Curable resin composition, cured product, and adhesive

Abstract

A curable resin composition that contains (A) a cyanate ester resin, (B) an epoxy resin, (C) an active hydrogen–containing amine latent curing agent, and (D) an ion scavenger. The (A) cyanate ester resin is preferably one type of compound selected from the group that consists of compounds represented by formula (1), compounds represented by formula (2), and polymers of at least one type of compound selected therefrom. (1) NC-O-A1-Y1-A2-O-CN (See the description for the symbols in the formula.) (2) (See the description for the symbols in the formula.)

Description

[Technical Field]

[0001] The present invention relates to a curable resin composition, and more particularly to a curable resin composition containing a cyanate ester resin, an epoxy resin, a latent curing agent, and an ion scavenger. [Background technology]

[0002] Epoxy resins are widely used industrially as coating materials, adhesives, various molding materials, and the like.

[0003] Furthermore, when existing epoxy resins, when used alone or in combination, are insufficient in terms of properties such as curing speed and heat resistance, cyanate-epoxy composite resin compositions, which are mixtures of epoxy resins and cyanate ester resins, have come to be widely used as useful materials with fast curing and high heat resistance (see, for example, Patent Documents 1 to 5).

[0004] On the other hand, Patent Document 6 and the like disclose resin compositions containing ion scavengers, but do not disclose their use in cyanate-epoxy composite resin compositions. Patent Document 7 describes an insulating adhesive obtained by combining an epoxy resin, a cyanate ester-based curing agent, and an inorganic ion exchange agent, but does not suggest the use of an amine-based latent curing agent containing active hydrogen in combination. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] U.S. Patent No. 6,469,074 [Patent Document 2] Japanese Patent Application Publication No. 60-250026 [Patent Document 3] U.S. Patent No. 6,342,577 [Patent Document 4] US Patent Application Publication No. 2012 / 178853 [Patent Document 5] US Patent Application Publication No. 2012 / 309923 [Patent Document 6] US Patent Application Publication No. 2019 / 031790 [Patent Document 7] Japanese Patent Application Laid-Open No. 2017-103332 Summary of the Invention

[0006] Cured products of the cyanate-epoxy resin compositions described in Patent Documents 1 to 5 may become cloudy under high-temperature and high-humidity conditions, which is particularly problematic when the cyanate-epoxy resin composition is used as an adhesive for optical components such as lenses. Patent Documents 6 and 7 do not take anti-fogging properties into consideration. In particular, as described in Patent Document 7, a curing system that uses an epoxy resin and a cyanate ester-based curing agent without an amine-based latent curing agent containing active hydrogen is insufficient in curing properties and requires curing at high temperatures, making it unsuitable for applications such as adhesives.

[0007] Therefore, an object of the present invention is to provide a curable resin composition that has excellent curability and that can give a cured product that has excellent anti-fogging properties even when placed under high temperature and high humidity conditions.

[0008] The present inventors have conducted extensive research and found that the above-mentioned object can be achieved by a curable resin composition containing a cyanate ester resin, an epoxy resin, an amine-based latent curing agent containing active hydrogen, and an ion scavenger, and have arrived at the present invention.

[0009] That is, the present invention provides a curable resin composition containing (A) a cyanate ester resin, (B) an epoxy resin, (C) an amine-based latent curing agent containing active hydrogen, and (D) an ion scavenger.

[0010] The present invention also provides a cured product of the curable resin composition and an adhesive containing the curable resin composition. DETAILED DESCRIPTION OF THE INVENTION

[0011] The curable resin composition of the present invention will be described below. The present inventors speculated that the cause of cloudiness in cyanate-epoxy curable resin compositions is the precipitation of components produced by the reaction of components resulting from the decomposition of adhesive components in a high-temperature, high-humidity environment with silicon, sodium, etc. derived from glass. They then considered that the components produced by the decomposition of a cured product of a cyanate-epoxy curable resin composition in a high-temperature, high-humidity environment could be captured by an ion scavenger, and arrived at the use of an ion scavenger in a specific formulation containing a cyanate-epoxy resin composition.

[0012] The cyanate ester resin, which is the component (A) used in the present invention, is a compound having two or more cyanate groups, and can be used without any particular restrictions on the molecular structure, molecular weight, etc.

[0013] The cyanate ester resin of component (A) may be, for example, one or more selected from the group consisting of compounds represented by the following formula (1), compounds represented by the following formula (2), and at least one polymer selected from the compounds represented by formula (1) and formula (2). The polymer referred to here is also referred to as a prepolymer.

[0014] NC-OA 1 -Y 1 -A 2 -O-CN (1) (Y in the formula 1 represents a divalent hydrocarbon group that is unsubstituted or substituted with a fluorine atom or a cyanato group, or represents -O-, -S-, or a single bond; A 1 and A 2 are each independently an unsubstituted phenylene group or a phenylene group in which 1 to 4 hydrogen atoms on the ring are substituted with alkyl groups.

[0015] [ka] (wherein m is an integer of 1 or more, and Y2 and Y 3 R each independently represents -S- or a divalent hydrocarbon group that is unsubstituted or substituted with a fluorine atom or a cyanato group. 1 ~R 6 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[0016] In this specification, examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a s-butyl group, and a t-butyl group.

[0017] A in equation (1) 1 and A 2 When a hydrogen atom on the ring of the phenylene group represented by the following formula is substituted with an alkyl group, the alkyl group may be an alkyl group having 1 to 4 carbon atoms.

[0018] Y in the formula (1) 1 And Y in the formula (2) 2 and Y 3 The unsubstituted or fluorine atom-substituted divalent hydrocarbon group represented by the formula (1) preferably includes those having 1 to 20 carbon atoms. 1 And Y in the formula (2) 2 and Y 3 As the compound, those having a structure represented by any one of the following formulas (Y-1) to (Y-9) are preferred because they are easily available.

[0019] [ka] where n is an integer from 4 to 12, and R 7 and R 8 are each independently a hydrogen atom or an unsubstituted or fluorine-substituted methyl group. * represents a bond.

