Curable composition, cured product, adhesive and sealing agent

Abstract

To provide a curable composition having curability, low viscosity and mechanical strength at high levels and a cured product of the same, an adhesive and a sealing agent.SOLUTION: A curable composition contains an epoxy-oxetane compound represented by chemical formula (I). In the formula, R is the same or different, and represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a curable composition, a cured product, an adhesive, and a sealing agent.

Background Art

[0002] Epoxy-oxetane compounds have recently attracted attention as monomers capable of photocuring and thermocuring. A curable composition containing this as a component has a small shrinkage during curing, and the cured product (resin) is excellent in toughness, mechanical properties (mechanical strength), heat resistance, electrical properties, water resistance (moisture resistance), weather resistance, transparency, adhesion (adhesiveness) to other materials, and the like. Due to such excellent characteristics, curable compositions containing epoxy-oxetane compounds are being promoted for use as raw materials for coating materials, paints, inks, adhesive materials (adhesives), pressure-sensitive adhesive materials, films, pastes, optical materials, sealing materials (sealing agents), resist materials, and the like.

[0003] The prior art related to the present invention will be described below by citing literature. The invention described in Patent Document 1 relates to an active energy ray-curable ink composition containing a polymerizable compound having a molecular weight of 600 or less and containing three or more cationic polymerizable groups in the molecule. This document describes an epoxy compound represented by Chemical Formula (Ref-1) and an epoxy-oxetane compound represented by Chemical Formula (Ref-2) as polymerizable compounds.

[0004]

Chem.

[0005]

Chem.

[0006] The invention described in Patent Document 2 relates to a thin film adhesive composition containing a cyclic ether compound having an epoxy group and an oxetanyl group. This document describes an epoxy-oxetane compound represented by the chemical formula (Ref-3) as an example of a cyclic ether compound having an epoxy group and an oxetanyl group.

[0007] [ka]

[0008] Curable compositions containing epoxy-oxetane compounds used in various applications are required to have the following characteristics: a cured product can be obtained by curing; and a low viscosity is required from the viewpoint of workability during preparation and use of the curable composition. In addition, the cured product obtained by curing the curable composition is required to have the following characteristics: high elasticity and excellent rigidity, high bending strength, and excellent mechanical strength due to the formation of a uniform three-dimensional network with few structural defects in the cured product. Curable compositions containing epoxy-oxetane compounds represented by chemical formulas (Ref-1) to (Ref-3) and their cured products do not have these characteristics at a high level, and have problems with curability, viscosity, and / or mechanical strength. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] JP 2010-111713 A [Patent Document 2] JP 2019-189789 A Summary of the Invention [Problem to be solved by the invention]

[0010] An object of the present invention is to provide a curable composition having high curability, low viscosity, and high mechanical strength, a cured product thereof, an adhesive, and a sealing agent.

Means for Solving the Problems

[0011] The present inventors have recognized that a curable composition containing an epoxy-oxetane compound represented by chemical formula (I) can achieve the intended purpose as the curable composition, and have completed the present invention.

[0012] That is, a first invention is a curable composition containing an epoxy-oxetane compound represented by chemical formula (I).

[0013]

Chemical formula

[0014] Moreover, it may contain a cationic polymerization initiator.

[0015] A second invention is a cured product obtained by curing the curable composition of the first invention.

[0016] A third invention is an adhesive containing the curable composition of the first invention.

[0017] A fourth invention is a sealing agent containing the curable composition of the first invention.

Effects of the Invention

[0018] A curable composition containing an epoxy-oxetane compound represented by chemical formula (I) can be a curable composition having excellent curability, low viscosity, and excellent workability. Further, the cured product obtained by curing the curable composition has high elasticity, excellent rigidity, high flexural strength, and can be a cured product having excellent mechanical strength by forming a uniform three-dimensional network with few structural defects in the cured product.

Brief Description of the Drawings

[0019]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Embodiments for Carrying Out the Invention

[0020] The curable compound of the present invention contains an epoxy-oxetane compound represented by the chemical formula (I). The epoxy-oxetane compound represented by the chemical formula (I) has a structure in which two epoxy groups are symmetrically arranged with respect to one oxetane ring having an ethyl group, and each of the oxetane ring and the two epoxy groups is bonded via a linker having one ether bond.

[0021]

Chemical formula

[0022] In the above chemical formula (I), R represents the same or different hydrogen atoms or alkyl groups having 1 to 3 carbon atoms. The alkyl group may be linear or branched. Specifically, examples include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. From the viewpoint of easy availability of raw materials and simplification of the synthesis process, it is preferable that R is the same and is a hydrogen atom or a methyl group.

[0023] Examples of the epoxy-oxetane compound represented by the chemical formula (I) include compounds represented by the chemical formula (I-1) to the chemical formula (I-6).

[0024]

Chem.

[0025] The epoxy - oxetane compound represented by Chemical Formula (I) is preferably an epoxy - oxetane compound represented by Chemical Formula (I - 1) to Chemical Formula (I - 6) from the viewpoints of easy availability of raw materials and simplification of the synthesis process, and more preferably an epoxy - oxetane compound represented by Chemical Formula (I - 1). The epoxy - oxetane compound represented by Chemical Formula (I) may be used alone or as a mixture of two or more.

[0026] <On the synthesis method of the epoxy - oxetane compound represented by Chemical Formula (I)> A bifunctional olefin compound having a hydroxy group represented by Chemical Formula (II) is reacted with an oxetane compound having a leaving group represented by Chemical Formula (III) to produce an olefin - oxetane compound represented by Chemical Formula (Ia), and then the double bond of this compound is epoxidized to synthesize the epoxy - oxetane compound represented by Chemical Formula (I) (see Reaction Scheme (A)).

[0027]

Chem.

