Curing resin composition

Abstract

The object of this invention is to provide a curable resin composition that achieves an excellent balance between curability and storage stability. This invention provides a curable resin composition comprising (A) an epoxy resin, (B) a curing agent, and (C) at least one imide compound selected from those represented by formulas (1-1), (1-2), and (1-3). Wherein, R... 11 R indicates alkyl groups, etc., that may have substituents and have 1 to 10 carbon atoms. 1 ~R 4 R represents hydrogen atoms, alkyl groups with 1 to 10 carbon atoms, etc., respectively. 12 and R 13 Each can be independently represented by a hydrogen atom, an alkyl group having 1 to 10 carbon atoms that may have substituents, etc.

Description

Technical Field

[0001] This invention relates to curable resin compositions, and more specifically, to curable resin compositions comprising an epoxy resin, a curing agent, and an imide compound having an aromatic ring structure. Background Technology

[0002] Epoxy resins are widely used in industry as components of coatings, adhesives, and various molding materials.

[0003] When epoxy resin is used for the above-mentioned purposes, it is usually used in combination with a curing agent. Various curing agents such as anhydride-based curing agents, amine-based curing agents, and phenol-based curing agents are known.

[0004] The above-mentioned curing agents are used separately according to their applications. For example, imidazole-based curing agents are different from addition-polymer curing agents. Since they are anionic polymeric curing agents, they can be cured by adding a small amount. In addition, they are useful for their low volatility and low toxicity, so they are suitable for use in electrical and electronic components.

[0005] However, when epoxy resin curing agents are used alone, it is difficult to achieve a balance between curing properties and storage stability. To improve storage stability, for example, Patent Document 1 proposes using the reaction product of imidazole compounds and epoxy resins in an epoxy group curing system, and Patent Document 2 proposes an epoxy resin curing agent composition formed from modified imidazole, modified amine, and phenol compounds.

[0006] However, under these various modifications, the viscosity of the modified material increased, and its handling and workability were impaired, resulting in unsatisfactory modified materials.

[0007] Existing technical documents

[0008] Patent documents

[0009] Patent Document 1: US Patent No. 4066625

[0010] Patent Document 2: Japanese Patent Application Publication No. 2007-297493

[0011] Non-patent literature

[0012] Non-patent literature 1: JORNAL OF POLYMER SCIENCE, PART A POLYMER CHEMISTRY 2016, 54, 2680-2688

[0013] Non-Patent Literature 2: JORNAL OF POLYMER SCIENCE, PART A POLYMER CHEMISTRY 2018, 56, 471-474

[0014] Non-patent literature 3: Composits Part B 17(2019)107380

[0015] Non-patent literature 4: Materials Leters 234(2019)379-383 Summary of the Invention

[0016] Therefore, the problem to be solved by the present invention is to provide a curable resin composition that has an excellent balance between curability and storage stability.

[0017] The inventors conducted in-depth research and found that the curable resin composition containing epoxy resin, curing agent, and specific imide compound has an excellent balance between curability and storage stability, thus completing the present invention.

[0018] That is, the present invention is a curable resin composition, wherein it contains (A) an epoxy resin, (B) a curing agent, and (C) at least one of an imide compound selected from the following formulas (1-1), (1-2) and (1-3).

[0019] [Chemical Formula 1]

[0020]

[0021] In the formula, R 11 This indicates an alkyl group having 1 to 10 carbon atoms that may have substituents, an aryl group having 6 to 20 carbon atoms that may have substituents, or an arylalkyl group having 7 to 20 carbon atoms that may have substituents.

[0022] R 1 ~R 4 Each of the following can independently represent a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, a haloalkyl group with 1 to 10 carbon atoms, a haloalkoxy group with 1 to 10 carbon atoms, an alkoxycarbonyl group with 2 to 10 carbon atoms, a halogen atom, a nitro group, a nitrile group, an amino group, or a glycidyloxy group.

[0023] R 12 and R 13 Each of the following can be independently represented: a hydrogen atom, an alkyl group having 1 to 10 carbon atoms that may have substituents, an aryl group having 6 to 20 carbon atoms that may have substituents, or an arylalkyl group having 7 to 20 carbon atoms that may have substituents.

[0024] The above-mentioned substituents are alkyl groups with 1 to 10 carbon atoms, alkoxy groups with 1 to 10 carbon atoms, haloalkyl groups with 1 to 10 carbon atoms, haloalkoxy groups with 1 to 10 carbon atoms, halogen atoms, nitro groups, nitrile groups, amino groups, or glycidoxy groups.

[0025] Invention Effects

[0026] According to the present invention, a curable resin composition with excellent curability and excellent storage stability can be provided. The curable resin composition of the present invention is suitable for use as a single-component curable resin composition. Detailed Implementation

[0027] The curable resin composition of the present invention will be described below.

[0028] The curable resin composition of the present invention contains (A) an epoxy resin, (B) a curing agent, and (C) a specific imide compound.

[0029] As for the epoxy resin used as component (A), it is sufficient that it has at least two epoxy groups in the molecule, and there are no particular restrictions on its molecular structure, molecular weight, etc.