[0020] Among the cyanate ester resins, bisphenol E type cyanate ester resins, biphenyl type, novolak phenol type, bisphenol A type, and other cyanate ester resins are preferred because they can provide a cured product with excellent heat resistance. Bisphenol type cyanate ester resins such as bisphenol E type and bisphenol A type are cyanate ester resins represented by the formula (1) above, 1 The biphenyl-type cyanate ester resin may be a resin represented by the formula (1) where Y 1 The novolak phenol type cyanate ester resin is a resin in which Y 2 and Y 3 are each independently (Y-1).

[0021] From the viewpoint of heat resistance, bisphenol type, biphenyl type or novolac phenol type Noshi When a cyanate ester resin is used, it is preferable that bisphenol-, biphenyl-, or novolac phenol-type cyanate ester resins account for 80% by mass or more of the total cyanate ester resins, and more preferably 90% by mass or more of the bisphenol-, biphenyl-, or novolac phenol-type cyanate ester resins. In particular, in the present invention, it is preferable that bisphenol-type cyanate ester resins account for 80% by mass or more of the total cyanate ester resins, more preferably 90% by mass or more of the bisphenol-type cyanate ester resins, and particularly preferably 95% by mass or more of the bisphenol-type cyanate ester resins.

[0022] From the viewpoint of the balance between curability and storage stability, the content of the cyanate ester resin is more preferably 5 to 80 parts by mass, and particularly preferably 10 to 60 parts by mass, per 100 parts by mass of the solid content of the composition. The solid content refers to the total amount of all components other than the solvent. The curable resin composition may or may not contain a solvent, but if it does contain a solvent, its content is preferably 5% by mass or less, and more preferably 2% by mass or less, of the curable resin composition.

[0023] The epoxy resin used as component (B) in the present invention has at least two epoxy groups in the molecule, and can be used without any particular restrictions on the molecular structure, molecular weight, etc.

[0024] Examples of the epoxy resin include polyglycidyl ether compounds of mononuclear polyhydric phenol compounds such as hydroquinone, resorcinol, pyrocatechol, and phloroglucinol; and polynuclear polyhydric phenols such as dihydroxynaphthalene, biphenol, methylene bisphenol (bisphenol F), methylene bis(ortho-cresol), ethylidene bisphenol, isopropylidene bisphenol (bisphenol A), isopropylidene bis(ortho-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, sulfobisphenol, oxybisphenol, phenol novolac, orthocresol novolac, ethylphenol novolac, butylphenol novolac, octylphenol novolac, resorcinol novolac, and terpene phenols. polyglycidyl ether compounds of polyhydric phenol compounds; polyglycidyl ether compounds of polyhydric alcohol compounds such as ethylene glycol, propylene glycol, butylene glycol, hexanediol, polyethylene glycol, polypropylene glycol, thioglycol, dicyclopentadiene dimethanol, 2,2-bis(4-hydroxycyclohexyl)propane (hydrogenated bisphenol A), glycerin, trimethylolpropane, pentaerythritol, sorbitol, and bisphenol A-alkylene oxide adducts; glycidyl ester compounds of aliphatic, aromatic, or alicyclic polybasic acids such as maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, suberic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, trimer acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, and endomethylenetetrahydrophthalic acid, and homopolymers or copolymers of glycidyl methacrylate;Epoxy compounds having a glycidylamino group such as N,N-diglycidylaniline, bis(4-(N-methyl-N-glycidylamino)phenyl)methane, diglycidyl orthotoluidine, N,N-bis(2,3-epoxypropyl)-4-(2,3-epoxypropoxy)-2-methylaniline, N,N-bis(2,3-epoxypropyl)-4-(2,3-epoxypropoxy)aniline, and N,N,N',N'-tetra(2,3-epoxypropyl)-4,4-diaminodiphenylmethane; vinylcyclohexene diepoxide, Examples of epoxy resins include epoxidized cyclic olefin compounds such as cyclopentanediene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6-methylcyclohexanecarboxylate, 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. These epoxy resins may be internally crosslinked with a terminal isocyanate prepolymer or may be polymerized with a polyvalent active hydrogen compound (such as a polyphenol, polyamine, carbonyl group-containing compound, or polyphosphate ester). These epoxy resins may be used alone or in combination of two or more.

[0025] Among the epoxy resins, from the viewpoint of reactivity, it is preferable to have a glycidyl-type epoxy resin having a glycidyl group, and in particular, it is preferable to contain one or more of a polyglycidyl ether compound of a polynuclear polyhydric phenol compound, an epoxy compound having a glycidylamino group, and a polyglycidyl ether compound of dicyclopentadiene dimethanol (specifically, a diglycidyl ether compound). The inclusion of a polyglycidyl ether compound of a polynuclear polyhydric phenol compound is preferable in terms of heat resistance. The inclusion of an epoxy compound having a glycidylamino group is preferable in terms of both excellent reactivity and excellent heat resistance. The inclusion of a polyglycidyl ether compound of dicyclopentadiene dimethanol is preferable in terms of the effect of imparting adhesion. In this specification, the term "glycidylamino group" may be monofunctional or bifunctional, but preferably refers to the difunctional "diglycidylamino group." All of the preferred numerical ranges of the amount of the "epoxy compound having a glycidylamino group" in this specification can be considered to be preferred numerical ranges of the amount of the "epoxy compound having a diglycidylamino group."

[0026] The epoxy resin (B) preferably has 1.1 or more and 10 or less epoxy groups in one molecule, and more preferably 2 or more and 4 or less, for excellent heat resistance and one-component stability.

[0027] The epoxy equivalent (g / eq) of the epoxy resin of component (B) is preferably 50 or more from the viewpoint of heat resistance, more preferably 60 or more and 30,000 or less, and even more preferably 70 or more and 20,000 or less.

