to 30 parts by weight, more preferably 1 to 10 parts by weight, per 100 parts by weight of the curing agent (c).

[0077] (d-2) The reaction product of an epoxy compound and an amine is a solid that is hardly soluble in epoxy resins at room temperature, but becomes soluble (easily soluble) when heated and functions as a curing accelerator, and is therefore also called a latent curing accelerator (hereinafter, the reaction product of an epoxy compound and an amine may be referred to as a "latent curing accelerator").

[0078] Epoxy compounds used as raw materials for latent curing accelerators include the above-mentioned epoxy compound (a), as well as glycidylamine compounds obtained by reacting 4,4'-diaminodiphenylmethane, m-aminophenol, or the like with epichlorohydrin; Examples thereof include monofunctional epoxy compounds such as butyl glycidyl ether, phenyl glycidyl ether, and glycidyl methacrylate.

[0079] Examples of amines used as raw materials for latent curing accelerators include the above-mentioned (d-1) amines. Among these amines, amines having a tertiary amino group in the molecule are raw materials that provide latent curing accelerators with excellent curing acceleration properties. Examples of such amines include: amines such as dimethylaminopropylamine, diethylaminopropylamine, di-n-propylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine, and N-methylpiperazine; Amines having a tertiary amino group in the molecule, such as imidazole compounds such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, and 2-phenylimidazole, 2-Dimethylaminoethanol, 1-methyl-2-dimethylaminoethanol, 1-phenoxymethyl-2-dimethylaminoethanol, 2-diethylaminoethanol, 1-butoxymethyl-2-dimethylaminoethanol, 1-(2-hydroxy-3-phenoxypropyl)-2-methylimidazole, 1-(2-hydroxy-3-phenoxypropyl)-2-ethyl-4-methylimidazole, 1-(2-hydroxy-3-butoxypropyl)-2-methylimidazole, 1-(2-hydroxy-3-butoxypropyl)-2-ethyl-4-methylimidazole, 1-(2-hydroxy-3-phenoxypropyl)-2-phenylimidazoline, 1-(2-hydroxy-3-butoxypropyl)-2-methyl Examples of the tertiary amino acid include alcohols, phenols, thiols, carboxylic acids, and hydrazides having a tertiary amino group in the molecule, such as thiimidazoline, 2-(dimethylaminomethyl)phenol, 2,4,6-tris(dimethylaminomethyl)phenol, N-β-hydroxyethylmorpholine, 2-dimethylaminoethanethiol, 2-mercaptopyridine, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 4-mercaptopyridine, N,N-dimethylaminobenzoic acid, N,N-dimethylglycine, nicotinic acid, isonicotinic acid, picolinic acid, N,N-dimethylglycine hydrazide, N,N-dimethylpropionic acid hydrazide, nicotinic acid hydrazide, and isonicotinic acid hydrazide.

[0080] In order to further improve the storage stability of the first resin composition of the present invention, in addition to the above-mentioned epoxy compound (a) and (d-1) amines, an active hydrogen compound having two or more active hydrogens in the molecule may be used as a third component as raw materials for the latent curing accelerator. Examples of active hydrogen compounds include: Polyhydric phenols such as bisphenol A, bisphenol F, bisphenol S, hydroquinone, catechol, resorcinol, pyrogallol, and phenol novolac resins; Polyhydric alcohols such as trimethylolpropane; Polycarboxylic acids such as adipic acid and phthalic acid; Examples include 1,2-dimercaptoethane, 2-mercaptoethanol, 1-mercapto-3-phenoxy-2-propanol, mercaptoacetic acid, anthranilic acid, and lactic acid.

[0081] Furthermore, the latent curing accelerator may be surface-treated with an isocyanate compound or an acidic compound. Examples of the isocyanate compound include: Monofunctional isocyanate compounds such as n-butyl isocyanate, isopropyl isocyanate, phenyl isocyanate, and benzyl isocyanate; Examples of the polyfunctional isocyanate compound include 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.

[0082] Instead of this polyfunctional isocyanate compound, a compound containing a terminal isocyanate group obtained by reacting a polyfunctional isocyanate compound with an active hydrogen compound can also be used.Specific examples include an addition reaction product having a terminal isocyanate group obtained by reacting toluylene diisocyanate with trimethylolpropane, and an addition reaction product having a terminal isocyanate group obtained by reacting toluylene diisocyanate with pentaerythritol.

[0083] The acidic substance used for the surface treatment of the latent curing accelerator may be any of a gas, liquid, or solid, and may be any of an inorganic acid or an organic acid. Examples of the acid include carbon dioxide gas, sulfurous acid gas, sulfuric acid, hydrochloric acid, oxalic acid, phosphoric acid, acetic acid, formic acid, propionic acid, adipic acid, caproic acid, lactic acid, succinic acid, tartaric acid, sebacic acid, p-toluenesulfonic acid, salicylic acid, boric acid, tannic acid, alginic acid, polyacrylic acid, polymethacrylic acid, phenol, pyrogallol, phenolic resin, and resorcinol resin.

[0084] The latent curing accelerator can be easily obtained by mixing an epoxy compound, an amine, and, if necessary, an active hydrogen compound, reacting them at a temperature between room temperature and 200°C, solidifying the mixture, and pulverizing it; alternatively, by reacting them in a solvent such as methyl ethyl ketone, dioxane, or tetrahydrofuran, removing the solvent, and then pulverizing the solid content.

[0085] Alternatively, commercially available latent curing accelerators may be used. Examples include Amicure PN-23 (trade name), Amicure PN-H (trade name), Amicure PN-50 (trade name), Amicure PN-23J (trade name), Amicure PN-40J (trade name), and Amicure MY-24 (trade name) manufactured by Ajinomoto Fine Techno; Novacure HX-3088 (trade name), Novacure HX-3721 (trade name), Novacure HX-3722 (trade name), Novacure HX-3742 (trade name), Novacure HX-3941HP (trade name), and Novacure HXA3922HP (trade name) manufactured by Asahi Kasei; and Fujicure FXR-1030 (trade name), Fujicure FXR-1081 (trade name), and Fujicure FXR-1121 (trade name) manufactured by T&K TOKA.

[0086] The content of the latent curing accelerator in the first resin composition of the present invention is preferably 0.1 to 1000 parts by weight, more preferably 1 to 80 parts by weight, and even more preferably 1 to 30 parts by weight, relative to 100 parts by weight of the epoxy compound (a).

[0087] (d-3) A reaction product of a compound having one or more isocyanate groups in the molecule and a compound having at least one of a primary amino group and a secondary amino group in the molecule can be obtained by reacting the two in an organic solvent such as dichloromethane.