[0030] Examples of epoxy resins mentioned above include polyglycidyl ethers of mononuclear polyphenolic compounds such as hydroquinone, resorcinol, pyrocatechol, and phloroglucinol; dihydroxynaphthalene, biphenol, methylene bisphenol (bisphenol F), methylene bis(o-cresol), ethylidene bisphenol, isopropylidene bisphenol (bisphenol A), isopropylidene bis(o-cresol), tetrabromobisphenol A, 1,3-bis(4-hydroxycumylbenzene), 1,4-bis(4-hydroxycumylbenzene), 1,1,3-tris(4-hydroxyphenyl)butane, 1,1,2,2-tetra(4-hydroxyphenyl)ethane, thiobisphenol, sulfonylbisphenol, oxobisphenol, phenolic varnish, o-cresol varnish, and ethylbenzene. Polyglycidyl ethers of polynuclear polyphenolic compounds such as phenolic varnish, butylphenol varnish, octylphenol varnish, resorcinol varnish, and terpene phenols; polyglycidyl ethers of polyol compounds such as ethylene glycol, propylene glycol, butanediol, hexanediol, polyethylene glycol, polypropylene glycol, thioglycol, dicyclopentadienedimethylethanol, 2,2-bis(4-hydroxycyclohexyl)propane (hydrogenated bisphenol A), glycerol, trimethylolpropane, pentaerythritol, sorbitol, and bisphenol A-epoxide alkane adducts; polyglycidyl ethers of polyol compounds such as maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, octanoic acid, adipic acid, azelaic acid, sebacic acid, dimeric acid, trimeric acid, and phthalic acid. Glycidyl esters of aliphatic, aromatic, or alicyclic polyacids such as isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, pyromellitic tetracarboxylic acid, tetrahydrophthalic acid, and bridged methylenetetrahydrophthalic acid, as well as homopolymers or copolymers of glycidyl methacrylate; N,N-diglycidylaniline, bis(4-(N-methyl-N-glycidylamino)phenyl)methane, diglycidyl o-toluidine, N,N-bis(2,3-epoxypropyl)-4-(2,3-epoxypropoxy)-2-methylaniline, N,N-bis(2,3-epoxypropyl)-4-(2,3-epoxypropoxy)aniline, and... Epoxy compounds containing glycidyl amino groups, such as N,N,N',N'-tetratetra(2,3-epoxypropyl)-4,4-diaminodiphenylmethane; epoxides of cyclic olefin compounds, such as vinylcyclohexene diepoxide, cyclopentadiene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6-methylcyclohexane carboxylate, and bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate; epoxidized conjugated diene polymers, such as epoxidized polybutadiene and epoxidized styrene-butadiene copolymers; and heterocyclic compounds, such as triglycidyl isocyanurate. Furthermore, these epoxy resins can also be used in the form of internal crosslinking via prepolymers with terminal isocyanates, or in the form of high molecular weight via polyvalent active hydrogen compounds (polyphenols, polyamines, carbonyl-containing compounds, polyphosphates, etc.). Epoxy resins can be used alone or in combination of two or more.

[0031] As an epoxy resin, polyglycidyl ethers of polyphenolic compounds or their high molecular weight derivatives are preferred, and polyglycidyl ethers of bisphenols such as bisphenol A and bisphenol F or their high molecular weight derivatives are more preferred. In particular, liquid epoxy resins can yield single-component curable resin compositions, and are therefore preferred.

[0032] As component (B), namely curing agent, examples include anhydride-based curing agents, phenol-based curing agents, amine-based curing agents, polythiol-based curing agents, and imidazole-based curing agents.

[0033] Examples of anhydride-based curing agents include norbornene, phthalic anhydride, maleic anhydride, methyl norbornene, succinic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, benzophenone tetracarboxylic anhydride, trimellitic anhydride, pyromellitic tetracarboxylic anhydride, and hydrogenated methylnadic anhydride.

[0034] Examples of phenolic curing agents include phenolic varnish resin, cresol varnish resin, aromatic hydrocarbon formaldehyde resin modified phenolic resin, dicyclopentadiene phenol addition resin, phenol aralkyl resin (Xyloc resin), naphthol aralkyl resin, trisphenylol methane resin, tetraphenylol ethane resin, naphthol varnish resin, naphthol-phenol cocondensed phenolic varnish resin, naphthol-cresol cocondensed phenolic varnish resin, biphenyl modified phenolic resin (a polyphenolic compound in which the phenolic nucleus is linked by dimethylene groups), biphenyl modified naphthol resin (a polyphenolic compound in which the phenolic nucleus is linked by dimethylene groups), aminotriazine modified phenolic resin (a compound in which the molecular structure has a phenol skeleton, a triazine ring and a primary amino group), and alkoxy-containing aromatic ring modified phenolic varnish resin (a polyphenolic compound in which the phenolic nucleus and an alkoxy-containing aromatic ring are linked by formaldehyde).

[0035] Examples of amine-based curing agents include alkylene diamines such as ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,3-diaminobutane, 1,4-diaminobutane, hexamethylenediamine, and m-xylenediamine; polyalkyl polyamines such as diethylenetriamine, triethylenetriamine, and tetraethylenepentamine; and 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 1,3-diaminomethylcyclohexane, 1,2-diaminocyclohexane, 1,4-diamino-3,6-diethylcyclohexane, 4,4'-diaminodicyclohexylmethane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 4,4'-diaminodicyclohexylpropane, and bis(4-aminocyclohexyl)cyclohexane. Alicyclic polyamines such as sulfone, 4,4'-diaminodicyclohexyl ether, 2,2'-dimethyl-4,4'-diaminodicyclohexylmethane, isophorone diamine, and norbornene diamine; aromatic polyamines such as diaminodiphenylmethane, diaminodiphenyl sulfone, diethyltoluene diamine, 1-methyl-3,5-diethyl-2,4-diaminobenzene, 1-methyl-3,5-diethyl-2,6-diaminobenzene, 1,3,5-triethyl-2,6-diaminobenzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, and 3,5,3',5'-tetramethyl-4,4'-diaminodiphenylmethane; and N,N-dimethylaminoethylamine, N,N-diethylaminoethylamine, and N,N-diisopropylaminoethylamine. Amines, N,N-diallylaminoethylamine, N,N-benzylmethylaminoethylamine, N,N-dibenzylaminoethylamine, N,N-cyclohexylmethylaminoethylamine, N,N-dicyclohexylaminoethylamine, N-(2-aminoethyl)pyrrolidine, N-(2-aminoethyl)piperidine, N-(2-aminoethyl)morpholine, N-(2-aminoethyl)piperazine, N-(2-aminoethyl)-N'-methylpiperazine, N,N-dimethylaminopropylamine, N,N-diethylaminopropylamine, N,N-diisopropylaminopropylamine, N,N-diallylaminopropylamine, N,N-benzylmethylaminopropylamine, N,N-dibenzylaminopropylamine, N,N-cyclohexylmethylaminopropylamine, N,N- Dicyclohexylaminopropylamine, N-(3-aminopropyl)pyrrolidine, N-(3-aminopropyl)piperidine, N-(3-aminopropyl)morpholine, N-(3-aminopropyl)piperazine, N-(3-aminopropyl)-N'-methylpiperidine, 4-(N,N-dimethylamino)benzylamine, 4-(N,N-diethylamino)benzylamine, 4-(N,N-diisopropylamino)benzylamine, N,N'-dimethylisophorone diamine, N,N-dimethyldiaminocyclohexane, N,N,N'-trimethylethylenediamine, N'-ethyl-N,N-dimethylethylenediamine, N,N,N'-triethylethylenediamine, N'-ethyl-N,N-dimethylpropane diamine, N'-ethyl-N,N-dibenzylaminopropylamine;N,N-(diaminopropyl)-N-methylamine, N,N-diaminopropylethylamine, N,N-diaminopropylpropylamine, N,N-diaminopropylbutylamine, N,N-diaminopropylpentylamine, N,N-diaminopropylhexylamine, N,N-diaminopropyl-2-ethylhexylamine, N,N-diaminopropylcyclohexylamine, N,N-diaminopropylbenzylamine, N,N-diaminopropylallylamine, bis[3-(N,N-dimethylaminopropyl)] [Amines, bis[3-(N,N-diethylaminopropyl)]amine, bis[3-(N,N-diisopropylaminopropyl)]amine, bis[3-(N,N-dibutylaminopropyl)]amine; dicarboxylic acid dihydrazides such as oxalate dihydrazide, malonate dihydrazide, succinate dihydrazide, glutarate dihydrazide, adipic acid dihydrazide, octanoic acid dihydrazide, azelaic acid dihydrazide, sebacic acid dihydrazide, and phthalic acid dihydrazide; guanidine compounds such as dicyandiamide, benzoguanidine, and acetylguanidine; melamine, etc.