[0028] The epoxy resin of component (B) preferably has a molecular weight of 150 or more and 80,000 or less in terms of heat resistance, and more preferably 200 or more and 10,000 or less. When the epoxy resin is a polymer, the molecular weight can be measured as a weight average molecular weight, and can be measured by the following method. The weight average molecular weight can be determined, for example, by GPC (gel permeation chromatography) measurement as a value converted into standard polystyrene, and can be measured, for example, under the following conditions. The weight-average molecular weight can be measured using, for example, a GPC (LC-2000plus series) manufactured by JASCO Corporation, using tetrahydrofuran as the elution solvent, polystyrene standards for calibration curves of Mw 1,110,000, 707,000, 397,000, 189,000, 98,900, 37,200, 13,700, 9,490, 5,430, 3,120, 1,010, and 589 (TSKgel standard polystyrene manufactured by Tosoh Corporation), and measurement columns KF-804, KF-803, and KF-802 (manufactured by Showa Denko K.K.). The measurement temperature can be 40°C, and the flow rate can be 1.0 mL / min.

[0029] The amount of the epoxy resin as component (B) used is preferably 1 to 1000 parts by mass, more preferably 3 to 500 parts by mass, and even more preferably 5 to 200 parts by mass, relative to 100 parts by mass of the cyanate ester resin as component (A), in order to obtain excellent physical properties of the cured product.

[0030] In the present invention, when an epoxy compound having a glycidyl group is contained as component (B), the content ratio of the compound relative to 100 parts by mass of the epoxy resin (B) is preferably 80 parts by mass or more and 100 parts by mass or less, and more preferably 95 parts by mass or more and 100 parts by mass or less.

[0031] In the present invention, when a polyglycidyl ether compound of a polynuclear polyhydric phenol compound is contained as component (B), the content ratio of the compound relative to 100 parts by mass of the epoxy resin (B) is preferably 10 parts by mass or more and 90 parts by mass or less, and more preferably 20 parts by mass or more and 80 parts by mass or less.

[0032] In the present invention, when an epoxy compound having a glycidylamino group is contained as component (B), the content of the compound relative to 100 parts by mass of the epoxy resin (B) is preferably 5 parts by mass or more, more preferably 10 parts by mass or more and 80 parts by mass or less, and particularly preferably 20 parts by mass or more and 80 parts by mass or less.

[0033] In the present invention, when a polyglycidyl ether compound of dicyclopentadiene dimethanol is contained as component (B), the content of the compound relative to 100 parts by mass of the epoxy resin (B) is preferably 5 parts by mass or more, more preferably 10 parts by mass or more and 80 parts by mass or less, and more preferably 15 parts by mass or more and 80 parts by mass or less.

[0034] In the present invention, by using an amine-based latent curing agent having active hydrogen as the curing agent, the effect of excellent reactivity and one-component stability is achieved. Examples of the amine-based latent curing agent having active hydrogen, which is the component (C) used in the present invention, include dibasic acid dihydrazides such as oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, suberic acid dihydrazide, azelaic acid dihydrazide, sebacic acid dihydrazide, and phthalic acid dihydrazide; guanidine compounds such as dicyandiamide, benzoguanamine, and acetoguanamine; melamine; and modified amines such as dehydration condensates of amine and carboxylic acid, adducts of amine and epoxy, adducts of amine and isocyanate, Michael adducts of amine, Mannich reaction products of amine, condensates of amine and urea, and condensates of amine and ketone.

[0035] Among the amine-based latent curing agents having active hydrogen, preferred examples include guanidine compounds such as dicyandiamide, benzoguanamine, and acetoguanamine; or (C-1) modified amines obtained by reacting an amine compound having one or more active hydrogens with an epoxy compound, (C-2) modified amines obtained by reacting an amine compound having one or more active hydrogens with an isocyanate compound, (C-3) modified amines obtained by reacting an amine compound having one or more active hydrogens with an epoxy compound and an isocyanate compound, and (C-4) latent curing agents containing a phenolic resin in addition to at least one modified amine selected from (C-1), (C-2), or (C-3).

[0036] Examples of the amine compound having one or more active hydrogens include alkylenediamines such as ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,3-diaminobutane, 1,4-diaminobutane, and hexamethylenediamine; polyalkylpolyamines such as diethylenetriamine, triethylenetriamine, and tetraethylenepentamine; 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 1,3-diaminomethylcyclohexane, 1,2-diaminocyclohexane, and 1, Alicyclic polyamines such as 4-diamino-3,6-diethylcyclohexane, 4,4'-diaminodicyclohexylmethane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 4,4'-diaminodicyclohexylpropane, bis(4-aminocyclohexyl)sulfone, 4,4'-diaminodicyclohexyl ether, 2,2'-dimethyl-4,4'-diaminodicyclohexylmethane, isophoronediamine, and norbornenediamine; m-xylylenediamine, diamino Aromatic polyamines such as diphenylmethane, diaminodiphenyl sulfone, diethyltoluenediamine, 1-methyl-3,5-diethyl-2,4-diaminebenzene, 1-methyl-3,5-diethyl-2,6-diaminobenzene, 1,3,5-triethyl-2,6-diaminobenzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,5,3',5'-tetramethyl-4,4'-diaminodiphenylmethane, etc.; guanamines such as benzoguanamine and acetoguanamine; 2-methylimidazole, 2 Imidazoles such as 2-ethyl-4-methylimidazole, 2-isopropylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and 2-aminopropylimidazole; dihydrazides such as oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, suberic acid dihydrazide, azelaic acid dihydrazide, sebacic acid dihydrazide, and phthalic acid dihydrazide;N,N-Dimethylaminoethylamine, N,N-Diethylaminoethylamine, N,N-Diisopropylaminoethylamine, 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-Diisopropylaminoethylamine isopropylaminopropylamine, 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-Dimethylisophoronediamine, N,N-dimethylbisaminocyclohexane, N,N,N'-trimethylethylenediamine, N'-ethyl-N,N-dimethylethylenediamine, N,N,N'-trimethylethylenediamine, N'-ethyl-N,N-dimethylpropanediamine, N'-ethyl-N,N-dibenzylaminopropylamine; N,N-(bisaminopropyl)-N-methylamine, N,N-bisaminopropylethylamine, N,N-bisaminopropylpropylamine, N,N-bisaminopropylbutylamine, N,N-bisaminopropyl aminopropyl pentylamine, N,N-bisaminopropyl hexylamine, N,N-bisaminopropyl-2-ethylhexylamine, N,N-bisaminopropyl cyclohexylamine, N,N-bisaminopropyl benzylamine, N,N-bisaminopropyl allylamine, bis[3-(N,N-dimethylaminopropyl)]amine, bis[3-(N,N-diethylaminopropyl)]amine, bis[3-(N,N-diisopropylaminopropyl)]amine, bis[3-(N,N-dibutylaminopropyl)]amine, and the like.