[0088] Examples of isocyanate compounds having one or more isocyanate groups in the molecule include: n-Butyl isocyanate, isopropyl isocyanate, 2-chloroethyl isocyanate, phenyl isocyanate, p-bromophenyl isocyanate, m-chlorophenyl isocyanate, o-chlorophenyl isocyanate, p-chlorophenyl isocyanate, 2,5-dichlorophenyl isocyanate, 3,4-dichlorophenyl isocyanate, 2,6-dimethylphenyl isocyanate, o-fluorophenyl isocyanate, p-fluorophenyl isocyanate, m-tolyl isocyanate, p-tolyl isocyanate, o-trifluoromethylphenyl isocyanate, m-trifluoromethylphenyl isocyanate, benzyl isocyanate, hexamethylene Examples of the isocyanate include diphenylmethane diisocyanate, 2,4-toluylene diisocyanate, 2,6-toluylene diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethane-4,4'-diisocyanate, 2,2-dimethyldiphenylmethane-4,4'-diisocyanate, tolidine diisocyanate, isophorone diisocyanate, xylylene diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, p-phenylene diisocyanate, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, tris-(3-isocyanato-4-methylphenyl)isocyanurate, and tris-(6-isocyanatohexyl)isocyanurate.

[0089] Examples of compounds having at least one of a primary amino group and a secondary amino group in the molecule include: Examples of the alkylamine include dimethylamine, diethylamine, di-n-propylamine, di-n-butylamine, di-n-hexylamine, di-n-octylamine, di-n-ethanolamine, dimethylaminopropylamine, diethylaminopropylamine, morpholine, piperidine, 2,6-dimethylpiperidine, 2,2,6,6-tetramethylpiperidine, piperazine, pyrrolidine, benzylamine, N-methylbenzylamine, cyclohexylamine, metaxylylenediamine, 1,3-bis(aminomethyl)cyclohexane, isophoronediamine, N-aminoethylpiperazine, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-phenylimidazole, and 1,1-dimethylhydrazine.

[0090] In the first resin composition of the present invention, the content of (d-3) the reaction product of a compound having one or more isocyanate groups in the molecule and a compound having at least one of a primary amino group and a secondary amino group in the molecule is preferably 1 to 10 parts by weight per 100 parts by weight of the epoxy compound (a).

[0091] The first resin composition of the present invention may contain a photopolymerization initiator (e). Examples of the photopolymerization initiator (e) include a photoradical polymerization initiator and a photoanionic polymerization initiator.

[0092] Examples of the photoradical polymerization initiator include: acetophenones such as 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, and 2-methyl-1-{4-(methylthio)phenyl}-2-morpholinopropan-1-one; benzoins such as benzil dimethyl ketal; benzophenones such as benzophenone, 4-phenylbenzophenone, and hydroxybenzophenone; Examples include thioxanthones such as isopropylthioxanthone and 2,4-diethylthioxanthone, and methylphenyl glyoxylate, and these may be used in combination. If necessary, the photoradical polymerization initiator may be used in combination with a known photopolymerization accelerator such as a benzoic acid such as 4-dimethylaminobenzoic acid or a tertiary amine.

[0093] Examples of the photoanionic polymerization initiator include onium salts and carbamates. Examples of onium salts include 1,2-diisopropyl-3-(bis(dimethylamino)methylene)guanidinium 2-(3-benzoylphenyl)propionate and 1,2-dicyclohexyl-4,4,5,5-tetramethylbiguanidinium n-butyltriphenylborate. Examples of carbamates include 2-nitrophenylmethylpiperidine-1-carboxylate, 1-(anthraquinone-2-yl)ethylimidazolecarboxylate, 1-(3-(2-hydroxyphenyl)-2-propenoyl)piperidine, and 9-anthranylmethyldiethylcarbamate.

[0094] In addition, in the first resin composition of the present invention, a sensitizer such as pyrene, perylene, acridine orange, thioxanthone, 2-chlorothioxanthone, or benzoflavin can be used.

[0095] The content of the photopolymerization initiator (e) in the first resin composition of the present invention is preferably 0.001 to 10% by weight, and more preferably 0.01 to 5% by weight, based on the entire first resin composition (total amount).

[0096] The first resin composition of the present invention may contain a thermal polymerization initiator (f) in addition to the photopolymerization initiator (e). Examples of the thermal polymerization initiator (f) include a thermal radical polymerization initiator and a thermal anionic polymerization initiator.

[0097] Examples of the thermal radical polymerization initiator include diisopropyl peroxydicarbonate, benzoyl peroxide, t-butyl peroxyisobutyrate, t-hexyl peroxyisopropyl monocarbonate, t-hexyl peroxy 2-ethylhexanoate, 1,1,3,3-tetramethylbutyl peroxy 2-ethylhexanoate, t-butyl peroxypivalate, t-hexyl peroxypivalate, t-butyl peroxyneodecanoate, and t-hexyl peroxyneodecanoate. Examples of the peroxides include peroxides such as benzoyl peroxide, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1,1-bis(t-hexylperoxy)cyclohexane, benzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, and lauroyl peroxide; and azo compounds such as 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2-methylbutyronitrile), and dimethyl 2,2'-azobis(2-methylpropionate), and these may be used in combination.

[0098] Examples of the thermal anionic polymerization initiator include amines and imidazoles, and these may be used in combination. Examples of amines include diethylenetriamine, triethylenetetramine, isophoronediamine, xylylenediamine, diaminodiphenylmethane, and 1,3,4,6-tetrakis(3-aminopropyl)glycoluril. Examples of imidazoles include 2-methylimidazole, 2-ethyl-4-methylimidazole, and 2-phenylimidazole.

[0099] The content of the thermal polymerization initiator (f) in the first resin composition of the present invention is preferably 0.001 to 20% by weight, and more preferably 0.01 to 10% by weight, based on the entire first resin composition (total amount).

[0100] The first resin composition of the present invention may contain a stabilizer (g) as long as it does not impair the effects of the present invention. Examples of the stabilizer (g) include liquid borate ester compounds, aluminum chelates (aluminum trisacetylacetonate, etc.), and organic acids (acetic acid, propionic acid, butyric acid, succinic acid, malic acid, citric acid, barbituric acid, etc.).

[0101] Examples of liquid boric acid ester compounds include trimethyl borate, triethyl borate, tri-n-propyl borate, triisopropyl borate, triallyl borate, tri-n-butyl borate, tripentyl borate, trihexyl borate, tricyclohexyl borate, trioctyl borate, trinonyl borate, tridecyl borate, tridodecyl borate, trihexadecyl borate, trioctadecyl borate, tris(2-ethylhexyloxy)borane, triphenyl borate, tri-o-tolyl borate, tri-m-tolyl borate, tribenzyl borate, triethanolamine borate, and 2,2′-oxybis(5,5′-dimethyl-1,3,2-oxaborinane). The liquid borate ester compound is liquid at room temperature, and therefore can suppress an increase in viscosity of the resin composition.