[0028] In Chemical Formula (III), X is a leaving group and represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a mesyloxy group (OMs), a tosyloxy group (OTs), or a trifluoromethanesulfonyloxy group (OTf). Also, in Chemical Formulas (II) and (Ia), R has the same meaning as R in Chemical Formula (I), and the wavy line represents a trans form, a cis form, or a mixture thereof.

[0029] Examples of the oxetane compound having a leaving group represented by the above chemical formula (III) include 3-ethyl-3-methanesulfonyloxymethyloxetane, 3-bromomethyl-3-ethyloxetane, and the like.

[0030] Examples of the bifunctional olefin compound having a hydroxy group represented by the above chemical formula (II) include compounds represented by chemical formula (II-1) to chemical formula (II-15). The bifunctional olefin compound may be used alone or in combination of two kinds.

[0031] [Chemical formula]

[0032] The bifunctional olefin compound having a hydroxy group represented by the above chemical formula (II) can be synthesized, for example, by the method described in Chinese Patent Publication Gazette No. 102267878. In the synthesis of the bifunctional olefin compound, raw materials derived from biomass can also be used. From the viewpoint of reducing environmental load, it is preferable to use the bifunctional olefin compound synthesized from raw materials derived from biomass. Specifically, the bifunctional olefin compound derived from biomass can be synthesized by using 2-chloromethyloxirane (epichlorohydrin) derived from biomass and an olefin compound having a terminal hydroxy group derived from biomass as raw materials.

[0033] The oxetane compound having a leaving group represented by the above chemical formula (III) can be synthesized, for example, by the method described in JP-A-2007-332294. In the synthesis of the oxetane compound, raw materials derived from biomass can also be used, and from the viewpoint of reducing the environmental load, it is preferable to use the oxetane compound synthesized from raw materials derived from biomass. By using a bifunctional olefin compound having a hydroxy group represented by the chemical formula (II) derived from biomass and / or an oxetane compound having a leaving group represented by the chemical formula (III) derived from biomass as raw materials, an epoxy-oxetane compound represented by the chemical formula (I) derived from biomass can be synthesized.

[0034] The amount (charged amount) of the bifunctional olefin compound having a hydroxy group represented by the above chemical formula (II) is preferably an appropriate ratio in the range of 0.8 to 2 times the molar amount relative to the amount (charged amount) of the oxetane compound having a leaving group represented by the above chemical formula (III).

[0035] When the bifunctional olefin compound represented by the chemical formula (II-1) and the bifunctional olefin compound represented by the chemical formula (II-2) are each used alone in the reaction as the bifunctional olefin compound, an epoxy-oxetane compound represented by the chemical formula (I-1) and an epoxy-oxetane compound represented by the chemical formula (I-2) can be obtained, respectively.

[0036] The olefin-oxetane compound represented by the chemical formula (Ia) can be synthesized in the presence of a base (i), and a catalyst (ii) may be used to accelerate the reaction. Further, as long as the reaction is not inhibited, a reaction solvent (iii) may be used. In the reaction for epoxidizing the double bond of the same compound, a general epoxidation (oxidation) method can be employed. For example, a method using a peracid, a method using hydrogen peroxide with sodium tungstate as a catalyst, a method using hydrogen peroxide together with a base in an acetonitrile-alcohol solvent, etc. can be mentioned.

[0037] Examples of the base (i) include hydrides, hydroxides, carbonates, bicarbonates, alkoxides, or organic amine compounds of alkali metals or alkaline earth metals. For example, sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium alkoxide, potassium alkoxide (e.g., t-butoxypotassium, etc.), triethylamine, etc. can be mentioned. The amount of the base used (charged amount) is preferably an appropriate ratio in the range of usually 1.1 to 20 times the molar amount with respect to the amount of the oxetane compound having a leaving group (charged amount).

[0038] Examples of the catalyst (ii) include quaternary ammonium salts, quaternary phosphonium salts, etc. Examples of the quaternary ammonium salt include salts such as halides (fluoride, chloride, bromide, iodide) of tetrabutylammonium, tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrahexylammonium, tetraoctylammonium, tetradecylammonium, hexadecyltriethylammonium, dodecyltrimethylammonium, trioctylmethylammonium, octyltriethylammonium, benzyltrimethylammonium, benzyltriethylammonium, benzyltributylammonium, benzyldimethyloctadecylammonium, phenyltrimethylammonium.

[0039] Examples of the quaternary phosphonium salt include salts such as halides (fluoride, chloride, bromide, iodide) of tetrabutylphosphonium, tetramethylphosphonium, tetraethylphosphonium, tetrapropylphosphonium, tetrahexylphosphonium, tetradecylphosphonium, tetraoctylphosphonium, triethyloctadecylphosphonium, trioctylethylphosphonium, hexadecyltriethylphosphonium, tetraphenylphosphonium, methyltriphenylphosphonium.

[0040] These substances may be combined and used as catalyst (ii). The amount of catalyst (ii) used (charged amount) is preferably an appropriate ratio in the range of 0.0001 to 1.0 times the molar amount of the oxetane compound having a leaving group (charged amount).

[0041] The reaction solvent (iii) is not particularly limited as long as it does not inhibit the reaction. For example, solvents such as water, tetrahydrofuran, diethyl ether, dioxane, 4-methyltetrahydropyran, dimethoxyethane, ethyl acetate, propyl acetate, butyl acetate, propylene glycol monomethyl ether acetate (PGMEA), acetonitrile, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, N,N-dimethylformamide (DMF), dimethylacetamide (DMA), dimethyl sulfoxide (DMSO), hexamethylphosphoric triamide (HMPA) etc. may be mentioned, and one or more selected from these can be combined and used in an appropriate amount.