[0037] The active hydrogen equivalent (g / eq) of the amine compound is preferably 10 or more and 300 or less, more preferably 15 or more and 150 or less, from the viewpoint of the balance between curability and storage stability.

[0038] Examples of the epoxy compound include polyglycidyl ether compounds of mononuclear polyhydric phenol compounds such as hydroquinone, resorcinol, pyrocatechol, and phloroglucinol; and polynuclear polyhydric phenols such as dihydroxynaphthalene, biphenol, methylenebisphenol (bisphenol F), methylenebis(ortho-cresol), ethylidenebisphenol, isopropylidenebisphenol (bisphenol A), isopropylidenebis(ortho-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, oxybisphenol, phenol novolac, orthocresol novolac, ethylphenol novolac, butylphenol novolac, octylphenol novolac, resorcinol novolac, and terpene phenol. Polyglycidyl ether compounds of alcohol compounds; polyglycidyl ethers of polyhydric alcohols such as ethylene glycol, propylene glycol, butylene glycol, hexanediol, polyglycol, thiodiglycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, and bisphenol A-alkylene oxide adducts; maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, suberic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, trimer acid, Glycidyl esters of aliphatic, aromatic, or alicyclic polybasic acids, such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, and endomethylenetetrahydrophthalic acid, and homopolymers or copolymers of glycidyl methacrylate; epoxy compounds having a glycidylamino group, such as N,N-diglycidylaniline, bis(4-(N-methyl-N-glycidylamino)phenyl)methane, and diglycidyl orthotoluidine;Examples of epoxy compounds include epoxidized cyclic olefin compounds such as vinylcyclohexene diepoxide, dicyclopentanediene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6-methylcyclohexanecarboxylate, 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.

[0039] The epoxy compound may be either a glycidyl-type epoxy compound, which is an epoxy compound having a glycidyl group, or a cycloalkene oxide-type epoxy compound, typified by an epoxidized product of a cyclic olefin compound. In addition, when the epoxy compound is a glycidyl-type, it may be either an aromatic epoxy compound having an aromatic ring or an aliphatic epoxy compound not having an aromatic ring. Preferably, a glycidyl-type epoxy compound is used as the epoxy compound from the viewpoint of reactivity, and more preferably a glycidyl-type aromatic epoxy compound from the viewpoint of heat resistance.

[0040] Examples of the isocyanate compound include aromatic diisocyanates such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, phenylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, 1,5-naphthylene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, 3,3'-dimethyldiphenyl-4,4'-diisocyanate, dianisidine diisocyanate, and tetramethylxylylene diisocyanate; isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate; Aliphatic diisocyanates such as tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4 and / or (2,4,4)-trimethylhexamethylene diisocyanate, lysine diisocyanate, etc.; isocyanurate trimer, biuret trimer, trimethylolpropane adduct of the above-exemplified diisocyanates, etc.; triphenylmethane triisocyanate, 1-methylbenzene-2,4,6-triisocyanate, dimethyltriphenylmethane tetraisocyanate, etc. Furthermore, these isocyanate compounds may be used in a carbodiimide-modified, isocyanurate-modified, biuret-modified or other form, or may be used in the form of a blocked isocyanate blocked with various blocking agents.

[0041] Here, in the modified amine (C-1), the amount of the amine compound having one or more active hydrogens and the epoxy compound used is preferably such that 0.1 to 0.9 equivalents, particularly 0.2 to 0.8 equivalents of epoxy groups of the epoxy compound are reacted with 1 equivalent of active hydrogen of the amine compound. In the modified amine (C-2), the amount of the amine compound having one or more active hydrogens and the isocyanate compound used is preferably such that 0.1 to 0.9 equivalents, particularly 0.2 to 0.8 equivalents of the isocyanate group of the isocyanate compound are reacted with 1 equivalent of the active hydrogen of the amine compound. Furthermore, in the modified amine (C-3), an amine compound having one or more active hydrogen atoms is ,workman Poxy compounds and Bii The amount of the isocyanate compound used is preferably such that the total amount of epoxy groups of the epoxy compound and isocyanate groups of the polyisocyanate compound is 0.1 to 0.9 equivalents, particularly 0.2 to 0.8 equivalents, per equivalent of active hydrogen of the amine compound. Here, it is preferable to set the amount of the epoxy compound and / or the isocyanate compound relative to the amine compound having one or more active hydrogens to the above lower limit or more, since this can improve the storage stability of the curable resin composition, and it is preferable to set the amount to the above upper limit or less, since this can reliably obtain curability.

[0042] The method for producing the modified amines (C-1), (C-2), and (C-3) is not particularly limited, but examples thereof include a method in which a solvent is used as needed, and the reaction is carried out at room temperature to 140°C under heating for 1 to 10 hours. In the case of the modified amine (C-3), it is usually preferable to react the amine compound with the epoxy compound and then with the polyisocyanate compound. When a solvent is used, the solvent can be removed by heating under normal pressure or reduced pressure after the reaction is completed.

[0043] Examples of the solvent used in producing the modified amine include ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, propylene glycol monomethyl ether acetate, and cyclohexane; ethers such as tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, and propylene glycol monomethyl ether; esters such as ethyl acetate and n-butyl acetate; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated aliphatic hydrocarbons such as carbon tetrachloride, chloroform, trichloroethylene, and methylene chloride; and halogenated aromatic hydrocarbons such as chlorobenzene.