[0102] The content of the stabilizer (g) in the first resin composition of the present invention is preferably 0.1 to 9 wt %, more preferably 0.1 to 5 wt %, and even more preferably 0.1 to 4 wt %, based on the entire first resin composition (total amount).

[0103] The first resin composition of the present invention may contain triphenylsilanol (h). By containing triphenylsilanol (h), the pot life of the first resin composition of the present invention can be maintained and the curing end temperature when the resin composition is cured can be lowered.

[0104] The content of triphenylsilanol (h) in the first resin composition of the present invention is preferably 0.1 to 10% by weight, more preferably 0.3 to 7% by weight, and even more preferably 0.5 to 6% by weight, based on the entire first resin composition (total amount).

[0105] The first resin composition of the present invention may contain talc (j). By containing talc (j), the heat resistance, low thermal expansion property, and impact resistance of the first resin composition of the present invention can be improved. The shape of the talc (j) is preferably plate-like or flat. The aspect ratio of the talc (j) is preferably 5-20.

[0106] The content of talc (j) in the first resin composition of the present invention is preferably 5 to 20 parts by weight, more preferably 5 to 15 parts by weight, based on 100 parts by weight of the epoxy compound (a).

[0107] The first resin composition of the present invention may contain a filler (k). By containing the filler (k), the linear expansion coefficient of the cured product decreases, resulting in improved moisture resistance and thermal cycle resistance. Examples of the filler (k) include silica fillers (e.g., fused silica, spherical silica, etc.), alumina fillers (e.g., spherical alumina, crushed alumina, etc.), kaolin, clay, mica, barium sulfate, lithopone, gypsum, zinc stearate, perlite, quartz, quartz glass, oxides such as magnesium oxide, beryllium oxide, and titanium oxide, nitrides such as boron nitride, silicon nitride, and aluminum nitride, carbides such as silicon carbide, hydroxides such as aluminum hydroxide and magnesium hydroxide, metals and alloys such as copper, silver, iron, aluminum, nickel, and titanium, and carbon-based materials such as diamond and carbon. The filler (k) preferably has an average particle size of 0.005 to 10 μm, more preferably 0.1 to 6 μm. The shape of the filler (k) may be spherical, irregular, flaky, etc. When the shape of the filler (k) is other than spherical, the average particle size of the filler (k) means the average maximum diameter of the filler (k).

[0108] The content of the filler (k) in the first resin composition of the present invention is preferably 0 to 400 parts by weight, more preferably 5 to 300 parts by weight, and even more preferably 5 to 200 parts by weight, relative to 100 parts by weight of the entire first resin composition (total amount) excluding the filler (k).

[0109] The first resin composition of the present invention may contain calcium carbonate (1), which improves the drop impact resistance of the cured product. The average particle size of calcium carbonate (1) is not particularly limited, but is preferably 0.1 to 15 μm.

[0110] The content of calcium carbonate (l) in the first resin composition of the present invention is preferably 5 to 200 parts by weight based on 100 parts by weight of the epoxy compound (a).

[0111] The first resin composition of the present invention may contain a reactive diluent (m). In this specification, the reactive diluent refers to a compound that has one epoxy group (glycidyl group) and has a relatively low viscosity at room temperature. The reactive diluent (m) may have, in addition to the epoxy group, other polymerizable functional groups such as alkenyl groups such as vinyl and allyl; and unsaturated carboxylic acid residues such as acryloyl and methacryloyl, depending on the purpose.

[0112] Examples of the reactive diluent (m) include monoepoxide compounds such as n-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, ps-butylphenyl glycidyl ether, styrene oxide, and α-pinene oxide; Examples include monoepoxide compounds having other functional groups such as allyl glycidyl ether, glycidyl methacrylate, and 1-vinyl-3,4-epoxycyclohexane.

[0113] The content of the reactive diluent (m) in the first resin composition of the present invention is preferably 1 to 150 parts by weight based on 100 parts by weight of the epoxy compound (a).

[0114] The first resin composition of the present invention may be any of the following, as long as it does not impair the effects of the present invention: Pigments (titanium white, cyanine blue, watching red, red iron oxide, carbon black, aniline black, manganese blue, iron black, ultramarine blue, Hansa red, chrome yellow, chrome green, etc.), Thermoplastic resins and / or thermosetting resins (homopolymers such as various high-density, medium-density, and low-density polyethylenes, polypropylene, polybutene, and polypentene; ethylene-propylene copolymers; polyamide resins such as nylon-6 and nylon-6,6; vinyl chloride resins; nitrocellulose resins; vinylidene chloride resins; acrylic resins; acrylamide resins; styrene resins; vinyl ester resins; polyester resins; phenolic resins (phenolic compounds); silicone resins; fluorine-based resins; various elastomer resins such as acrylic rubber and urethane rubber; graft copolymers such as methyl methacrylate-butadiene-styrene graft copolymers and acrylonitrile-butadiene-styrene graft copolymers); Reinforcing agents (glass fiber, carbon fiber, etc.), Anti-sagging agents (hydrogenated castor oil, fine silica anhydride particles, etc.), Matting agents (fine silica, paraffin wax, etc.), Abrasives (zinc stearate, etc.), Internal mold release agents (fatty acids such as stearic acid, fatty acid metal salts of calcium stearate, fatty acid amides such as stearic acid amide, fatty acid esters, polyolefin wax, paraffin wax, etc.), Additives (modifiers) (n) such as surfactants, leveling agents, antifoaming agents, viscosity adjusting diluents (organic solvents), flexibility imparting agents, coupling agents (silane coupling agents such as glycidyl silane coupling agents, titanium coupling agents, etc.), fragrances, flame retardants, antioxidants, etc. may be contained in an amount of 0.01 to 50% by weight based on the entire first resin composition (total amount), as needed. Furthermore, when the first resin composition of the present invention contains an isocyanate group-containing compound as the additive (modifier) ​​(n), the adhesive strength of the resin composition can be improved while suppressing a decrease in the curability of the resin composition.

[0115] Examples of the isocyanate group-containing compound include: Examples of the isocyanate include n-butyl isocyanate, isopropyl isocyanate, 2-chloroethyl isocyanate, phenyl isocyanate, p-chlorophenyl isocyanate, benzyl isocyanate, hexamethylene diisocyanate, 2-ethylphenyl isocyanate, 2,6-dimethylphenyl isocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethane-4,4'-diisocyanate, tolidine diisocyanate, isophorone diisocyanate, xylylene diisocyanate, paraphenylene diisocyanate, 1,3,6-hexamethylene triisocyanate, and bicycloheptane triisocyanate.