[0042] The reaction temperature for synthesizing the olefin-oxetane compound represented by chemical formula (Ia) is preferably set in the range of 0 to 150 °C, more preferably in the range of 20 to 120 °C. Also, the reaction time is appropriately set according to the set reaction temperature, but it is preferably set in the range of 1 to 48 hours.

[0043] After completion of this reaction, the olefin-oxetane compound, which is a precursor of the target product, can be separated and taken out from the obtained reaction solution by means such as solvent extraction method. Furthermore, if necessary, it can be purified by means such as washing with water, activated carbon treatment, silica gel chromatography, etc.

[0044] In the reaction of epoxidizing an olefin-oxetane compound using the above-mentioned peracid, a peracid such as an oxone reagent, peracetic acid, or metachloroperbenzoic acid (3-chloroperbenzoic acid) can be used. The amount of peracid used (charged amount) is preferably set at an appropriate ratio within the range of 1.0 to 5.0 times the molar amount relative to the double bond of the olefin-oxetane compound.

[0045] In this epoxidation reaction, the reaction solvent is not particularly limited as long as it does not inhibit the reaction. Examples include alcohols such as water, methanol, ethanol, and 2-propanol; aliphatic hydrocarbons such as hexane and heptane; ketones such as acetone and 2-butanone; esters such as ethyl acetate and butyl acetate; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as methylene chloride (dichloromethane), chloroform, carbon tetrachloride, chlorotrifluoromethane, dichloroethane, chlorobenzene, and dichlorobenzene; ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, dimethoxyethane, and diethylene glycol dimethyl ether; amides such as formamide, N,N-dimethylformamide (DMF), dimethylacetamide (DMA), N-methyl-2-pyrrolidone, N-methylpyrrolidinone, and hexamethylphosphoramide; and sulfoxides such as dimethyl sulfoxide (DMSO). These reaction solvents can be used alone or in combination of two or more, and an appropriate amount is used.

[0046] In this epoxidation reaction, the reaction temperature is usually in the range of -10 to 150 °C, preferably set in the range of 0 to 100 °C. The reaction time is appropriately set according to the reaction temperature, but is usually set within the range of 1 to 48 hours, preferably 1 to 24 hours.

[0047] After completion of this reaction, the target epoxy-oxetane compound represented by chemical formula (I) can be separated and extracted from the obtained reaction solution by means such as solvent extraction. If necessary, purification can be carried out by means such as washing with water or the like, activated carbon treatment, silica gel chromatography, etc.

[0048] In the reaction of epoxidizing an olefin-oxetane compound using hydrogen peroxide with sodium tungstate as a catalyst, hydrogen peroxide is used in a proportion of 1.0 to 5.0 times the molar amount relative to the double bond of the olefin-oxetane compound. Also, the amount of sodium tungstate used (charged amount) is preferably set at an appropriate proportion within the range of 0.001 to 0.5 times the molar amount relative to the double bond of the olefin-oxetane compound.

[0049] In this epoxidation reaction, there is no particular limitation as long as the reaction is not inhibited. For example, the same reaction solvent as in the case of epoxidation using the above-mentioned peracid can be used.

[0050] Also, in this epoxidation reaction, the reaction temperature is usually in the range of -10 to 150°C, preferably set in the range of 0 to 100°C, similar to the case of epoxidation using the above-mentioned peracid. The reaction time is appropriately set according to the reaction temperature, but is usually set within the range of 1 to 48 hours, preferably within the range of 1 to 24 hours.

[0051] After completion of the reaction, similar to the case of epoxidation with the above-mentioned peracid, the epoxy-oxetane compound represented by chemical formula (I) can be separated and taken out from the obtained reaction solution by means such as solvent extraction method. Also, purification may be carried out if necessary.

[0052] In the reaction of epoxidizing an olefin-oxetane compound using hydrogen peroxide together with a base in the above-mentioned acetonitrile-alcohol solvent, the amount of hydrogen peroxide used (charged amount) is preferably set at an appropriate proportion within the range of 1.0 to 5.0 times the molar amount relative to the double bond of the olefin-oxetane compound. Also, the amount of acetonitrile used (charged amount) is preferably set at an appropriate ratio within the range of 0.5 to 5.0 times the mole of the olefin oxetane compound. The amount of alcohol used (charged amount) is preferably set at an appropriate ratio within the range of 10 to 80% by weight in the state before the addition of hydrogen peroxide. Also, it is preferable to set the pH within the range of 7 to 13 using a base.

[0053] The alcohol used for this epoxidation is preferably a saturated alcohol having 1 to 4 carbon atoms, and examples thereof include methanol, ethanol, n-propanol, 2-propanol, n-butanol, sec-butanol (2-butanol), and isobutanol (2-methyl-1-propanol). These alcohols are used in an appropriate amount either singly or in combination of two or more.

[0054] Examples of the base used for this epoxidation include hydroxides, carbonates or bicarbonates of alkali metals or alkaline earth metals, or organic amine compounds. It is preferable to use sodium hydroxide, potassium hydroxide, potassium carbonate, or potassium bicarbonate, and an appropriate amount is used either singly or in combination of two or more.

[0055] Also, the reaction temperature of this epoxidation is usually set within the range of -10 to 150°C, preferably within the range of 0 to 100°C, in the same manner as in the case of epoxidation using the peracid described above. The reaction time is appropriately set according to the reaction temperature, but is usually set within the range of 1 to 48 hours, preferably within the range of 1 to 24 hours.

[0056] After completion of the reaction, in the same manner as in the case of epoxidation using the peracid described above, the epoxy oxetane compound represented by the chemical formula (I) can be separated and taken out from the obtained reaction solution by means such as solvent extraction. Further purification may be performed if necessary.