[0044] Examples of the phenolic resin used in the component (C-4) include polyhydric phenol compounds such as phenol novolak resins, cresol novolak resins, aromatic hydrocarbon formaldehyde resin-modified phenolic resins, dicyclopentadiene phenol adduct resins, phenol aralkyl resins (Xylok resins), naphthol aralkyl resins, trisphenylolmethane resins, tetraphenylolethane resins, naphthol novolak resins, naphthol-phenol co-condensed novolak resins, naphthol-cresol co-condensed novolak resins, biphenyl-modified phenolic resins (polyhydric phenol compounds in which phenol nuclei are linked via bismethylene groups), biphenyl-modified naphthol resins (polyhydric naphthol compounds in which phenol nuclei are linked via bismethylene groups), aminotriazine-modified phenolic resins (compounds having a phenol skeleton, a triazine ring, and a primary amino group in the molecular structure), and alkoxy group-containing aromatic ring-modified novolak resins (polyhydric phenol compounds in which phenol nuclei and alkoxy group-containing aromatic rings are linked via formaldehyde).

[0045] In the present invention, from the viewpoint of obtaining a curable resin composition with an excellent balance between storage stability and curability, it is preferable to use a phenolic resin (C-4) having a softening point of 50 to 200°C.

[0046] The amount of the phenolic resin used in (C-4) is preferably 10 to 100 parts by mass, and particularly preferably 20 to 60 parts by mass, per 100 parts by mass of the modified amines (components (C-1), (C-2), and (C-3)). An amount of 10 parts by mass or more ensures sufficient curability, while an amount of 100 parts by mass or less more reliably prevents deterioration in the physical properties of the cured product, which is preferable.

[0047] Furthermore, the latent curing agents (C-1) to (C-4) may be used after being pulverized using a pulverizer such as a jet mill.

[0048] Among the (C) amine-based latent curing agents having active hydrogen, commercially available products include ADEKA HARDNER EH-3636AS (manufactured by ADEKA Corporation; dicyandiamide-type latent curing agent), ADEKA HARDNER EH-4351S (manufactured by ADEKA Corporation; dicyandiamide-type latent curing agent), ADEKA HARDNER EH-5011S (manufactured by ADEKA Corporation; imidazole-type latent curing agent), ADEKA HARDNER EH-5046S (manufactured by ADEKA Corporation; imidazole-type latent curing agent), ADEKA HARDNER EH-4357S (manufactured by ADEKA Corporation; polyamine-type latent curing agent), ADEKA HARDNER EH-5057P (manufactured by ADEKA Corporation; polyamine-type latent curing agent), and ADEKA HARDNER Examples of such curing agents include EH-5057PK (manufactured by ADEKA Corporation; polyamine-type latent curing agent), Amicure PN-23 (manufactured by Ajinomoto Fine-Techno Co., Ltd.; amine adduct-type latent curing agent), Amicure PN-40 (manufactured by Ajinomoto Fine-Techno Co., Ltd.; amine adduct-type latent curing agent), Amicure VDH (manufactured by Ajinomoto Fine-Techno Co., Ltd.; hydrazide-type latent curing agent), and Fujicure FXR-1020 (manufactured by T&K TOKA Corporation; latent curing agent).

[0049] The amount of the (C) amine-based latent curing agent having active hydrogen used is not particularly limited, but for reasons of reactivity and one-component stability, it is preferably 1 to 70 parts by mass, and more preferably 3 to 60 parts by mass, per 100 parts by mass of the total amount of the (A) cyanate ester resin and the (B) epoxy resin.

[0050] In the present invention, if necessary, a known curing accelerator can be used in combination with the (C) active hydrogen-containing amine-based latent curing agent. Specific examples of these curing accelerators include phosphines such as triphenylphosphine; phosphonium salts such as tetraphenylphosphonium bromide; imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, and 1-cyanoethyl-2-methylimidazole; imidazole salts obtained by combining the imidazoles with trimellitic acid, isocyanuric acid, boron, or the like; benzyldimethylamine, 2,4,6-tris(trimethylsilyl)-2,4,6-trimethylisothiazolinone; Examples of curing accelerators include amines such as (dimethylaminomethyl)phenol; quaternary ammonium salts such as tetramethylammonium 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 tolylene diisocyanate-dimethylurea; and complex compounds of boron trifluoride with amines, ether compounds, or the like. These curing accelerators may be used alone or in combination of two or more. The content of the curing accelerator in the curable resin composition of the present invention is not particularly limited and can be appropriately set depending on the application of the curable resin composition.

[0051] The ion scavenger (component (D)) used in the present invention preferably has an ion exchange capacity of 1.0 meq / g or more, since this provides excellent anti-fogging properties under high temperature and high humidity conditions. The upper limit of the ion exchange capacity is usually 10 meq / g or less. The ion exchange capacity of the ion scavenger is measured by ICP emission spectroscopy, for example, the following method described in the pamphlet of WO2008 / 053694. 1.0 g of the sample to be measured and 50 mL of 0.1 mol / L sodium hydroxide solution are placed in a 100 mL polyethylene bottle and shaken at 40°C for 20 hours, after which the sodium ion concentration of the supernatant is measured using an ICP atomic emission spectrometer. The sodium ion concentration is measured in the same manner without the sample, and this is used as the blank value to calculate the ion exchange capacity. The ion scavenger used in the present invention preferably has at least a cation-scavenging ability, and more preferably has both ion-scavenging ability and cation-scavenging ability.

[0052] The ion scavenger, which is component (D) used in the present invention, is a material having ion-trapping ability that can capture decomposition components generated from the curable resin composition when exposed to a high-temperature, high-humidity environment. Examples of such an ion scavenger include organic and inorganic ion scavengers. From the viewpoint of excellent heat resistance, inorganic ion scavengers are preferred. In particular, inorganic fine particles having ion-trapping ability are preferred from the viewpoints of excellent heat resistance and ease of uniform dispersion in the curable resin composition.