[0116] The content of the isocyanate group-containing compound in the first resin composition of the present invention is preferably 0.1 to 20 parts by weight based on 100 parts by weight of the epoxy compound (a).

[0117] There are no particular limitations on the method for preparing (mixing) the first resin composition of the present invention. The above-mentioned components can be weighed out in predetermined amounts and mixed using a stirring and mixing device such as a three-roll mill or a planetary mixer, while heating as necessary.

[0118] Methods for polymerizing (curing) the first resin composition of the present invention include a thermal curing method and a photocuring method followed by thermal curing. For example, a curing device such as a sealed curing oven or a tunnel oven capable of continuous curing can be used as the thermal curing method. For example, means such as hot air circulation, infrared heating, and high-frequency heating can be used as the heat source. The curing temperature and curing time can be set appropriately.

[0119] Examples of photocuring methods include a method of irradiating with active energy rays, preferably a method of using a photopolymerization initiator (e) in combination. Examples of active energy rays include light, radiation, electromagnetic waves, and electron beams, with electron beams or light in the ultraviolet to infrared wavelength range being preferred. As the light source, for example, an ultra-high pressure mercury light source or a metal halide light source can be used for ultraviolet irradiation, a metal halide light source or a halogen light source can be used for visible light irradiation, and a halogen light source can be used for infrared irradiation. In addition, light sources such as lasers and LEDs that are compatible with emission of various wavelengths, which have become increasingly popular in recent years, may also be used. The irradiation amount of the active energy rays can be appropriately set depending on the type of light source, etc. By photocuring followed by thermal curing, production efficiency and the properties of the cured product can be improved. In the method of photocuring followed by thermal curing, the first resin composition of the present invention can be temporarily fixed by photocuring, so that displacement is less likely to occur during thermal curing.

[0120] (Second Resin Composition) The second resin composition of the present invention is a resin composition containing the compound of the present invention and an ene compound (b). That is, the second resin composition contains the compound of the present invention and the ene compound (b), and may optionally contain a curing agent (o), a photopolymerization initiator (e), a thermal polymerization initiator (f), an epoxy compound (a), an additive (modifier) ​​(n), and the like.

[0121] Examples of the ene compound (b) include: (1) (meth)acrylic acid alkyl ester monomers, (2) a hydroxyl group-containing monomer, (3) a carboxyl group-containing monomer, (4) an amino group-containing monomer, (5) Acetoacetyl group-containing monomers, (6) isocyanate group-containing monomers, (7) a glycidyl group-containing monomer, (8) Monomers containing one aromatic ring; (9) Monomers containing alkoxy groups and oxyalkylene groups, (10) Alkoxyalkyl(meth)acrylamide monomers, (11) (meth)acrylamide-based monomers, (12) monofunctional unsaturated compounds, (13) Polyfunctional unsaturated compounds (14) Other unsaturated compounds, etc.

[0122] (1) Examples of (meth)acrylic acid alkyl ester monomers include: methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, iso-butyl (meth)acrylate, tert-butyl (meth)acrylate, n-propyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, Cetyl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, Examples include isobornyl (meth)acrylate.

[0123] (2) Examples of hydroxyl group-containing monomers include: 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, (Meth)acrylic acid hydroxyalkyl esters such as 8-hydroxyoctyl (meth)acrylate; Caprolactone-modified monomers such as caprolactone-modified 2-hydroxyethyl (meth)acrylate; diethylene glycol (meth)acrylate, oxyalkylene-modified monomers such as polyethylene glycol (meth)acrylate; Others include 2-acryloyloxyethyl 2-hydroxyethyl phthalate, N-methylol (meth)acrylamide, Primary hydroxyl group-containing monomers such as hydroxyethyl acrylamide; 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-chloro 2-hydroxypropyl (meth)acrylate, propylene glycol diglycidyl ether-epoxy di(meth)acrylate, Phenol glycidyl ether-epoxy (meth)acrylate, Secondary hydroxyl group-containing monomers such as bisphenol A diglycidyl ether-epoxy di(meth)acrylate; Examples include tertiary hydroxyl group-containing monomers such as 2,2-dimethyl 2-hydroxyethyl (meth)acrylate.

[0124] (3) Examples of carboxyl group-containing monomers include: Examples include (meth)acrylic acid, acrylic acid dimer, crotonic acid, maleic acid, maleic anhydride, fumaric acid, citraconic acid, glutaconic acid, itaconic acid, acrylamido-N-glycolic acid, and cinnamic acid.

[0125] (4) Examples of amino group-containing monomers include: tert-butylaminoethyl (meth)acrylate, ethylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, Examples thereof include diethylaminoethyl (meth)acrylate.

[0126] (5) Examples of acetoacetyl group-containing monomers include: 2-(acetoacetoxy)ethyl (meth)acrylate, allyl acetoacetate and the like.

[0127] (6) Examples of isocyanate group-containing monomers include: 2-acryloyloxyethyl isocyanate, 2-Methacryloyloxyethyl isocyanate Examples thereof include alkylene oxide adducts thereof.

[0128] (7) Examples of glycidyl group-containing monomers include: In addition to glycidyl (meth)acrylate, Ethylene glycol diglycidyl ether-epoxy (meth)acrylate, Resorcinol diglycidyl ether-epoxy (meth)acrylate, Bis(4-hydroxyphenyl)sulfide diglycidyl ether-epoxy(meth)acrylate, Phenol novolac epoxy resin-(meth)acrylate, Cresol novolac epoxy resin-(meth)acrylate, Bisphenol (e.g., bisphenol A, bisphenol F) type epoxy resin-(meth)acrylate, Biphenol (e.g., 3,3',5,5'-tetramethylbiphenol) type epoxy resin-(meth)acrylate, Epoxy (meth)acrylates, which are reaction products of epoxy compounds such as tris(2,3-epoxypropyl)isocyanurate-(meth)acrylate with (meth)acrylic acid; Examples include glycidyl (meth)acrylates such as 4-hydroxybutyl (meth)acrylate glycidyl ether.

[0129] (8) Examples of monomers containing one aromatic ring include: phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, styrene, Examples include α-methylstyrene.

[0130] (9) Examples of monomers containing an alkoxy group and an oxyalkylene group include: 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, 2-butoxydiethylene glycol (meth)acrylate, methoxydiethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, Methoxydipropylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, Octoxypolyethylene glycol-polypropylene glycol-mono(meth)acrylate, Lauroxy polyethylene glycol mono(meth)acrylate, Examples include stearoxy polyethylene glycol mono(meth)acrylate.