[0057] <Regarding the curable composition of the present invention> The epoxy oxetane compound represented by the chemical formula (I) exhibits excellent curing performance. That is, for a curable composition containing an epoxy-oxetane compound represented by the chemical formula (I) (hereinafter sometimes referred to as "the first curable compound"), by curing, a cured product (resin) with excellent properties is expected to be obtained. In the curable composition of the present invention, it is also possible to use in combination the first curable compound and another curable compound different therefrom (hereinafter sometimes referred to as "the second curable compound").

[0058] When the curable composition of the present invention is cured (polymerized), by coexisting the second curable compound separately from the first curable compound, a cured product obtained by copolymerizing the first curable compound and the second curable compound can be obtained. The second curable compound includes both a polymerizable monomer and a polymerizable oligomer (semicured product) having a structure in which the polymerizable monomer is polymerized.

[0059] Examples of this polymerizable monomer include known epoxy compounds (note: sometimes referred to as epoxy resins), oxetane compounds, epoxy-oxetane compounds (having an oxirane ring and an oxetane ring in the molecule), acrylic compounds (note: sometimes referred to as acrylic resins), and the like.

[0060] As the epoxy compound, any compound having an oxirane ring (epoxy group / glycidyl group) in the molecule can be used without particular limitation. For example, Polyglycidyl ethers obtained by reacting polyhydric phenols such as bisphenol A, bisphenol F, bisphenol AD, catechol, resorcinol, or polyhydric alcohols such as glycerin and polyethylene glycol with epichlorohydrin; Glycidyl ether esters obtained by reacting hydroxycarboxylic acids such as p-hydroxybenzoic acid and β-hydroxynaphthoic acid with epichlorohydrin; Polyglycidyl esters obtained by reacting polycarboxylic acids such as phthalic acid and terephthalic acid with epichlorohydrin; A glycidyl glycoluril compound having two or more epoxy groups in the molecule, such as 1,3,4,6-tetraglycidyl glycoluril; An alicyclic epoxy compound, such as 3′,4′-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate; A nitrogen-containing cyclic epoxy compound, such as triglycidyl isocyanurate and a hydantoin-type epoxy compound; Furthermore, in addition to an epoxidized phenol novolak resin, an epoxidized cresol novolak resin, an epoxidized polyolefin, an alicyclic epoxy resin, and a urethane-modified epoxy resin, an epoxy-modified organopolysiloxane compound by a hydrosilylation addition reaction of an organic compound having a carbon-carbon double bond and a glycidyl group and a silicon compound having an SiH group (for example, an epoxy-modified organopolysiloxane compound disclosed in JP-A-2004-99751 and JP-A-2006-282988) and the like can be mentioned, and these may be used in combination.

[0061] As the oxetane compound, any compound having an oxetane ring (oxetanyl group / oxetane group) in the molecule can be used without particular limitation. For example, 3-ethyl-3-hydroxymethyloxetane, 3-(meth)allyloxymethyl-3-ethyloxetane, (3-ethyl-3-oxetanylmethoxy)methylbenzene, 4-fluoro-[1-(3-ethyl-3-oxetanylmethoxy)methyl]benzene, 4-methoxy-[1-(3-ethyl-3-oxetanylmethoxy)methyl]benzene, [1-(3-ethyl-3-oxetanylmethoxy)ethyl]phenyl ether, Isobutoxymethyl(3-ethyl-3-oxetanylmethyl)ether, Isobornyloxyethyl(3-ethyl-3-oxetanylmethyl)ether, Isobornyl(3-ethyl-3-oxetanylmethyl)ether, 2-Ethylhexyl (3-ethyl-3-oxetanilylmethyl) ether, Ethyl diethylene glycol (3-ethyl-3-oxetanilylmethyl) ether, Dicyclopentadiene (3-ethyl-3-oxetanilylmethyl) ether, Dicyclopentenyl oxyethyl (3-ethyl-3-oxetanilylmethyl) ether, Dicyclopentenyl (3-ethyl-3-oxetanilylmethyl) ether, Tetrahydrofurfuryl (3-ethyl-3-oxetanilylmethyl) ether, 2-Hydroxyethyl (3-ethyl-3-oxetanilylmethyl) ether, 2-Hydroxypropyl (3-ethyl-3-oxetanilylmethyl) ether, Butoxyethyl (3-ethyl-3-oxetanilylmethyl) ether, Borneol (3-ethyl-3-oxetanilylmethyl) ether, 3,7-Bis(3-oxetanyl)-5-oxa-nonane, 3,3′-[1,3-(2-Methylenyl)propanediylbis(oxymethylene)]bis-(3-ethyloxetane), 1,4-Bis[(3-ethyl-3-oxetanilylmethoxy)methyl]benzene, 1,2-Bis[(3-ethyl-3-oxetanilylmethoxy)methyl]ethane, 1,3-Bis[(3-ethyl-3-oxetanilylmethoxy)methyl]propane, Ethylene glycol bis(3-ethyl-3-oxetanilylmethyl) ether, Dicyclopentenyl bis(3-ethyl-3-oxetanilylmethyl) ether, Triethylene glycol bis(3-ethyl-3-oxetanilylmethyl) ether, Tetraethylene glycol bis(3-ethyl-3-oxetanilylmethyl) ether, Tricyclodecandiyldimethylene (3-ethyl-3-oxetanilylmethyl) ether, Trimethylolpropane tris(3-ethyl-3-oxetananylmethyl) ether, 1,4-bis(3-ethyl-3-oxetananylmethoxy) butane, 1,6-bis(3-ethyl-3-oxetananylmethoxy) hexane, Pentaerythritol tris(3-ethyl-3-oxetananylmethyl) ether, Pentaerythritol tetrakis(3-ethyl-3-oxetananylmethyl) ether, Polyethylene glycol bis(3-ethyl-3-oxetananylmethyl) ether, Dipentaerythritol hexakis(3-ethyl-3-oxetananylmethyl) ether, Dipentaerythritol pentakis(3-ethyl-3-oxetananylmethyl) ether, Dipentaerythritol tetrakis(3-ethyl-3-oxetananylmethyl) ether, Caprolactone-modified dipentaerythritol hexakis(3-ethyl-3-oxetananylmethyl) ether, Caprolactone-modified dipentaerythritol pentakis(3-ethyl-3-oxetananylmethyl) ether, Ditrimethylolpropane tetrakis(3-ethyl-3-oxetananylmethyl) ether, EO-modified bisphenol A bis(3-ethyl-3-oxetananylmethyl) ether, PO-modified bisphenol A bis(3-ethyl-3-oxetananylmethyl) ether, EO-modified hydrogenated bisphenol A bis(3-ethyl-3-oxetananylmethyl) ether, PO-modified hydrogenated bisphenol A bis(3-ethyl-3-oxetananylmethyl) ether, EO-modified bisphenol F(3-ethyl-3-oxetananylmethyl) ether and the like can be mentioned.