[0053] The inorganic fine particles having ion-trapping ability are preferably inorganic fine particles containing at least one metal element selected from zirconium, antimony, bismuth, aluminum, magnesium, yttrium, lanthanum, and neodymium, in particular, from the viewpoint of excellent ability to trap decomposed substances derived from glass under high temperature and high humidity. The composition of the inorganic fine particles containing a metal element may be either a simple metal or a metal compound, but a metal compound is preferred in terms of excellent ability to trap decomposed substances derived from glass under high temperature and high humidity. Specific examples of the composition of inorganic fine particles having ion-trapping ability include zirconium phosphate, zirconium tungstate, zirconium molybdate, zirconium tungstate, zirconium antimonate, zirconium selenate, zirconium tellurite, zirconium silicate, zirconium phosphosilicate, zirconium polyphosphate, bismuth oxide compounds, bismuth hydroxide compounds, yttrium oxide, lanthanum oxide, neodymium oxide, composite oxides of magnesium and aluminum, hydrotalcite, hydrocalumite, hydroohmite, zeolite, other metal composite compounds, and mixtures thereof. These may be natural or artificial. The particle size of these ion scavengers is preferably 0.001 to 100 μm, particularly 0.01 to 20 μm, because they have excellent ability to capture glass-derived decomposition products under high-temperature and high-humidity conditions. The particle size referred to here is the average particle size, which can be measured by a laser diffraction / scattering method. Specifically, a particle size distribution of the inorganic ion scavengers is created on a volume basis using a laser diffraction / scattering particle size distribution analyzer, and the median diameter is taken as the particle size (average particle size) described above.

[0054] Among the ion scavengers, inorganic fine particles containing magnesium, aluminum, and zirconium are preferred because of their excellent anti-fogging property improving effect, and among these, ion scavengers that are fine particles containing magnesium, aluminum, and zirconium and having a particle diameter (median diameter) of 0.01 to 10 μm are more preferred, and among these, those that do not contain bismuth are particularly preferred because of their excellent anti-fogging property improving effect.

[0055] Examples of commercially available ion scavengers include IXE-100, IXE-300, IXE-500, IXE-530, IXE-550, IXE-600, IXE-633, IXE-700F, IXE-770D, IXE-800, IXE-1000, IXE-6107, IXE-6136, IXEPLAS-A1, IXEPLAS-A2, and IXEPLAS-B1 (manufactured by Toagosei Co., Ltd.); Kyoward 200, Kyoward 500, Kyoward 600, Kyoward 700, KW-2000, and DHT-4A (manufactured by Kyowa Chemical Industry Co., Ltd.). Examples of commercially available particularly preferred ion scavengers include IXEPLAS-A1 and A2.

[0056] The amount of the ion scavenger (component (D)) used in the present invention is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 5 parts by mass, particularly preferably 1 to 5 parts by mass, and most preferably 1.5 to 5 parts by mass, based on 100 parts by mass of the total amount of components (A), (B), and (C). By using an amount of 0.01 part by mass or more, the possibility of not achieving an improvement in anti-fogging properties can be avoided, and by using an amount of 10 parts by mass or less, the possibility of adversely affecting the physical properties of the cured product of the resin composition can be avoided.

[0057] The curable resin composition of the present invention may further contain a phosphorus-based antioxidant, a phenol-based antioxidant or a sulfur-based antioxidant.

[0058] Examples of the phosphorus-based antioxidant include triphenyl phosphite, tris(2,4-di-tert-butylphenyl) phosphite, tris(nonylphenyl) phosphite, tris(dinonylphenyl) 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, diphenyl decyl phosphite, and phenyl diisopropyl phosphate. Decyl phosphite, tributyl phosphite, tris(2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, dibutyl acid phosphite, dilauryl acid phosphite, trilauryl trithiophosphite, bis(neopentyl glycol)·1,4-cyclohexanedimethyl diphosphite, bis(2,4-ditert-butylphenyl)pentaerythritol diphosphite, bis(2,6-ditert-butyl-4-methylphenyl)pentaerythritol diphosphite, di Stearyl pentaerythritol diphosphite, phenyl-4,4'-isopropylidenediphenol pentaerythritol diphosphite, tetra(C12-15 mixed alkyl)-4,4'-isopropylidenediphenyl phosphite, bis[2,2'-methylenebis(4,6-diamylphenyl)]isopropylidenediphenyl phosphite, hydrogenated-4,4'-isopropylidenediphenol polyphosphite, bis(octylphenyl)bis[4,4'-n-butylidenebis(2-tert-butyl-5-methyl) tetratridecyl-4,4'-butylidenebis(2-tert-butyl-5-methylphenol) diphosphite, hexa(tridecyl)-1,1,3-tris(2-methyl-5-tert-butyl-4-hydroxyphenyl)butane triphosphonite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2-butyl-2-ethylpropanediol-2,4,6-tri-tert-butylphenol monophosphite, etc.

[0059] Examples of the phenolic antioxidant include 2,6-di-tert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, distearyl (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-di(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)butylic acid]glycol ester, 4,4'-butylidenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(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]isocyanurate, tetramethylbenzyl Examples include kis[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].

[0060] Examples of the sulfur-based antioxidant include dialkyl thiodipropionates such as dilauryl, dimyristyl, myristylstearyl, and distearyl esters of thiodipropionic acid, and β-alkyl mercaptopropionic acid esters of polyols such as pentaerythritol tetra(β-dodecylmercaptopropionate).

[0061] The curable resin composition of the present invention may also contain an ultraviolet absorber or a hindered amine light stabilizer.

[0062] Examples of the ultraviolet absorber include 2-hydroxybenzophenones such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-tert-butyl-4'-(2-methacryloyloxyethoxyethoxy)benzophenone, and 5,5'-methylenebis(2-hydroxy-4-methoxybenzophenone); 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, and 2-hydroxybenzophenone; triazole, 2-(2-hydroxy-3,5-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- 2-(2-hydroxyphenyl)benzotriazoles such as polyethylene glycol esters of benzotriazolylphenol, 2-(2-hydroxy-3-tert-butyl-5-carboxyphenyl)benzotriazole; 2-(2-hydroxy-4-hexyloxyphenyl)-4,6-diphenyl-1,3,5-triazine, 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine, 2-(2-hydroxy-4-octoxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1, 2-(2-hydroxyphenyl)-1,3,5-triazines such as 3,5-triazine; benzoates such as phenyl salicylate, resorcinol monobenzoate, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2,4-di-tert-amylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, and hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate; substituted oxanilides such as 2-ethyl-2'-ethoxyoxanilide and 2-ethoxy-4'-dodecyloxanilide;Examples include cyanoacrylates such as ethyl-α-cyano-β,β-diphenylacrylate and methyl-2-cyano-3-methyl-3-(p-methoxyphenyl)acrylate;