[0036] Alternatively, modified amine curing agents obtained by modifying the aforementioned amines can also be used. Examples of modification methods include dehydration condensation with carboxylic acids, addition reaction with epoxy resins, addition reaction with isocyanates, Michael addition reaction, Mannich reaction, condensation reaction with urea, and condensation reaction with ketones.

[0037] Carboxylic acids that can be used in the modification of the aforementioned amines include, for example, maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, octanoic acid, adipic acid, azelaic acid, sebacic acid, dimer acids, trimer acids, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, pyromellitic tetraphthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, and bridged methylenetetrahydrophthalic acid, as well as aliphatic, aromatic, or alicyclic polyacids.

[0038] Epoxy compounds that can be used in the modification of the above-mentioned amines include, for example, the epoxy compounds exemplified as the epoxy resin mentioned in component (A) above.

[0039] Examples of isocyanate compounds that can be used in the modification of the aforementioned amines include, for instance, aromatic diisocyanates such as 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane-4,4'-diisocyanate, phenyl diisocyanate, phenyl dimethyl diisocyanate, tetramethylphenyl diisocyanate, 1,5-naphthalene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, 3,3'-dimethyldiphenyl-4,4'-diisocyanate, dianisidine diisocyanate, and tetramethylphenyl diisocyanate; isophorone diisocyanate, dicyclohexylmethane- Alicyclic diisocyanates such as 4,4'-diisocyanate, trans-1,4-cyclohexyl diisocyanate, and norbornene diisocyanate; aliphatic diisocyanates such as tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4- and / or 2,4,4-trimethylhexamethylene diisocyanate, and lysine diisocyanate; isocyanurate trimers, biuret trimers, and trimethylolpropane adducts of the diisocyanates exemplified above; triphenylmethane triisocyanate, 1-methylbenzene-2,4,6-triisocyanate, and dimethyltriphenylmethane tetraisocyanate, etc. Furthermore, these isocyanate compounds can also be used in the form of modified carbodiimide-modified, isocyanurate-modified, biuret-modified, etc., or in the form of end-capped isocyanates capped by various end-capping agents.

[0040] Examples of polythiol-based curing agents include pentaerythritol tetra(3-mercaptopropionate), pentaerythritol tetra(mercaptoacetate), dipentaerythritol hexa(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptobutyrate), 1,3,4,6-tetra(2-mercaptoethyl)-1,3,4,6-tetraazaoctahydropentaden-2,5-dione, 1,3,5-tris(3-mercaptopropyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-, 4,7- or 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and 1,3,4,6-tetra(2-mercaptoethyl)glycourea.

[0041] Examples of imidazole-based curing agents include 2-methylimidazolium, 2-ethyl-4-methylimidazolium, 2-isopropylimidazolium, 2-undecylimidazolium, 2-heptadecanylimidazolium, 2-phenylimidazolium, 2-phenyl-4-methylimidazolium, 2-aminopropylimidazolium, 1-phenylmethyl-2-imidazolium, 1-phenylmethyl-2-ethyl-4-methylimidazolium, 1-phenylmethyl-2-phenylimidazolium, 1-butoxycarbonylethyl-2-methylimidazolium, and 1-butoxycarbonyl. 1-Butoxycarbonylethyl-2-phenylimidazolium, 1-(2-ethylhexyl)carbonylethyl-2-methylimidazolium, 1-(2-ethylhexyl)carbonylethyl-2-ethyl-4-methylimidazolium, 1-(2-ethylhexyl)carbonylethyl-2-phenylimidazolium, 1-octoxycarbonylethyl-2-methylimidazolium, 1-octoxycarbonylethyl-2-ethyl-4-methylimidazolium, 1-octoxycarbonylethyl-2-phenylimidazolium Hexanediol bis(2-methylimidazolyl ethane), hexanediol bis(2-ethyl-4-methylimidazolyl ethane), hexanediol bis(2-phenylimidazolyl ethane), decanediol bis(2-methylimidazolyl ethane), decanediol bis(2-ethyl-4-methylimidazolyl ethane), decanediol bis(2-phenylimidazolyl ethane), tricyclopentanediethanol bis(2-methylimidazolyl ethane), tricyclopentanediethanol bis(2-methylimidazolyl ethane) (2-Ethyl-4-methylimidazolyl ethane) ester, tricyclopentanediethanol·bis(2-phenylimidazolyl ethane) ester, 1-(2-hydroxynaphthylmethyl)-2-methylimidazol, 1-(2-hydroxynaphthylmethyl)-2-ethyl-4-methylimidazol, 1-(2-hydroxynaphthylmethyl)-2-phenylimidazol and imidazolium silanes (e.g., manufactured by Shikoku Chemical Industry; 2MUSIZ), etc., can also be used in the form of salts with trimellitic acid, isocyanuric acid and boron, etc. Furthermore, modified imidazolium-based curing agents obtained by modifying these imidazolium compounds in the same way as the aforementioned modified amine-based curing agents can also be used.