[0062] As the epoxy-oxetane compound, any compound having an oxirane ring (the same as above) and an oxetane ring (the same as above) in the molecule can be used without particular limitation, and examples thereof include those described in Patent Documents 1 and 2 mentioned above. By referring to the epoxy-oxetane compounds described in these documents, they are included in the disclosure of this specification.

[0063] Examples of the acrylic compound include allyl (meth)acrylate, vinyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyl oxyethyl (meth)acrylate, modified allyl glycidyl ether (meth)acrylate (manufactured by Nagase ChemteX Corporation, "Denacol Acrylate DA111 (trade name)"), urethane (meth)acrylates, epoxy (meth)acrylates, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, butanediol di(meth)acrylate, nonanediol di(meth)acrylate, polypropylene glycol-based (meth)acrylate, bisphenol A di(meth)acrylate, tris(2-(meth)acryloyloxyethyl) isocyanurate, (meth)acrylate group-containing polyorganosiloxane, and the like.

[0064] In the curable composition of the present invention, as the second curable compound, the above-mentioned polymerizable monomer and polymerizable oligomer may be used in combination. As the polymerizable monomer, the polymerizable monomers exemplified above may be used in combination (different types of polymerizable monomers may be used in combination), and for the polymerizable oligomer, different types of polymerizable oligomers may be used in combination.

[0065] Regarding the ratio of the content of the first curable compound to the content of the second curable compound in the curable composition of the present invention, the content of the second curable compound is preferably an appropriate ratio in the range of 0 to 1000 times the amount (weight ratio) of the content of the first curable compound, and more preferably an appropriate ratio in the range of 0.01 to 100 times the amount (weight ratio).

[0066] Examples of the method for curing (polymerizing) the curable composition of the present invention include methods of photo-curing and thermo-curing. Examples of the method of photo-curing include methods of irradiating active energy rays and methods of using a photoinitiator in combination. Active energy rays include light, radiation, electromagnetic waves, electron beams, etc., but typically represent light, particularly ultraviolet light. As the photoinitiator, a photo-cationic polymerization initiator or a photo-anionic polymerization initiator can be employed, and if necessary, a photo-radical polymerization initiator can be used in combination, and these can be contained in the curable composition. In photo-curing, in order to improve production efficiency and the properties of the cured product, a means of thermo-curing may be used in combination.

[0067] As the photo-cationic polymerization initiator, any commonly used one can be used without particular limitation, and examples include onium salts and organometallic complexes. Examples of onium salts include diazonium salts, sulfonium salts, and iodonium salts, and examples of organometallic complexes include iron-allyl complexes, titanocene complexes, and arylsilanol-aluminum complexes. Examples of commercially available industrial chemicals as photo-cationic polymerization initiators include "Optomer SP-150 (trade name)" manufactured by ADEKA Corporation, "Optomer SP-170 (trade name)" of the same company, "CPI-100P (trade name)" manufactured by San-Apro Ltd., "UVE-1014 (trade name)" manufactured by General Electronics Company, "CD-1012 (trade name)" manufactured by Sartomer Company, etc. As the counter anion of the photo-cationic polymerization initiator, SbF6 - , AsF6 - , B(C6F5)4 -, PF6 - etc. can be mentioned.

[0068] As the photoanionic polymerization initiator, any commonly used one can be used without particular limitation, and examples include onium salts and carbamates. Examples of onium salts include 1,2 - diisopropyl - 3 - (bis(dimethylamino)methylene)guanidinium 2 - (3 - benzoylphenyl)propionate, 1,2 - dicyclohexyl - 4,4,5,5 - tetramethylbiguanidinium n - butyltriphenylborate, etc. Examples of carbamates include 2 - nitrophenylmethylpiperidine - 1 - carboxylate, 1 - (anthraquinone - 2 - yl)ethylimidazole carboxylate, 1 - (3 - (2 - hydroxyphenyl)-2 - propenoyl)piperidine, 9 - anthranylmethyldiethylcarbamate, etc.

[0069] The content of the photo - cationic polymerization initiator or photo - anionic polymerization initiator in the curable composition of the present invention is preferably in the range of 0.001 to 20% by weight, and more preferably in the range of 0.01 to 10% by weight.

[0070] As the photo - radical polymerization initiator, ketal compounds having 16 to 17 carbon atoms (for example, acetophenone dimethyl ketal, benzyl dimethyl ketal, etc.), acetophenone compounds having 8 to 18 carbon atoms (for example, acetophenone, 2,2 - dimethoxy - 2 - phenylacetophenone, 2,2 - diethoxy - 2 - phenylacetophenone, 1,1 - dichloroacetophenone, 2 - hydroxy - 2 - methyl - phenylpropan - 1 - one, diethoxyacetophenone, 1 - hydroxycyclohexyl phenyl ketone, 2 - methyl - 1 - [4 - (methylthio)phenyl]-2 - morpholinopropan - 1 - one, etc.), Benzophenone compounds having 13 to 21 carbon atoms (for example, benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 4,4'-bismethylaminobenzophenone, etc.), benzoin compounds having 14 to 18 carbon atoms (for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, etc.), Anthraquinone compounds having 14 to 19 carbon atoms (for example, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-chloroanthraquinone, 2-amylanthraquinone, etc.), Thioxanthone compounds having 13 to 17 carbon atoms (for example, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, etc.), Acylphosphine oxide compounds having 22 to 28 carbon atoms (for example, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, etc.) and the like can be mentioned.