[0063] Examples of the hindered amine light stabilizer include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6-tetramethyl-4-piperidyl benzoate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, tetrakis(1,2,2,6,6- pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, bis(2,2,6,6-tetramethyl-4-piperidyl)·bis(tridecyl)-1,2,3,4-butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)·bis(tridecyl)-1,2,3,4-butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)-2-butyl-2-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, 1-(2-hydroxyethyl)-2,2,6 ,6-Tetramethyl-4-piperidinol / diethyl succinate polycondensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane / dibromoethane polycondensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane / 2,4-dichloro-6-tert-octylamino-s-triazine polycondensate, 1,5,8,12-tetrakis[2,4-bis(N-butyl -N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-s-triazin-6-yl]-1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)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-piperidyl)amino-s-triazin-6-ylamino]undecane, 1,6,11-tris[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino-s-triazin-6-ylamino)undecane, etc.

[0064] The curable resin composition of the present invention can contain a silane coupling agent. Examples of the silane coupling agent include γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-N'-β-(aminoethyl)-γ-aminopropyltriethoxysilane, γ-anilinopropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, vinyltriethoxysilane, N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, and γ-glycidoxypropyltrimethoxysilane.

[0065] The curable resin composition of the present invention can contain a filler. Examples of the filler 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, beryllia, zirconia, zircon, fosterite, steatite, spinel, mullite, and titania, or spherical beads thereof, inorganic fillers such as glass fiber, pulp fiber, synthetic fiber, and ceramic fiber; organic fillers such as acrylic resin, silicone resin, polystyrene resin, and polydivinylbenzene; rubber fillers such as acrylonitrile-butadiene rubber (NBR) and styrene-butadiene rubber (SBR); and core-shell fillers having a core made of butadiene rubber or the like and a shell made of acrylic resin, epoxy resin, or the like. Go Examples include Mufilah. Commercially available fillers include, for example, the Metablen (registered trademark) E series, Metablen (registered trademark) C series, and Metablen (registered trademark) W series manufactured by Mitsubishi Rayon Co., Ltd.; the MX series, SX series, and SGP series manufactured by Soken Chemical & Engineering Co., Ltd.; the Zefiac series manufactured by Aica Kogyo Co., Ltd.; the ChromoSphere-T series manufactured by ThermoFisherScientific; the Estapor (registered trademark) series manufactured by MerckChimie; Finepearl (registered trademark) manufactured by Matsuura Co., Ltd.; XER-91P and XER-81P manufactured by JSR Corporation; and TMS-2670 manufactured by The Dow Chemical Company.

[0066] When the curable resin composition of the present invention contains a filler, the content of the filler is preferably 20 parts by mass or more and 1,000 parts by mass or less, and more preferably 50 parts by mass or more and 500 parts by mass or less, relative to 100 parts by mass of the total amount of the (A) cyanate ester resin, the (B) epoxy resin, and the (C) active hydrogen-containing amine-based latent curing agent, from the viewpoint of workability when prepared as a one-component composition.

[0067] The curable resin composition of the present invention can be dissolved in various solvents, preferably organic solvents, before use. Suitable organic solvents include ethers such as tetrahydrofuran, 1,2-dimethoxyethane, and 1,2-diethoxyethane, alcohols such as iso- or n-butanol, iso- or n-propanol, amyl 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, triethylamine, pyridine, dioxane, and acetonitrile.

[0068] The curable resin composition of the present invention may further contain various other additives as necessary. Examples of such additives include phenolic compounds such as biphenol; reactive diluents such as monoalkyl glycidyl ether; 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, Japan wax, Ibota wax, beeswax, lanolin, spermaceti, montan wax, petroleum wax, aliphatic wax, aliphatic esters, aliphatic ethers, aromatic esters, and aromatic ethers; thickeners; thixotropic agents; antifoaming agents; rust inhibitors; and commonly used additives such as colloidal silica, colloidal alumina, carbon black, titanium black, benzimidazolidinone, and dicyclohexylurea. In the present invention, adhesive resins such as xylene resins and petroleum resins may also be used in combination.

[0069] In the curable resin composition of the present invention, the amounts of components other than (A) cyanate ester resin, (B) epoxy resin, (C) amine-based latent curing agent having active hydrogen, and (D) ion scavenger (excluding fillers and solvents) may be any amounts that do not impair curability and anti-fogging properties, but are preferably 10% by mass or less, and more preferably 5% by mass or less, of the solid content of the composition in order to ensure sufficient amounts of (A) to (D).

[0070] When curing the curable resin composition of the present invention, it is preferable to heat it at, for example, 80 to 200° C., since this allows the cured product to exhibit its physical properties. The curable resin composition of the present invention is useful as a one-component curable resin composition that is cured by heating.

[0071] The curable resin composition of the present invention can be used as a coating material or adhesive for concrete, cement mortar, various metals, leather, glass, rubber, plastics, wood, cloth, paper, etc. In particular, since it has excellent fast curing properties, heat resistance, and anti-fogging properties, it is suitably used as a coating material or adhesive for optical materials.

[0072] In the present invention, even when the cured product is left at high temperatures, for example, from 50 to 100°C and a relative humidity of from 0 to 90%, particularly at high temperatures and high humidity for a long period of time, for example, for 500 hours or more, it is possible to effectively prevent fogging of optical elements and optical components such as lenses, mirrors, prisms, filters, and fibers, solar cell components such as solar panels, display components such as liquid crystal panels and touch panels, etc. [Example]

[0073] Next, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples in any way.

[0074] Production Example 1 (Synthesis of modified polyamine) A flask was charged with 201 g (2.71 mol) of 1,2-diaminopropane and heated to 60°C. Then, 580 g (3.05 equivalents) of ADEKA RESIN EP-4100E (a bisphenol A-type epoxy resin with an epoxy equivalent of 190, manufactured by ADEKA Corporation) was added in small increments to maintain the system temperature at 100–110°C. After the ADEKA RESIN EP-4100E was completely added, the reaction system was heated to 140°C and reacted for 1.5 hours to obtain a modified polyamine. Next, 30 g of MP-800K (a phenolic resin with a softening point of 100°C, manufactured by Asahi Organic Chemicals Co., Ltd.) was added to 100 g of the resulting modified polyamine. The mixture was degassed under reduced pressure at 180–190°C and 30–40 Torr for 1 hour to remove unreacted material, and then pulverized using a jet mill to obtain the latent curing agent (EH-1).