[0042] Commercially available products that can be used as curing agents as component (B) include, for example, Adeka Hardener EH-3636AS, Adeka Hardener EH-4351S (manufactured by ADEKA; dicyandiamide type latent curing agent), Adeka Hardener EH-5011S, Adeka Hardener EH-5046S (manufactured by ADEKA; imidazole type latent curing agent), Adeka Hardener EH-4357S, Adeka Hardener EH-5057P, Adeka Hardener EH-5057PK (manufactured by ADEKA; polyamine type latent curing agent), Amicure PN-23, Amicure PN-40 (manufactured by Ajinomoto Finetechno; amine adduct latent curing agent), Amicure VDH (manufactured by Ajinomoto Finetechno; hydrazide type latent curing agent), and Fujicure FXR-1020 (T&K). TOKA (latent curing agent), CUREZOL (Imidazole-based curing agent, manufactured by Shikoku Chemical Industry), TS-G (Polythiol-based curing agent, manufactured by Shikoku Chemical Industry), DPMP, PEMP (Polythiol-based curing agent, manufactured by SC Organic Chemicals), and PETG (Polythiol-based curing agent, manufactured by Starch Chemicals), etc.

[0043] Hardeners can be used alone or in combination of two or more.

[0044] In this invention, imidazole-based curing agents are preferred, especially unmodified compounds such as 2-methylimidazole and 2-ethyl-4-methylimidazole, which can be cured with relatively small amounts and can also act as curing accelerators when combined with other curing agents, and are therefore preferred.

[0045] The amount of component (B), i.e., the curing agent, is not particularly limited, but it is preferably 1 to 70 moles, more preferably 1 to 50 moles, and particularly preferably 3 to 30 moles, relative to 100 moles of epoxy resin as component (A). It should be noted that when component (A) and / or component (B) are substances with a molecular weight distribution, the above molar ratio refers to the molar ratio calculated based on the weight-average molecular weight determined by GPC.

[0046] In this invention, the above-mentioned curing agent can be used in combination with known epoxy resin curing accelerators as needed. Examples of curing accelerators include phosphine salts such as triphenylphosphine; phosphonium salts such as tetraphenylphosphonium bromide; amines such as benzyl dimethylamine and 2,4,6-tris(dimethylaminomethyl)phenol; quaternary ammonium salts such as trimethylammonium chloride; ureas such as 3-(p-chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-phenyl-1,1-dimethylurea, isophorone diisocyanate-dimethylurea, and toluene diisocyanate-dimethylurea; complexes of boron trifluoride with amines, and complexes of boron trifluoride with ether compounds, etc. These curing accelerators can be used alone or in combination of two or more. The content of the epoxy resin curing accelerator can be appropriately set according to the intended use of the curable resin composition without particular limitation.

[0047] (C) The imide compound is selected from at least one of the imide compounds represented by the following formulas (1-1), (1-2) and (1-3). By using an imide compound with such a structure, a curable resin composition with excellent curability and storage stability can be provided.

[0048] [Chemical Formula 2]

[0049]

[0050] In the formula, R 11 This indicates an alkyl group having 1 to 10 carbon atoms that may have substituents, an aryl group having 6 to 20 carbon atoms that may have substituents, or an arylalkyl group having 7 to 20 carbon atoms that may have substituents.

[0051] R 1 ~R 4 Each of the following can independently represent a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, a haloalkyl group with 1 to 10 carbon atoms, a haloalkoxy group with 1 to 10 carbon atoms, an alkoxycarbonyl group with 2 to 10 carbon atoms, a halogen atom, a nitro group, a nitrile group, an amino group, or a glycidyloxy group.

[0052] R 12 and R 13 Each of the following can be independently represented: a hydrogen atom, an alkyl group having 1 to 10 carbon atoms that may have substituents, an aryl group having 6 to 20 carbon atoms that may have substituents, or an arylalkyl group having 7 to 20 carbon atoms that may have substituents.

[0053] The above-mentioned substituents are alkyl groups with 1 to 10 carbon atoms, alkoxy groups with 1 to 10 carbon atoms, haloalkyl groups with 1 to 10 carbon atoms, haloalkoxy groups with 1 to 10 carbon atoms, halogen atoms, nitro groups, nitrile groups, amino groups, or glycidoxy groups.

[0054] Examples of alkyl groups having 1 to 10 carbon atoms in formulas (1-1), (1-2), and (1-3) include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, sec-pentyl, tert-pentyl, hexyl, heptyl, octyl, isooctyl, tert-octyl, 2-ethylhexyl, nonyl, isononyl, decyl, and isodecyl. Examples of alkoxy groups having 1 to 10 carbon atoms include methoxy, ethoxy, propoxy, isopropoxy, butoxy, pentoxy, hexoxy, heptoxy, octoxy, and 2-ethylhexoxy. Examples of aryl groups having 6 to 20 carbon atoms include phenyl, naphthyl, and anthracene. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. Furthermore, as arylalkyl groups with 7 to 20 carbon atoms, examples include groups with 7 to 20 carbon atoms whose structures are obtained by replacing one or more hydrogen atoms of the groups exemplified as alkyl groups with the groups exemplified as aryl groups. As haloalkyl and haloalkoxy groups with 1 to 10 carbon atoms, examples include groups whose structures are obtained by replacing part or all of the hydrogen atoms of the groups exemplified as alkyl and alkoxy groups with the halogen atoms. As alkoxycarbonyl groups with 2 to 10 carbon atoms, examples include groups whose structures have a carbonyl group bonded to the oxygen atom of the groups exemplified as alkoxy groups with 1 to 10 carbon atoms.