[0071] The content of the photo radical polymerization initiator in the curable composition of the present invention is preferably in the range of 0.001 to 20% by weight, and more preferably in the range of 0.01 to 10% by weight.

[0072] When the curable composition of the present invention is photocured, for example, sensitizers such as pyrene, perylene, acridine orange, thioxanthone, 2-chlorothioxanthone, and benzoflavin can be used.

[0073] On the other hand, when the curable composition of the present invention is thermally cured, a thermal polymerization initiator can be used. As the thermal polymerization initiator, a thermal cationic polymerization initiator, a thermal radical polymerization initiator, or a thermal anionic polymerization initiator can be employed, and it may be contained in the curable composition.

[0074] As the thermal cationic polymerization initiator, any commonly used one can be used without particular limitation, and various onium salts such as quaternary ammonium salts, phosphonium salts, and sulfonium salts, as well as organometallic complexes, etc. can be exemplified. Examples of onium salts commercially available as industrial chemicals include "ADEKA Opton CP-66 (trade name)", "ADEKA Opton CP-77 (trade name)" manufactured by ADEKA Corporation, "Sun-Aid SI-60L (trade name)", "Sun-Aid SI-80L (trade name)", "Sun-Aid SI-100L (trade name)" manufactured by Sanshin Chemical Industry Co., Ltd., and "CI series (trade name)" manufactured by Nippon Soda Co., Ltd., etc. Examples of organometallic complexes include alkoxysilane-aluminum complexes, etc.

[0075] As the thermal radical polymerization initiator, any commonly used one can be used without particular limitation. For example, diisopropyl peroxydicarbonate, benzoyl peroxide, t-butyl peroxyisobutyrate, t-hexyl peroxyisopropyl monocarbonate, t-hexyl peroxy 2-ethylhexanoate, 1,1,3,3-tetramethylbutyl peroxy 2-ethylhexanoate, t-butyl peroxy pivalate, t-hexyl peroxy pivalate, t-butyl peroxy neodecanoate, t-hexyl peroxy neodecanoate, 1,1,3,3-tetramethylbutyl peroxy neodecanoate, 1,1-bis(t-hexylperoxy) cyclohexane, benzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, peroxides such as lauroyl peroxide, and azo compounds such as azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), dimethyl 2,2'-azobis(2-methylpropionate) can be exemplified, and these may be used in combination.

[0076] As the thermal anionic polymerization initiator, any commonly used one can be used without particular limitation. For example, amines, imidazoles, etc. can be exemplified, and these may be used in combination.

[0077] Regarding the thermosetting conditions, the heating temperature / heating time can be appropriately set, but it is preferably set in the range of 60 to 200 °C / 30 to 240 minutes, and more preferably set in the range of 70 to 180 °C / 30 to 120 minutes.

[0078] The content of the thermal polymerization initiator in the curable composition of the present invention is preferably in the range of 0.001 to 20% by weight, and more preferably in the range of 0.01 to 10% by weight.

[0079] In the present invention, the cationic polymerization initiator refers to the above-mentioned photo cationic polymerization initiator and / or thermal cationic polymerization initiator, the anionic polymerization initiator refers to the above-mentioned photo anionic polymerization initiator and / or thermal anionic polymerization initiator, and the radical polymerization initiator refers to the above-mentioned photo radical polymerization initiator and / or thermal radical polymerization initiator.

[0080] Also, as another method for curing (polymerizing) the curable composition of the present invention, there is a method of containing a curing agent and performing photo-curing and thermosetting. When performing thermosetting, a thermal polymerization initiator can be used in combination.

[0081] Examples of the curing agent include acid anhydride compounds, thiol compounds, amine compounds, etc.

[0082] Examples of the acid anhydride compound include, for example, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, trimellitic anhydride, nadic anhydride, hymic anhydride, methylnadic anhydride, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride, bicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride, methylnorbornane-2,3-dicarboxylic acid, etc.

[0083] Examples of the thiol compound include, for example, Aliphatic thiol compounds such as ethanedithiol, propanedithiol, hexamethylenedithiol, decamethylenedithiol, tolylene-2,4-dithiol, 2,2-bis(mercaptomethyl)-1,3-propanedithiol, 2-(mercaptomethyl)-2-methyl-1,3-propanedithiol, 2-ethyl-2-(mercaptomethyl)-1,3-propanedithiol; Cyclic sulfide compounds such as 1,4-dithiane ring-containing polythiol compounds represented by formula (XIV); Mercaptoalkyl sulfide compounds such as 3-thiapentane-1,5-dithiol, 4-mercaptomethyl-3,6-dithia-1,8-octanedithiol; Mercaptopropionic acid esters such as pentaerythritol tetrakis(3-mercaptopropionate); Epoxy resin terminal mercapto compounds; 3,6-dioxa-1,8-octanedithiol, mercaptoalkyl ether disulfide compounds represented by formula (XV), 2,2′-[[2,2-bis[(2-mercaptoethoxy)methyl]-1,3-propanediyl]bis(oxy)]bisethanethiol, 3,3′-[[2,2-bis[(3-mercaptopropoxy)methyl]-1,3-propanediyl]bis(oxy)]bis-1-propanethiol, 3-[2,2-bis[(3-mercaptopropoxy)methyl]butoxy]-1-propanethiol, 3-(3-mercaptopropoxy)-2,2-bis[(3-mercaptopropoxy)methyl]-1-propanol, Mercaptoalkyl ether compounds such as 2,2-bis[(3-mercaptopropoxy)methyl]-1-butanol; 1,3,4,6-tetrakis(2-mercaptoethyl)glycoluril, 1,3,4,6-tetrakis(3-mercaptopropyl)glycoluril and the like can be mentioned, and 1,3,4,6-tetrakis(2-mercaptoethyl)glycoluril and 1,3,4,6-tetrakis(3-mercaptopropyl)glycoluril are preferred. These other thiol compounds may be used alone or in combination of two or more thereof.