[0075] [Examples 1 to 4 and Comparative Example 1] Resin compositions were prepared by mixing the components according to the formulation shown in Table 1 below, and the following tests were carried out. The evaluation results are shown in Table 1 below. The numerical values ​​for the formulations shown in Table 1 represent parts by mass. In addition, "ion scavenger to resin" in Table 1 indicates the mass ratio (% by mass) of component (D) to the total amount of components (A) to (C).

[0076] <Curing degree> The resin composition was placed in an aluminum pan and the total calorific value was measured using a DSC. The resin composition was also placed in an aluminum pan and cured by heating in an oven set at 120°C for 1 hour, and the residual calorific value was measured using a DSC. The degree of cure (%) was calculated using the following formula. Degree of cure (%) = [(total heat generation - residual heat generation) / total heat generation] x 100

[0077] <Anti-fogging> 0.1 g of the resin composition was spread thinly in the center of a glass petri dish (75 mm outer diameter x 20 mm height, made of ordinary glass) and heat-cured for 1 hour in an oven set to 120°C. The dish was covered with a lid leaving a gap of approximately 500 μm and placed in a thermo-hygrostat set to a temperature of 85°C and a relative humidity of 85% for 2000 hours. After the test was completed, the petri dish was removed and the glass surface around the cured product was observed with an optical microscope. The anti-fogging property was evaluated on a 4-point scale based on the time until fogging occurred. D: Clouding occurs by 500 hours. C: Almost no clouding is observed up to 500 hours, but clouding occurs by 1000 hours. B: Almost no clouding is observed up to 1000 hours, but clouding occurs by 2000 hours. A: There is almost no cloudiness until 2000 hours.

[0078] [Table 1]

[0079] EP-1: ADEKA Corporation EP-4300E (bisphenol A type epoxy resin (polyglycidyl ether compound of polynuclear polyhydric phenol compound)) EP-2: ADEKA Corporation EP-3950S (aminophenol type epoxy resin (epoxy compound with glycidylamino group)) EP-3: ADEKA Corporation EP-4088S (dicyclopentadiene-type epoxy resin (polyglycidyl ether compound of dicyclopentadiene dimethanol)) CY-1: Lonza Lecy (bisphenol-type cyanate ester resin) Silica: 200SX-E1 manufactured by Admatechs Co., Ltd. IC-1: IXEPLAS-A1 (Mg, Al, Zr-based ion scavenger, median diameter 0.5 μm, ion exchange capacity Na) manufactured by Toagosei Co., Ltd. + 1 meq / g or more and 10 meq / g or less: catalog value)

[0080] As shown by the above examples, the curable resin composition of the present invention has excellent curability since no decrease in the degree of cure is observed, and the resulting cured product has excellent anti-fogging properties under high temperature and high humidity conditions. [Industrial Applicability]

[0081] The curable resin composition of the present invention is particularly excellent in curability and in the anti-fogging properties of the resulting cured product under high temperature and high humidity conditions, and therefore can be suitably used, for example, as an adhesive for optical components.

Claims

1. A curable resin composition comprising (A) a cyanate ester resin, (B) an epoxy resin, (C) an amine-based latent curing agent having active hydrogen, and (D) an ion scavenger, wherein the amine-based latent curing agent having active hydrogen, which is component (C), is at least one selected from the following (C-1) to (C-4), and the ion scavenger, which is component (D), is inorganic fine particles containing at least one metal element selected from zirconium, antimony, bismuth, aluminum, magnesium, yttrium, lanthanum, and neodymium, and has an ion exchange capacity for Na + of 1.0 meq / g or more. (C-1): A modified amine obtained by reacting an amine compound having one or more active hydrogen atoms with an epoxy compound. (C-2): Modified amine obtained by reacting an amine compound having one or more active hydrogens with an isocyanate compound. (C-3): Modified amine obtained by reacting an amine compound having one or more active hydrogen atoms, an epoxy compound, and an isocyanate compound. (C-4): A latent curing agent containing at least one modified amine selected from (C-1), (C-2) and (C-3) and a phenolic resin.

2. 2. The curable resin composition according to claim 1, wherein the cyanate ester resin (A) is at least one selected from the group consisting of a compound represented by the following formula (1), a compound represented by the following formula (2), and at least one polymer selected from these: NC-O-A １ -y １ - A ２ - O - CN (1) (Y in the formula １ represents a divalent hydrocarbon group that is unsubstituted or substituted with a fluorine atom or a cyanato group, or represents —O—, —S—, or a single bond; A １ and A ２ are each independently a phenylene group that is unsubstituted or substituted with 1 to 4 alkyl groups. 【Chemistry 1】 (wherein m is an integer of 1 or more, and Y ２ and Y ３ R each independently represents -S- or a divalent hydrocarbon group that is unsubstituted or substituted with a fluorine atom or a cyanato group. １ , R ２ , R ３ , R ４ , R ５ and R ６ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

3. Y in the formula (1) １ And Y in the formula (2) ２ and Y ３ The curable resin composition according to claim 2, wherein each independently represents at least one selected from the following formulas (Y-1) to (Y-9): 【Chemistry 2】 where n is an integer from 4 to 12, and R ７ and R ８ are each independently a hydrogen atom or an unsubstituted or fluorine-substituted methyl group. * represents a bond.

4. 2. The curable resin composition according to claim 1, wherein the active hydrogen-containing amine-based latent curing agent of component (C) is a latent curing agent of component (C-4).

5. 5. The curable resin composition according to claim 1, wherein the ion scavenger (D) is inorganic fine particles containing magnesium, aluminum, and zirconium.

6. A cured product obtained by curing the curable resin composition according to any one of claims 1 to 5.

7. An adhesive comprising the curable resin composition according to any one of claims 1 to 5.

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