[0131] (10) Examples of alkoxyalkyl(meth)acrylamide monomers include: methoxymethyl (meth)acrylamide, ethoxymethyl (meth)acrylamide, propoxymethyl (meth)acrylamide, isopropoxymethyl (meth)acrylamide, n-butoxymethyl (meth)acrylamide, isobutoxymethyl(meth)acrylamide and the like.

[0132] (11) Examples of (meth)acrylamide-based monomers include: (meth)acryloylmorpholine, dimethyl(meth)acrylamide, diethyl(meth)acrylamide, (Meth)acrylamide N-methylol (meth)acrylamide and the like.

[0133] (12) Examples of monofunctional unsaturated compounds include biphenyl structure-containing (meth)acrylate compounds, more specifically, o-biphenyl (meth)acrylate, m-biphenyl (meth)acrylate, Biphenyl (meth)acrylates such as p-biphenyl (meth)acrylate; o-biphenyloxymethyl (meth)acrylate, m-biphenyloxymethyl (meth)acrylate, p-biphenyloxymethyl (meth)acrylate, o-biphenyloxyethyl (meth)acrylate, m-biphenyloxyethyl (meth)acrylate, p-biphenyloxyethyl (meth)acrylate, o-biphenyloxypropyl (meth)acrylate, m-biphenyloxypropyl (meth)acrylate, biphenyloxyalkyl (meth)acrylates such as p-biphenyloxypropyl (meth)acrylate; (o-biphenyloxy)diethylene glycol (meth)acrylate, (m-biphenyloxy)diethylene glycol (meth)acrylate, (p-biphenyloxy)diethylene glycol (meth)acrylate, (o-biphenyloxy)dipropylene glycol (meth)acrylate, (m-biphenyloxy)dipropylene glycol (meth)acrylate, (p-biphenyloxy)dipropylene glycol (meth)acrylate, (o-biphenyloxy)polyethylene glycol (meth)acrylate, (m-biphenyloxy)polyethylene glycol (meth)acrylate, (p-biphenyloxy)polyethylene glycol (meth)acrylate, (o-biphenyloxy)polypropylene glycol (meth)acrylate, (m-biphenyloxy)polypropylene glycol (meth)acrylate, (p-biphenyloxy)polypropylene glycol (meth)acrylate, etc. Examples include biphenyloxypolyalkylene glycol (meth)acrylate.

[0134] (13) Examples of polyfunctional unsaturated compounds include difunctional monomers, trifunctional or higher functional monomers, urethane (meth)acrylates, the above-mentioned epoxy (meth)acrylates, polyester (meth)acrylates, and polyether (meth)acrylates.

[0135] Specific examples of bifunctional monomers include: ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, Polypropylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, Neopentyl glycol di(meth)acrylate, Ethylene oxide modified bisphenol A di(meth)acrylate, Propylene oxide modified bisphenol A di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,6-hexanediol ethylene oxide modified di(meth)acrylate, Glycerin di(meth)acrylate, pentaerythritol di(meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, Phthalic acid diglycidyl ester di(meth)acrylate, Hydroxypivalic acid modified neopentyl glycol di(meth)acrylate, Isocyanuric acid ethylene oxide modified diacrylate, 2-(meth)acryloyloxyethyl acid phosphate diester and the like.

[0136] Specific examples of tri- or higher functional monomers include: trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, Dipentaerythritol tri(meth)acrylate, Dipentaerythritol tetra(meth)acrylate, Dipentaerythritol penta(meth)acrylate, Dipentaerythritol hexa(meth)acrylate, Tri(meth)acryloyloxyethoxytrimethylolpropane, glycerin polyglycidyl ether poly(meth)acrylate, Tris(2-(meth)acryloyloxyethyl)isocyanurate, Isocyanuric acid ethylene oxide modified tri(meth)acrylate, Ethylene oxide modified dipentaerythritol penta(meth)acrylate, Ethylene oxide modified dipentaerythritol hexa(meth)acrylate, Ethylene oxide modified pentaerythritol tri(meth)acrylate, Ethylene oxide modified pentaerythritol tetra(meth)acrylate, Examples include succinic acid-modified pentaerythritol tri(meth)acrylate.

[0137] (14) Other unsaturated compounds include, for example: Divinylbenzene, piperylene, isoprene, pentadiene, vinylcyclohexene, chloroprene, butadiene, methylbutadiene, cyclopentadiene, methylpentadiene, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl propionate, vinyl stearate, vinyl chloride, vinylidene chloride, alkyl vinyl ether, vinyltoluene, vinylpyridine, vinylpyrrolidone, itaconic acid dialkyl ester, fumaric acid dialkyl ester, allyl alcohol, acryloyl chloride, methyl vinyl ketone, N-acrylamidomethyltrimethylammonium chloride acrylate, allyltrimethylammonium chloride, dimethylallyl vinyl ketone, 2-chloroethyl vinyl ether, triallyl isocyanurate, tetraallyl glycoluril, N-vinylpyrrolidone, N-vinylcaprolactam, ethylene glycol diallyl carbonate, trimellitic acid triallyl ester, trifluoroethyl (meth)acrylate, tribromobenzyl (meth)acrylate, perfluorooctylethyl (meth)acrylate, sulfur-containing (meth)acrylate, (meth)acryloyloxypropyl tris(methoxy)silane, and the like.

[0138] In the second resin composition of the present invention, the ene compound (b) may be a combination of the above-mentioned polymerizable monomer and polymerizable oligomer (a polymerizable oligomer (semi-cured product) having a structure in which the above-mentioned polymerizable monomer is polymerized), the polymerizable monomer may be a combination of the above-mentioned polymerizable monomer (different types of polymerizable monomers may be combined), and the polymerizable oligomer may be a combination of different types of polymerizable oligomers.

[0139] The content of the ene compound (b) in the second resin composition of the present invention is preferably 0.1 to 70% by weight, more preferably 1 to 60% by weight, and even more preferably 20 to 50% by weight, based on the entire second resin composition (total amount).

[0140] The content of the compound of the present invention in the second resin composition of the present invention is preferably 0.1 to 70% by weight, more preferably 1 to 60% by weight, and even more preferably 20 to 50% by weight, based on the entire second resin composition (total amount).

[0141] The second resin composition of the present invention may contain a curing agent (o). Examples of the curing agent (o) include the thiol compounds listed above as the curing agent (c) and the amines listed above as (d-1). The content of the curing agent (o) in the second resin composition of the present invention is preferably 10 to 300 parts by weight, more preferably 50 to 200 parts by weight, based on 100 parts by weight of the ene compound (b).