[0084]

Chemical formula

[0085]

Chemical formula

[0086] As the amine compound, as is conventionally known, any compound having at least one amino group selected from a primary amino group, a secondary amino group, and a tertiary amino group in the molecule may be used.

[0087] Examples of such amine compounds include aliphatic amines such as diethylenetriamine, triethylenetetramine, isophoronediamine, xylylenediamine, diaminodiphenylmethane, 1,3,4,6 - tetrakis(3 - aminopropyl) glycoluril, n - propylamine, 2 - hydroxyethylaminopropylamine, cyclohexylamine, 4,4′ - diaminodicyclohexylmethane, dimethylbenzylamine; aromatic amines such as 4,4′ - diaminodiphenylmethane, o - methylaniline; nitrogen - containing heterocyclic compounds such as 2 - ethyl - 4 - methylimidazole, 2 - methylimidazole, 2 - ethyl - 4 - methylimidazoline, 2,4 - dimethylimidazoline, piperidine, piperazine, etc.

[0088] The content of the curing agent in the curable composition of the present invention is preferably 0.1 to 50 parts by weight, more preferably 1 to 40 parts by weight, based on 100 parts by weight of the epoxy - oxetane compound.

[0089] The reaction product of an epoxy compound and an amine compound or the reaction product of a compound having one or more isocyanate groups in the molecule and a compound having at least one of a primary amino group and a secondary amino group in the molecule is a solid that is poorly soluble in an epoxy resin at room temperature and becomes solubilized (easily solubilized) by heating, functioning as a curing accelerator, and is thus also referred to as a latent curing accelerator (hereinafter, these reaction products may sometimes be referred to as "latent curing accelerators").

[0090] As the epoxy compound used as a raw material for the latent curing accelerator composed of the reaction product of an epoxy compound and an amine compound, in addition to the above-mentioned epoxy compounds, glycidylamine compounds obtained by reacting 4,4'-diaminodiphenylmethane, m-aminophenol, etc. with epichlorohydrin; Examples thereof include monofunctional epoxy compounds such as butyl glycidyl ether, phenyl glycidyl ether, and glycidyl methacrylate.

[0091] As the amine compound used as a raw material for the latent curing accelerator composed of the reaction product of an epoxy compound and an amine compound, the above-mentioned amine compounds can be mentioned. Among these amine compounds, amine compounds having a tertiary amino group in the molecule are raw materials that give latent curing accelerators having excellent curing acceleration properties. Such amine compounds include, for example, amines such as dimethylaminopropylamine, diethylaminopropylamine, di-n-propylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine, and N-methylpiperazine; amines having a tertiary amino group in the molecule such as imidazole compounds such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, and 2-phenylimidazole; 2-Dimethylaminoethanol, 1-methyl-2-dimethylaminoethanol, 1-phenoxymethyl-2-dimethylaminoethanol, 2-diethylaminoethanol, 1-butoxymethyl-2-dimethylaminoethanol, 1-(2-hydroxy-3-phenoxypropyl)-2-methylimidazole, 1-(2-hydroxy-3-phenoxypropyl)-2-ethyl-4-methylimidazole, 1-(2-hydroxy-3-butoxypropyl)-2-methylimidazole, 1-(2-hydroxy-3-butoxypropyl)-2-ethyl-4-methylimidazole, 1-(2-hydroxy-3-phenoxypropyl)-2-phenylimidazoline, 1-(2-hydroxy-3-butoxypropyl)-2-methylimidazoline, 2-(dimethylaminomethyl)phenol, 2,4,6-tris(dimethylaminomethyl)phenol, N-β-hydroxyethylmorpholine, 2-dimethylaminoethanethiol, 2-mercaptopyridine, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 4-mercaptopyridine, N,N-dimethylaminobenzoic acid, N,N-dimethylglycine, nicotinic acid, isonicotinic acid, picolinic acid, N,N-dimethylglycine hydrazide, N,N-dimethylpropionic acid hydrazide, nicotinic acid hydrazide, isonicotinic acid hydrazide, and the like, including alcohols, phenols, thiols, carboxylic acids, hydrazides, etc. having a tertiary amino group in the molecule.

[0092] In order to further improve the storage stability of the curable composition of the present invention, as a raw material of a latent curing accelerator composed of a reaction product of an epoxy compound and an amine compound, in addition to the above epoxy compound and amine compound, an active hydrogen compound having two or more active hydrogens in the molecule may be used as a third component.

[0093] Examples of the active hydrogen compound include Polyhydric phenols such as bisphenol A, bisphenol F, bisphenol S, hydroquinone, catechol, resorcinol, pyrogallol, phenol novolak resin; Polyhydric alcohols such as trimethylolpropane; Polycarboxylic acids such as adipic acid and phthalic acid; Examples include 1,2-dimercaptoethane, 2-mercaptoethanol, 1-mercapto-3-phenoxy-2-propanol, mercaptoacetic acid, anthranilic acid, lactic acid, etc.