[0055] Of the compounds represented by formula (1-1) above, R is preferred. 11 Compounds that are groups represented by the following formula (A).

[0056] [Chemical Formula 3]

[0057]

[0058] In the formula, R 5 ~R 8 Each of the following groups independently represents a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, a haloalkyl group with 1 to 10 carbon atoms, a haloalkoxy group with 1 to 10 carbon atoms, a halogen atom, a nitro group, a nitrile group, an amino group, or a glycidoxy group, R. 14 The term represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms that may have substituents, an aryl group having 6 to 20 carbon atoms that may have substituents, or an arylalkyl group having 7 to 20 carbon atoms that may have substituents.

[0059] The above-mentioned substituents are alkyl groups with 1 to 10 carbon atoms, alkoxy groups with 1 to 10 carbon atoms, haloalkyl groups with 1 to 10 carbon atoms, haloalkoxy groups with 1 to 10 carbon atoms, halogen atoms, nitro groups, nitrile groups, amino groups, or glycidoxy groups.

[0060] R is the preferred choice 5 ~R8 For hydrogen atoms, R 14 Compounds that are alkyl, phenethyl, or phenyl compounds having 1 to 10 carbon atoms as substituents.

[0061] Examples of groups exemplified as alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, haloalkyl groups having 1 to 10 carbon atoms, haloalkoxy groups having 1 to 10 carbon atoms, aryl groups having 6 to 20 carbon atoms, and arylalkyl groups having 7 to 20 carbon atoms that may have substituents in formula (A) above are groups exemplified as those in formulas (1-1), (1-2), and (1-3) above.

[0062] Of the compounds represented by formulas (1-2) above, R is preferred. 12 Compounds that are alkyl groups having 1 to 10 carbon atoms, or phenyl groups having trifluoromethyl or methoxy as substituents.

[0063] Of the compounds represented by formulas (1-3) above, R is preferred. 1 ~R 4 It can be a hydrogen atom, methyl group, halogen atom, nitro or butoxycarbonyl group, R 13 Compounds that are alkyl groups having 1 to 10 carbon atoms, or phenyl groups having a methoxy group as a substituent.

[0064] The following shows more specific compounds of the imide compounds represented by the above formulas (1-1), (1-2) and (1-3).

[0065] [Chemical Formula 4]

[0066]

[0067] [Chemical Formula 5]

[0068]

[0069] [Chemical Formula 6]

[0070]

[0071] [Chemical Formula 7]

[0072]

[0073] [Chemical Formula 8]

[0074]

[0075] [Chemical Formula 9]

[0076]

[0077] [Chemical Formula 10]

[0078]

[0079] [Chemical Formula 11]

[0080]

[0081] [Chemical Formula 12]

[0082]

[0083] [Chemical Formula 13]

[0084]

[0085] [Chemical Formula 14]

[0086]

[0087] [Chemical Formula 15]

[0088]

[0089] [Chemical Formula 16]

[0090]

[0091] [Chemical Formula 17]

[0092]

[0093] [Chemical Formula 18]

[0094]

[0095] (C) There are no particular restrictions on the manufacturing method of the component, i.e., the imide compound, but there are, for example, methods that react in the following ways.

[0096] (1) A method for synthesizing an amino acid compound by reacting an acid anhydride with an amino-containing compound at a low temperature below 150°C, specifically 0–120°C, preferably 40–100°C, followed by an imidization reaction at a temperature of 100–200°C (thermal imidization).

[0097] (2) In the same manner as (1) above, an amide acid compound is synthesized, and then an imidizing reaction is carried out chemically using an imidizing agent such as acetic anhydride (chemical imidization).

[0098] (3) In the same manner as (1) above, an amide acid compound is synthesized, and then an imidization reaction is carried out by heating under reflux in an azeotropic dehydration solvent, with or without a catalyst (azeotropic dehydration ring-closing method).

[0099] Of these methods, method (1) is preferred.

[0100] Examples of acid anhydrides used in the manufacture of the aforementioned imide compounds include succinic anhydride, phthalic anhydride, 3-bromophthalic anhydride, 3-methylphthalic anhydride, 3-nitrophthalic anhydride, norbornene-2,3-dicarboxylic anhydride, and methylnorbornene-2,3-dicarboxylic anhydride. Examples of amino-containing compounds include methylamine, ethylamine, propylamine, isopropylamine, butylamine, isobutylamine, pentylamine, hexylamine, heptylamine, octylamine, 2-ethylhexylamine, nonylamine, decylamine, benzylamine, 2-phenylethylamine, aniline, p-methoxyaniline, and p-trifluoromethylaniline.

[0101] The above imidization reaction is preferably carried out in an organic solvent. There are no particular limitations on the organic solvent used, but examples include saturated hydrocarbons such as pentane, hexane, heptane, and cyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, dichloroethane, chlorobenzene, and dichlorobenzene; ethers such as diethyl ether, diisopropyl ether, 1,2-dimethoxyethane, bis(2-methoxyethyl) ether, 1,2-bis(2-methoxyethoxy)ethane, bis[2-(2-methoxyethoxy)ethyl] ether, tetrahydrofuran, 1,3-dioxane, 1,4-dioxane, and anisole; and phenol, o-chlorophenol, m-chlorophenol, and p-chlorophenol. Phenolic solvents such as chlorophenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, and 3,5-xylenol; amides such as N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dimethylmethoxyacetamide, and hexamethylphosphoramide; lactams such as N-methyl-2-pyrrolidone and N-methylcaprolactam; sulfur-containing solvents such as dimethyl sulfoxide, diphenyl sulfoxide, dimethyl sulfone, diphenyl sulfone, and sulfolane; and 1,3-dimethyl-2-imidazolium ketones. These organic solvents can be used alone or in combination of two or more.