[0142] The second resin composition of the present invention may contain a photopolymerization initiator (e). Examples of the photopolymerization initiator (e) include the above-mentioned photopolymerization initiator (e). In addition, the above-mentioned photopolymerization accelerator and / or sensitizer may be used in combination with the photopolymerization initiator (e). The content of the photopolymerization initiator (e) in the second resin composition of the present invention is preferably 0.001 to 20% by weight, more preferably 0.01 to 10% by weight, based on the entire second resin composition (total amount).

[0143] The second resin composition of the present invention may contain a thermal polymerization initiator (f). Examples of the thermal polymerization initiator (f) include the thermal polymerization initiator (f) described above. The content of the thermal polymerization initiator (f) in the second resin composition of the present invention is preferably 0.001 to 20% by weight, more preferably 0.01 to 10% by weight, based on the entire second resin composition (total amount).

[0144] The second resin composition of the present invention contains the above-mentioned epoxy compound (a) as an additive (modifier). In this case, (1) the above-mentioned curing agent (o) or (2) a photocationic polymerization initiator (p) and / or a thermal cationic polymerization initiator (q) may be used to cure the epoxy compound (a). The content of the epoxy compound (a) in the second resin composition of the present invention is preferably 20 to 100 parts by weight, more preferably 40 to 80 parts by weight, based on 100 parts by weight of the ene compound (b).

[0145] Examples of the photocationic polymerization initiator (p) include onium salts and organometallic complexes. Examples of onium salts include diazonium salts, sulfonium salts, and iodonium salts. Examples of organometallic complexes include iron-allene complexes, titanocene complexes, and arylsilanol-aluminum complexes. Examples of commercially available cationic photopolymerization initiators include "ADEKA Optomer SP-150 (trade name)" and "ADEKA Optomer SP-170 (trade name)" manufactured by ADEKA, "UVE-1014 (trade name)" manufactured by General Electronics, "CD-1012 (trade name)" manufactured by Sartomer, and "CPI-100P (trade name)" manufactured by San-Apro. The counter anion of the photocationic polymerization initiator is SbF6 - , AsF6 - , B(C6F5)4 - , PF6 - etc.

[0146] Examples of the thermal cationic polymerization initiator (q) include various onium salts such as quaternary ammonium salts, phosphonium salts, and sulfonium salts, and organometallic complexes, and these may be used in combination. Examples of commercially available onium salts include "ADEKAOPTON CP-66 (trade name)" and "ADEKAOPTON CP-77 (trade name)" manufactured by ADEKA; "SAN-AID SI-60L (trade name)," "SAN-AID SI-80L (trade name)," and "SAN-AID SI-100L (trade name)" manufactured by Sanshin Chemical Industry; and "CI Series (trade name)" manufactured by Nippon Soda. Examples of organometallic complexes include alkoxysilane-aluminum complexes.

[0147] The second resin composition of the present invention may further contain the aforementioned stabilizer (g), triphenylsilanol (h), talc (j), filler (k), calcium carbonate (l), additive (modifier) ​​(n), etc., as long as the effects of the present invention are not impaired. The additive (modifier) ​​(n) may be contained in an amount of 0.01 to 50% by weight based on the entire second resin composition (total amount), if necessary.

[0148] The method for preparing (mixing) the second resin composition of the present invention is not particularly limited. For example, it can be prepared by mixing the compound of the present invention, the ene compound (b), the curing agent (o), the photopolymerization initiator (e) and / or the thermal polymerization initiator (f), and the additive (modifier) ​​(n). Known methods (e.g., the methods described in the section on the first resin composition) can be used as the mixing means. The compound of the present invention may be dissolved or dispersed in advance in a viscosity-adjusting diluent (organic solvent).

[0149] Methods for polymerizing (curing) the second resin composition of the present invention include a heat curing method, a photocuring method, and a photocuring followed by heat curing method. As a method for thermal curing, a method in which a thermal polymerization initiator (f) is used in combination can be mentioned. The heat curing conditions, ie, the heating temperature and heating time, can be set as appropriate, but are preferably set within the range of 60 to 130°C / 30 to 240 minutes, and more preferably within the range of 70 to 125°C / 30 to 120 minutes.

[0150] Examples of photocuring methods include a method of irradiating with active energy rays, preferably a method of using a photopolymerization initiator (e) in combination. Examples of active energy rays include light, radiation, electromagnetic waves, and electron beams, with electron beams or light in the ultraviolet to infrared wavelength range being preferred. As the light source, for example, an ultra-high pressure mercury light source or a metal halide light source can be used for ultraviolet irradiation, a metal halide light source or a halogen light source can be used for visible light irradiation, and a halogen light source can be used for infrared irradiation. In addition, light sources such as lasers and LEDs that are compatible with emission of various wavelengths, which have become increasingly popular in recent years, may also be used. The irradiation amount of the active energy rays can be appropriately set depending on the type of light source, etc. By photocuring followed by thermal curing, production efficiency and the properties of the cured product can be improved. In the method of photocuring followed by thermal curing, the second resin composition of the present invention can be temporarily fixed by photocuring, so that displacement is less likely to occur during thermal curing.

[0151] 4. Uses of resin compositions The resin composition of the present invention is not particularly limited in its use, and can be applied to products (parts and components) in various fields where resin materials are acceptable, and can be used as a raw material for materials in the fields of electricity and electronics, optics, architecture, civil engineering, automobiles and aircraft, and medicine, as well as for other daily necessities and miscellaneous goods.

[0152] For example, examples of parts, components and materials in the electrical and electronic fields include resin-coated copper foil, prepreg, copper-clad laminate, printed wiring board, solder resist ink, anisotropic conductive film, anisotropic conductive paste, interlayer insulating material, adhesive, pressure-sensitive adhesive, sealing material, encapsulant (sealing material), encapsulating sheet, insulating material, thermally conductive material, hot melt material, paint, potting agent, etc., but more specifically, Sealing materials (sealants) for printed wiring boards and electronic components such as interlayer insulating films and wiring coating films, sealing materials (sealants) for image display devices, sealing sheets for image display devices, sealing materials (sealants) for organic EL display elements, sealing sheets for organic EL display elements, layer-forming materials; Materials for forming display devices such as color filters, polarizing plates, display materials, resist materials, and alignment films; Materials for forming semiconductor devices such as resist materials and buffer coating films; Materials for forming optical components such as lenses, holograms, optical waveguides, optical circuits, optical circuit components, and anti-reflection films; Coating agents such as surface protective films, hard coating agents, antifouling films, and antireflection films for semiconductor elements and organic thin-film elements (for example, organic electroluminescence elements and organic thin-film solar cell elements); etc. Other examples include materials for organic electronics elements such as organic EL elements, organic transistors, and solar cells, materials for forming rigid wiring boards and flexible printed wiring boards for semiconductor mounting, mounting materials for semiconductor mounting, adhesives for flexible printed wiring boards, semiconductor encapsulants, solar cell encapsulants, insulating films for semiconductors, coverlay films for protecting flexible printed circuits, and coating agents for covering wiring.

[0153] Examples of materials in the optical field include lenses, prisms, films, core materials for optical fibers, cladding materials, abrasion-resistant coating agents for plastic lenses, materials for stereolithography, optical waveguides, filters, image display materials, lens arrays, sealing materials and reflector materials for optical semiconductor elements, light guide plates, light diffusion plates, diffraction elements, optical adhesives, etc. For example, lenses and prisms are not particularly limited as long as they utilize refraction on their surfaces. Also, materials for camera modules, LiDAR modules, and still camera lenses; Adhesives for finder prisms, target prisms, finder covers, light-receiving sensors, photographic lenses, projection lenses for projection televisions, etc.; Optical fiber materials around optical switches and optical connectors in optical communication systems; Encapsulants and adhesives for optical passive components, optical circuit components, and peripherals of optoelectronic integrated circuits; The bonding locations of a camera module include between an image sensor (imaging element) such as a CMOS or CCD and a substrate, between a cut filter and a substrate, between a substrate and a housing, between a housing and a cut filter, and between a housing and a lens unit.

[0154] As lenses and prisms, spherical lenses with spherical surfaces include convex lenses such as biconvex lenses, plano-convex lenses, and convex meniscus lenses, and concave lenses such as biconcave lenses, plano-concave lenses, and concave meniscus lenses; Aspherical lenses, such as lenses with aspherical surfaces, such as symmetric paraboloids, ellipsoids, hyperboloids, and polymorphic surfaces (e.g., quartic surfaces), and lenses with free-form surfaces without an axis of symmetry; Cylindrical lenses, which are semi-cylindrical and have a cylindrical surface; A toroidal lens with a toroidal surface with different radii of curvature in the longitudinal and transverse directions, like the surface of a doughnut; A thin Fresnel lens is a flat, concentrically arranged ring-shaped prism with a reflective surface that changes the direction of light and a refracting surface that transmits light, inclined in the same way as the curve of a thick convex lens, and these multiple prisms become successively smaller or larger as they move toward the center; A diffractive lens with a concentric relief pattern whose depth is approximately the wavelength of light; Examples include prisms having two or more optically flat surfaces, at least one pair of which is substantially non-parallel. Other examples of films include reflective films that are made by processing inorganic compounds such as MgF2 and SiO2 using vacuum deposition, sputtering, or CVD, or by adding a light absorber, and that transmit light in a desired wavelength range while reflecting light in an undesired wavelength range.

[0155] Examples of materials in the construction field include sealants, coating materials, and primers for exterior materials such as various metal panels and siding boards; Sealants, adhesives, injection materials, vibration damping materials, soundproofing materials, conductive materials for electromagnetic wave shielding, putty materials used between exterior materials, underlayment materials, ceiling materials and interior materials; Adhesives for bonding tiles and stone to exterior walls and substrates; Adhesives and pressure-sensitive adhesives for bonding wood flooring materials, polymeric floor sheets, and floor tiles to various floors; Examples include injection materials for repairing cracks in various exterior and interior materials.

[0156] Examples of materials used in the civil engineering field include joint sealants, coating materials, primers, paints, putty materials, injection materials, spray materials, and formwork for various concrete products such as roads, bridges, tunnels, and breakwaters.

[0157] Examples of materials in the automotive and aerospace sectors include structural materials, fiber-reinforced composites, adhesives for bodies and parts, sealing materials, coating materials, cushioning materials, vibration damping materials, soundproofing materials, and spray coating materials; adhesives, pressure sensitive adhesives, coatings and foams for automotive interiors; Examples include sealing materials for steel plate joints, adhesives, coating materials, etc. Furthermore, applications of substrates having a coating layer formed on the surface thereof from a cured product of the resin composition of the present invention include, for example, components for various industrial equipment such as transport vehicles (automobiles, aircraft, etc.) and electronic and electrical equipment (for example, sliding components such as cylinders, pistons, and bearings).

[0158] Examples of materials in the medical field include artificial bones, dental impression materials, medical rubber materials, medical adhesives, and medical device sealing materials.

[0159] Other examples include paints that are applied to substrates such as metals, resin films, glass, paper, and wood. [Example]

[0160] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. The main raw materials used in the synthesis examples and working examples are as follows:

[0161] [Main raw materials] 1,3-Bis(oxiranylmethyl)-5-(2-propenyl)isocyanurate: Shikoku Chemicals Corporation / See chemical formula (II-1) 1-Oxiranylmethyl-3,5-bis(2-propenyl)isocyanurate: Shikoku Chemicals Corporation / See chemical formula (II-2) 2,2'-Azobis(isobutyronitrile): Fujifilm Wako Pure Chemical Industries, Ltd. 2-Mercaptoethanol: Fujifilm Wako Pure Chemical Industries, Ltd. / See chemical formula (III-1) Triethylamine: Fujifilm Wako Pure Chemical Industries, Ltd. Acryloyl chloride: Fujifilm Wako Pure Chemical Industries, Ltd.

[0162] [Synthesis Example 1] <Synthesis of 1,3-bis(oxiranylmethyl)-5-[[(2-hydroxyethyl)thio]propyl]isocyanurate> A 1000 mL recovery flask was charged with 112.51 g (400.0 mmol) of 1,3-bis(oxiranylmethyl)-5-(2-propenyl)isocyanurate, 3.28 g (20.0 mmol) of 2,2'-azobis(isobutyronitrile), and 400.00 g of ethyl acetate, and the temperature was raised to 62° C. Then, 35.94 g (460.0 mmol) of 2-mercaptoethanol was added dropwise, and the mixture was stirred at 62° C. for 4 hours. The reaction mixture was then filtered, and the filtrate was concentrated, followed by the addition of 400.00 g of chloroform, followed by washing with water. The organic layer after washing was concentrated under reduced pressure to obtain 122.42 g of a pale yellow liquid (yield: 85.2%).

[0163] This pale yellow liquid 1 The H-NMR spectrum data was as follows: · 1 H-NMR (CDCl3) δ: 4.14(dd, 2H), 4.04(m, 4H), 3.73(q, 2H), 3.27(quin., 2H), 2.84(dd, 2H), 2.74(t, 2H), 2.70(dd, 2H), 2.61(t, 2H), 2.28(t, 1H), 1.97(quin., 2H). From this spectral data, the pale yellow liquid obtained is the title compound represented by the chemical formula (X). The compound was identified as 1,3-bis(oxiranylmethyl)-5-[[(2-hydroxyethyl)thio]propyl]isocyanurate.