[0102] There is no particular limitation on the amount of organic solvent used, but it is 1 to 10,000 parts by mass relative to the total of the acid anhydride and the amino-containing compound, preferably 10 to 500 parts by mass. The above imidization reaction is preferably carried out in solution after the raw materials are dissolved in the organic solvent, but it can also be carried out in a slurry state.

[0103] Imidization reactions can also be carried out in the presence of organic base catalysts or acid catalysts.

[0104] Examples of organic base catalysts include triethylamine, tributylamine, tripentylamine, N,N-dimethylaniline, N,N-diethylaniline, pyridine, α-picoline, β-picoline, γ-picoline, 2,4-dimethylpyridine, 2,6-dimethylpyridine, quinoline, and isoquinoline, but pyridine and γ-picoline are preferred. These organic base catalysts can be used alone or in combination of two or more.

[0105] Examples of suitable acid catalysts include inorganic acids such as hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, anhydrous sulfuric acid, nitric acid, phosphoric acid, phosphorous acid, phosphotungstic acid, and phosphomolybdic acid; sulfonic acids such as methanesulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, and p-toluenesulfonic acid; carboxylic acids such as acetic acid and oxalic acid; halocarboxylic acids such as chloroacetic acid, dichloroacetic acid, trichloroacetic acid, fluoroacetic acid, difluoroacetic acid, and trifluoroacetic acid; solid acids such as silica, alumina, and activated clay; and cation exchange resins. Sulfuric acid, phosphoric acid, and p-toluenesulfonic acid are particularly suitable. These acid catalysts can be used alone or in combination of two or more. Furthermore, these acid catalysts can also be salts of diamine compounds.

[0106] There is no particular limitation on the amount of catalyst used as long as the reaction rate is substantially increased, but it is 0.001 to 10 moles relative to the total of 1 mole of acid anhydride and amino-containing compound, preferably 0.005 to 5 moles, and more preferably 0.01 to 1 mole.

[0107] The combined reaction time for obtaining the amic acid compound and the imidization reaction varies depending on the type of raw materials used, the type of organic solvent, the type of catalyst, the type and amount of solvent used for azeotropic dehydration, and the reaction temperature, but as a standard, it is 1 to 24 hours, usually several hours. In direct thermal imidization, as a standard, the reaction is carried out until the amount of water distilled is essentially the theoretical amount.

[0108] There are no particular restrictions on the reaction pressure for obtaining the amic acid compound and the imidization reaction, but atmospheric pressure is usually sufficient. There are no particular restrictions on the reaction atmosphere, but air, nitrogen, helium, neon or argon atmospheres are usually preferred, with nitrogen and argon atmospheres being the least reactive gases.

[0109] There are no particular limitations on the method for separating the imide compound, which is the target substance, from the reaction mixture of acid anhydride and amino-containing compound. However, if the target substance precipitates from the reaction solvent, separation by filtration or centrifugation is sufficient. On the other hand, if the target substance is dissolved in the reaction solvent, separation by filtration or centrifugation is sufficient to precipitate it by distilling off the solvent under reduced pressure, adding a suitable unsuitable solvent to the reaction mixture, or discharging the reaction mixture into an unsuitable solvent.

[0110] When further purification of the separated imide compounds is required, purification can be carried out using methods known as conventional methods, such as distillation purification, recrystallization, column chromatography, sludge treatment, and activated carbon treatment.

[0111] The content of component (C), i.e., the imide compound, relative to 100 moles of component (B), is preferably 1 to 2000 moles, more preferably 10 to 1000 moles, and even more preferably 20 to 800 moles. When the content of the imide compound is less than 1 mole, the effect of imparting stability to the curable resin composition may not be obtained, and when it exceeds 2000 moles, it may have an adverse effect on curability.

[0112] The curable resin composition of the present invention may contain antioxidants such as phosphorus-based antioxidants, phenolic antioxidants, and sulfur-based antioxidants.

[0113] Examples of phosphorus-based antioxidants include triphenyl phosphite, tris(2,4-di-tert-butylphenyl) phosphite, tris(nonylphenyl) phosphite, tris(di-nonylphenyl) phosphite, tris(mono- and di-mixed nonylphenyl) phosphite, bis(2-tert-butyl-4,6-dimethylphenyl) ethyl phosphite, diphenyl acid phosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl) octyl phosphite, and diphenyl decyl phosphite. Phenyl diisodecyl phosphite, Tributyl phosphite, Tri(2-ethylhexyl) phosphite, Tridecyl phosphite, Trilauryl phosphite, Dibutyl phosphite, Dilauryl phosphite, Trilauryl trithiophosphite, Bis(neopentyl glycol)·1,4-cyclohexanedimethyl diphosphite, Bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, Bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, Distearate Pentaerythritol diphosphite, phenyl-4,4'-isopropylidene diphenol·pentaerythritol diphosphite, tetrakis(C12-15 mixed alkyl)-4,4'-isopropylidene diphenyl phosphite, bis[2,2'-methylenebis(4,6-dipentylphenyl)]·isopropylidene diphenyl phosphite, hydrogenated-4,4'-isopropylidene diphenol polyphosphite, bis(octylphenyl)·bis[4,4'-n-butylidene bis(2-tert-butyl-5-methylbenzene) Phenol)·1,6-hexanediol·diphosphite, tetra(tetrazyl)·4,4'-butylidene bis(2-tert-butyl-5-methylphenol)diphosphite, hexa(tetrazyl)·1,1,3-tris(2-methyl-5-tert-butyl-4-hydroxyphenyl)butane·triphosphonate, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 2-butyl-2-ethylpropanediol·2,4,6-tritert-butylphenol monophosphite, etc.