[0164] [ka]

[0165] [Synthesis Example 2] <Synthesis of 1-oxiranylmethyl-3,5-bis[[(2-hydroxyethyl)thio]propyl]isocyanurate> A 1000 mL recovery flask was charged with 66.32 g (250.0 mmol) of 1-oxiranylmethyl-3,5-bis(2-propenyl)isocyanurate, 2.05 g (12.5 mmol) of 2,2'-azobis(isobutyronitrile), and 250.00 g of ethyl acetate, and the temperature was raised to 62° C. Then, 42.97 g (550.0 mmol) of 2-mercaptoethanol was added dropwise, and the mixture was stirred at 62° C. for 4 hours. The reaction mixture was then filtered, and the filtrate was concentrated, after which 300.00 g of chloroform was added and washed with water. The organic layer after washing was concentrated under reduced pressure to obtain 100.80 g of a pale yellow liquid (yield: 95.7%).

[0166] This pale yellow liquid 1 The H-NMR spectrum data was as follows: · 1 H-NMR (CDCl3) δ: 4.12(dd, 1H), 4.04(m, 5H), 3.73(q, 4H), 3.27(quin., 1H), 2.83(dd, 1H), 2.74(t, 4H), 2.70(dd, 1H), 2.61(t, 4H), 2.46(t, 2H), 1.98(quin., 4H). From this spectral data, the obtained pale yellow liquid is the title compound represented by chemical formula (XI). The compound was identified as 1-oxiranylmethyl-3,5-bis[[(2-hydroxyethyl)thio]propyl]isocyanurate.

[0167] [ka]

[0168] Example 1 <Synthesis of 1,3-bis(oxiranylmethyl)-5-[[(2-vinylcarbonyloxyethyl)thio]propyl]isocyanurate> A 1000 mL recovery flask was charged with 121.71 g (338.6 mmol) of 1,3-bis(oxiranylmethyl)-5-[[(2-hydroxyethyl)thio]propyl]isocyanurate and 580.00 g of chloroform, and after cooling to 0°C with ice, 41.11 g (406.3 mmol) of triethylamine and 33.71 g (372.5 mmol) of acryloyl chloride were added dropwise so that the internal temperature was 5°C or less. The temperature was then raised to 25°C and stirred for 6 hours. The reaction solution was concentrated, and then 400.00 g of chloroform was added, followed by washing with water. The organic layer after washing with water was concentrated under reduced pressure to obtain 131.59 g of a pale yellow liquid (yield: 94.0%).

[0169] This pale yellow liquid 1 The H-NMR spectrum data was as follows: · 1 H-NMR (CDCl3) δ: 6.42(d, 1H), 6.13(dd, 1H), 5.85(d, 1H), 4.30(t, 2H), 4.15(dd, 2H), 4.04(m, 4H), 3.26(quin., 2H), 2.81(dd, 2H), 2.79(t, 2H), 2.70(dd, 2H), 2.65(t, 2H), 1.98(quin., 2H). The IR spectrum data of the resulting pale yellow liquid was as shown in the chart in FIG. From these spectral data, the obtained pale yellow liquid was identified as the title compound represented by chemical formula (I-1).

[0170] Example 2 <Synthesis of 1-oxiranylmethyl-3,5-bis[[(2-vinylcarbonyloxyethyl)thio]propyl]isocyanurate> A 1000 mL recovery flask was charged with 99.85 g (236.9 mmol) of 1-oxiranylmethyl-3,5-bis[[(2-hydroxyethyl)thio]propyl]isocyanurate and 350.00 g of chloroform, and after cooling to 0°C with ice, 52.74 g (521.2 mmol) of triethylamine and 47.17 g (521.2 mmol) of acryloyl chloride were added dropwise so that the internal temperature was 5°C or less. The temperature was then raised to 25°C and stirred for 6 hours. The reaction solution was concentrated, and then 350.00 g of chloroform was added and washed with water. The organic layer after washing was concentrated under reduced pressure to obtain 106.52 g of a compound having a hydroxyl group represented by chemical formula (I-3) as a pale yellow liquid (yield: 84.9%).

[0171] This pale yellow liquid 1 The H-NMR spectrum data was as follows: · 1 H-NMR (CDCl3) δ: 6.42(d, 2H), 6.13(dd, 2H), 5.85(d, 2H), 4.32(t, 4H), 4.14(dd, 1H), 4.00(m, 5H), 3.25(quin., 1H), 2.80(dd, 1H), 2.78(t, 4H), 2.70(dd, 1H), 2.64(t, 4H), 1.97(quin., 4H). The IR spectrum data of the resulting pale yellow liquid was as shown in the chart in FIG. From these spectral data, the obtained pale yellow liquid was identified as the title compound represented by chemical formula (I-3). [Industrial Applicability]

[0172] The (meth)acrylate compound of the present invention has one or more -CH2CH2CH2SCH2(CH2) n OCOCR 3 Because it contains a =CH2 group, its use as a raw material or modifier (crosslinking agent) for photocurable and thermosetting resins is expected to produce polymers (cured products) with lower crosslinking density than those produced using conventional (meth)acrylate compounds, i.e., cured products with excellent flexibility, adhesion, heat resistance, moisture resistance, etc. In addition, because it contains an isocyanuric acid skeleton, it is expected to produce cured products with excellent transparency and weather resistance. Therefore, the present invention has great industrial applicability.

Claims

1. A (meth)acrylate compound represented by chemical formula (I): 【Chemical 1】 (In the formula, R １ or R ２ are the same or different and represent a glycidyl group or a group represented by formula (1). ３ represents a hydrogen atom or a methyl group, and n represents an integer of 1 to 3. 【Chemistry 2】 (In the formula, R ３ and n is the same as above.

2. 2. The method for synthesizing a (meth)acrylate compound according to claim 1, characterized in that an isocyanuric acid compound represented by chemical formula (II) is reacted with a thiol compound represented by chemical formula (III), and then a (meth)acryloyl halide represented by chemical formula (IV) or a (meth)acrylic anhydride represented by chemical formula (V) is reacted therewith. 【Chemistry 3】 (In the formula, R ４ or R ５ are the same or different and represent a glycidyl group or an allyl group.) 【Chemistry 4】 (wherein n is the same as defined above). 【Chemistry 5】 (In the formula, R ３ is the same as above. X represents a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. 【Chemistry 6】 (In the formula, R ３ are the same or different and represent a hydrogen atom or a methyl group.

3. A resin composition comprising the (meth)acrylate compound according to claim 1.

4. A cured product obtained by curing the resin composition according to claim 3.

5. An adhesive comprising the resin composition according to claim 3 as a component.

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