[0114] Examples of phenolic antioxidants include 2,6-di-tert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-di-tert-butyl-4-hydroxyphenyl)propionate, distearate (3,5-di-tert-butyl-4-hydroxybenzyl)phosphonate, tridecyl 3,5-di-tert-butyl-4-hydroxybenzyl thioacetate, thiodiethylene bis[(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and 4,4'-thiobis(6-tert-butyl-m-cresol). 2-Octylthio-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-s-triazine, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), bis[3,3-bis(4-hydroxy-3-tert-butylphenyl)butyrate] glycol ester, 4,4'-butylidene bis(4,6-di-tert-butylphenol), 2,2'-ethidene bis(4,6-di-tert-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, bis[2-tert-butyl-4- [Methyl-6-(2-hydroxy-3-tert-butyl-5-methylbenzyl)phenyl] terephthalate, 1,3,5-tris(2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,3,5-tris[(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxyethyl] isocyanuric acid Esters, tetra[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, 2-tert-butyl-4-methyl-6-(2-acryloyloxy-3-tert-butyl-5-methylbenzyl)phenol, 3,9-bis[2-(3-tert-butyl-4-hydroxy-5-methylhydrocinnamoyloxy)-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane] and triethylene glycol bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate], etc.

[0115] Examples of sulfur-based antioxidants include dialkyl thiodipropionates such as dilaurate, dimyristyl ester, myristyl stearate, and distearate of thiodipropionates, as well as β-alkyl mercaptopropionates of polyols such as pentaerythritol tetra(β-dodecyl mercaptopropionate).

[0116] The curable resin composition of the present invention may contain light stabilizers such as ultraviolet absorbers and hindered amine light stabilizers.

[0117] Examples of UV absorbers mentioned above include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 2-hydroxy-4-tert-butyl-4'-(2-methacryloyloxyethoxyethoxy)benzophenone, and 5,5'-methylenebis(2-hydroxy-4-methoxybenzophenone), etc.; 2-hydroxybenzophenones such as 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, and 2-(2-hydroxy-3-methylphenyl)benzotriazole. 5-Di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3-dodecyl-5-methylphenyl)benzotriazole, 2-(2-hydroxy-3-tert-butyl-5-C7-9 mixed alkoxycarbonylethylphenyl)triazole, 2-(2-hydroxy-3,5-dicumylphenyl)benzotriazole, 2,2'-methylenebis(4-tert-octyl-6-benzotriazolylphenol) and 2-(2-hydroxy-3-tert-butyl-5-carboxyphenyl) 2-(2-hydroxyphenyl)benzotriazoles, such as polyethylene glycol esters of benzotriazoles; 2-(2-hydroxy-4-hexyloxyphenyl)-4,6-diphenyl-1,3,5-triazine, 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine, and 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, etc., are 2-(2-hydroxyphenyl)-1,3,5-triazines; phenyl salicylate, resorcinol monobenzoate, 2,4-di... Benzoate esters such as tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2,4-di-tert-pentylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, and hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate; substituted oxaloanilines such as 2-ethyl-2'-ethoxyoxaloaniline and 2-ethoxy-4'-dodecyloxaloaniline; and cyanoacrylates such as ethyl-α-cyano-β,β-diphenylacrylate and methyl-2-cyano-3-methyl-3-(p-methoxyphenyl)acrylate.

[0118] Examples of hindered amine light stabilizers include 2,2,6,6-tetramethyl-4-piperidinyl stearate, 1,2,2,6,6-pentamethyl-4-piperidinyl stearate, 2,2,6,6-tetramethyl-4-piperidinyl benzoate, bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, tetra(2,2,6,6-tetramethyl-4-piperidinyl)-1,2,3,4-butanetetracarboxylate, and tetra(1,2,2,6,6-pentamethyl-4-piperidinyl)-1, 2,3,4-Butanetetracarboxylate, bis(2,2,6,6-tetramethyl-4-piperidinyl)·bis(tetranyl)-1,2,3,4-butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)·bis(tetranyl)-1,2,3,4-butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-2-butyl-2-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate condensate, 1,6-bis(2 2,6,6-Tetramethyl-4-piperidinylamino)hexane / dibromoethane condensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidinylamino)hexane / 2,4-dichloro-6-morpholino-s-triazine condensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidinylamino)hexane / 2,4-dichloro-6-tert-octylamino-s-triazine condensate, 1,5,8,12-tetra[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidinyl)amino)-s-triazin-6-yl]-1,5,8,12-tetraaza Dodecane, 1,5,8,12-tetra[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidinyl)amino)-s-triazin-6-yl]-1,5,8,12-tetraazadodecane, 1,6,11-tris[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidinyl)amino-s-triazin-6-ylamino]undecane, and 1,6,11-tris[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidinyl)amino-s-triazin-6-ylamino)]undecane, etc.

[0119] The curable resin composition of the present invention may contain a silane coupling agent.

[0120] Examples of silane coupling agents include γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-N'-β-(aminoethyl)-γ-aminopropyltriethoxysilane, γ-anilinepropyltriethoxysilane, γ-epoxypropoxypropyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, vinyltriethoxysilane, N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, and γ-mercaptopropyltrimethoxysilane.

[0121] The curable resin composition of the present invention may contain fillers.

[0122] Examples of fillers mentioned above include silica such as fused silica and crystalline silica; powders such as magnesium hydroxide, aluminum hydroxide, zinc molybdate, calcium carbonate, silicon carbonate, calcium silicate, potassium titanate, beryllium oxide, zircon, zircon, forsterite, block talc, spinel, mullite, and titanium dioxide, as well as beads obtained by spheroidizing them; and fibers such as glass fiber, pulp fiber, synthetic fiber, and ceramic fiber.

[0123] The curable resin composition of the present invention may contain various solvents, preferably organic solvents.

[0124] Examples of organic solvents mentioned above include ethers such as tetrahydrofuran, 1,2-dimethoxyethane, and 1,2-diethoxyethane; alcohols such as isobutanol, n-butanol, isopropanol, n-propanol, pentyl alcohol, benzyl alcohol, furfuryl alcohol, and tetrahydrofurfuryl alcohol; ketones such as methyl ethyl ketone, methyl isopropyl ketone, and methyl butyl ketone; aromatic hydrocarbons such as benzene, toluene, and xylene; and triethylamine, pyridine, dioxane, and acetonitrile.

[0125] The curable resin composition of the present invention may contain various other additives as needed.

[0126] Examples of additives include phenolic compounds such as biphenol; reactive diluents such as monoalkyl glycidyl ethers; non-reactive diluents (plasticizers) such as dioctyl phthalate, dibutyl phthalate, benzyl alcohol, and coal tar; reinforcing materials such as glass cloth, aramid cloth, and carbon fiber; pigments; lubricants such as candelilla wax, carnauba wax, wood wax, beeswax, lanolin, cetearyl wax, lignite wax, petroleum wax, aliphatic wax, aliphatic esters, aliphatic ethers, aromatic esters, and aromatic ethers; thickeners; thixotropic agents; defoamers; rust inhibitors; and commonly used additives such as colloidal silica and colloidal alumina. In this invention, adhesive resins such as cyanate ester resin, xylene resin, and petroleum resin may also be used in combination.

[0127] The curable resin composition of the present invention can be used as a single-component curable resin composition because it can balance curing properties and storage stability. There are no particular limitations on the applications of the curable resin composition of the present invention, but examples include adhesives for electronic components, sealing materials for electronic components, casting materials, coatings, and structural adhesives.

[0128] Example

[0129] Next, the present invention will be further described in detail through embodiments and comparative examples, but the present invention is not limited to these embodiments in any way.

[0130] [Examples 1-17]

[0131] A curable resin composition was prepared by using bisphenol A type epoxy resin (BISAEP) as component (A), 2-ethyl-4-methylimidazolium (2E4MZ) as component (B), and an imide compound exemplified as a specific example of an imide compound represented by formulas (1-1), (1-2), and (1-3) above as component (C) in the molar ratios shown in Table 1. When the imide compound had a high melting point, BISAEP and the corresponding imide compound were mixed in the stated amounts, heated to a temperature until a completely homogeneous liquid was formed, cooled to room temperature, and then a specified amount of 2E4MZ was added to produce the curable resin composition. The curability and storage stability of the obtained curable resin composition were evaluated. The results are shown in Table 1.

[0132] [Comparative Example 1]

[0133] Except for the absence of imide compounds, the curable resin compositions were prepared in the same manner as in Examples 1-17, and their curability and storage stability were evaluated. The results are shown in Table 1.

[0134] [Manufacturing of phenylmaleimide oligomers (PMI)]

[0135] 522.1 g of phenylmaleimide and 14.8 g of AIBN (azobisisobutyronitrile) were added to a two-necked flask. After N2 replacement, 3 ml of DMF was added for five degassing cycles. The reaction was then carried out by heating at 60 °C for 24 hours. After the reaction was completed, methanol was added, and the precipitate was filtered and dried under reduced pressure (60 °C, 6 h) to obtain PMI as the target compound (yield: 0.2865 g, 55%).

[0136] GPC (solvent DMF (10mM LiBr)): Mn = 3.5 × 10⁻⁶ 3 Mw = 5.6 × 10 3Mw / Mn = 1.58

[0137] [Comparative Example 2]

[0138] Except for using PMI to replace the imide compound, the curable resin compositions were prepared in the same manner as in Examples 1-17, and their curability and storage stability were evaluated. The results are shown in Table 1.

[0139] <Curing properties>

[0140] Place the curing resin composition into a glass bottle and heat it at 150°C for 1 hour. Set the composition that is confirmed to be non-sticky and completely solid as 0, and set the composition that is not like this as ×.

[0141] Storage stability

[0142] Add one-fifth of the cured resin composition from the bottom up to a glass bottle with a diameter of 13 mm and a length of 40 mm, and cap the bottle. Tilt the bottle 90° on a platform and observe its condition after 1 minute to confirm its fluidity. A change in the shape of the cured resin composition is defined as fluidity, and no change is defined as non-fluidity. Evaluation is performed every day, ending when fluidity disappears. The number of days fluidity is maintained is shown in Table 1. If fluidity is maintained for more than 3 days, storage stability is considered acceptable (〇); otherwise, storage stability is considered unacceptable (×).

[0143]

[0144] As shown in Table 1, it is evident that the curable resin compositions of this invention containing specific imide compounds exhibit excellent curability and storage stability.

[0145] Industrial availability

[0146] According to the present invention, in particular due to its excellent curing properties and storage stability, it is possible to provide single-component curable resin compositions, which are suitable for use, for example, in electronic component adhesives, electronic component sealing materials, casting materials, coatings, structural adhesives, etc.

Claims

1. A curable resin composition comprising (A) an epoxy resin, (B) a curing agent, and (C) at least one imide compound selected from those represented by formulas (1-1), (1-2), and (1-3). In the formula, R 11 This indicates an alkyl group having 1 to 10 carbon atoms that may have substituents, an aryl group having 6 to 20 carbon atoms that may have substituents, or an arylalkyl group having 7 to 20 carbon atoms that may have substituents. R 1 ~R 4 Each of the following can independently represent a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, a haloalkyl group with 1 to 10 carbon atoms, a haloalkoxy group with 1 to 10 carbon atoms, an alkoxycarbonyl group with 2 to 10 carbon atoms, a halogen atom, a nitro group, a nitrile group, an amino group, or a glycidyloxy group. R 12 and R 13 Each of the following can be independently represented: a hydrogen atom, an alkyl group having 1 to 10 carbon atoms that may have substituents, an aryl group having 6 to 20 carbon atoms that may have substituents, or an arylalkyl group having 7 to 20 carbon atoms that may have substituents. The substituent is an alkyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, a haloalkyl group with 1 to 10 carbon atoms, a haloalkoxy group with 1 to 10 carbon atoms, a halogen atom, a nitro group, a nitrile group, or an amino group.

2. The curable resin composition according to claim 1, wherein, The curing agent used as component (B) contains an imidazole-based curing agent.

3. The curable resin composition according to claim 1 or 2, wherein, The content of the curing agent as component (B) is 0.01 to 100 moles relative to 100 moles of epoxy resin as component (A).

4. The curable resin composition according to claim 1 or 2, wherein, The content of the imide compound as component (C) is 1 to 2000 moles relative to 100 moles of the curing agent as component (B).

5. The curable resin composition according to claim 1 or 2, wherein it is a single-component curing type.

6. The cured product of the curable resin composition according to any one of claims 1 to 5.

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