[0094] Furthermore, the latent curing accelerator composed of the reaction product of an epoxy compound and an amine compound may be surface-treated with an isocyanate compound or an acidic compound. Examples of the isocyanate compound include Monofunctional isocyanate compounds such as n-butyl isocyanate, isopropyl isocyanate, phenyl isocyanate, benzyl isocyanate, etc.; Polyfunctional isocyanate compounds such as hexamethylene diisocyanate, toluylene diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, xylylene diisocyanate, para-phenylene diisocyanate, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, etc.

[0095] Instead of this polyfunctional isocyanate compound, a terminal isocyanate group-containing compound obtained by the reaction of a polyfunctional isocyanate compound and an active hydrogen compound can also be used in the same manner as the polyfunctional isocyanate compound. Examples of such terminal isocyanate group-containing compounds include addition reaction products having terminal isocyanate groups obtained by the reaction of toluylene diisocyanate and trimethylolpropane, addition reaction products having terminal isocyanate groups obtained by the reaction of toluylene diisocyanate and pentaerythritol, etc.

[0096] In addition, the acidic compound used for the surface treatment of the latent curing accelerator composed of the reaction product of an epoxy compound and an amine compound may be any of a gas, a liquid, or a solid, and may be either an inorganic acid or an organic acid. Examples of such acidic compounds include carbon dioxide gas, sulfur dioxide gas, sulfuric acid, hydrochloric acid, oxalic acid, phosphoric acid, acetic acid, formic acid, propionic acid, adipic acid, caproic acid, lactic acid, succinic acid, tartaric acid, sebacic acid, p-toluenesulfonic acid, salicylic acid, boric acid, tannic acid, alginic acid, polyacrylic acid, polymethacrylic acid, phenol, pyrogallol, phenolic resin, resorcinol resin, and the like.

[0097] The latent curing accelerator composed of the reaction product of an epoxy compound and an amine compound is obtained by mixing an epoxy compound, an amine compound, and, if necessary, an active hydrogen compound, reacting them at a temperature from room temperature to 200°C, and then solidifying and pulverizing them, or reacting them in a solvent such as methyl ethyl ketone, dioxane, or tetrahydrofuran, and pulverizing the solid content after removing the solvent.

[0098] In addition, a latent curing accelerator composed of a reaction product of a commercially available epoxy compound and an amine compound can also be used. Examples of commercially available products include "Amicure PN-23 (trade name)", "Amicure PN-H (trade name)", "Amicure PN-50 (trade name)", "Amicure PN-23J (trade name)", "Amicure PN-40J (trade name)", "Amicure MY-24 (trade name)" manufactured by Ajinomoto Fine-Techno Co., Inc.; "Novacure HX-3088 (trade name)", "Novacure HX-3721 (trade name)", "Novacure HX-3722 (trade name)", "Novacure HX-3742 (trade name)", "Novacure HX-3941HP (trade name)", "Novacure HXA3922HP (trade name)" manufactured by Asahi Kasei Corporation; "Fujicure FXR-1030 (trade name)", "Fujicure FXR-1081 (trade name)", "Fujicure FXR-1121 (trade name)" manufactured by T&K TOKA Co., Ltd., and the like.

[0099] In the curable composition of the present invention, the content of the latent curing accelerator composed of the reaction product of an epoxy compound and an amine compound is preferably 0.1 to 100 parts by weight, more preferably 1 to 90 parts by weight, and still more preferably 1 to 80 parts by weight with respect to 100 parts by weight of the epoxy-oxetane compound.

[0100] As the isocyanate compound having one or more isocyanate groups in the molecule, which is used as a raw material for the latent curing accelerator composed of the reaction product of a compound having one or more isocyanate groups in the molecule and a compound having at least one of a primary amino group and a secondary amino group in the molecule, for example, n-butyl isocyanate, isopropyl isocyanate, 2-chloroethyl isocyanate, phenyl isocyanate, p-bromophenyl isocyanate, m-chlorophenyl isocyanate, o-chlorophenyl isocyanate, p-chlorophenyl isocyanate, 2,5-dichlorophenyl isocyanate, 3,4-dichlorophenyl isocyanate, 2,6-dimethylphenyl isocyanate, o-fluorophenyl isocyanate, p-fluorophenyl isocyanate, m-tolyl isocyanate, p-tolyl isocyanate, o-trifluoromethylphenyl isocyanate, m-trifluoromethylphenyl isocyanate, benzyl isocyanate, hexamethylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethane-4,4'-diisocyanate, 2,2-dimethyldiphenylmethane-4,4'-diisocyanate, tolidine diisocyanate, isophorone diisocyanate, xylylene diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, p-phenylene diisocyanate, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, tris-(3-isocyanato-4-methylphenyl)isocyanurate, tris-(6-isocyanatohexyl)isocyanurate and the like can be mentioned.

[0101] As a raw material for a latent curing accelerator composed of a reaction product of a compound having one or more isocyanate groups in the molecule and a compound having at least one of a primary amino group and a secondary amino group in the molecule, examples of the compound having at least one of a primary amino group and a secondary amino group in the molecule include dimethylamine, diethylamine, di-n-propylamine, di-n-butylamine, di-n-hexylamine, di-n-octylamine, di-n-ethanolamine, dimethylaminopropylamine, diethylaminopropylamine, morpholine, piperidine, 2,6-dimethylpiperidine, 2,2,6,6-tetramethylpiperidine, piperazine, pyrrolidine, benzylamine, N-methylbenzylamine, cyclohexylamine, metaxylylenediamine, 1,3-bis(aminomethyl)cyclohexane, isophoronediamine, N-aminoethylpiperazine, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-phenylimidazole, 1,1-dimethylhydrazine and the like.

[0102] The reaction product of a compound having one or more isocyanate groups in the molecule and a compound having at least one of a primary amino group and a secondary amino group in the molecule can be obtained by reacting the two in an organic solvent such as dichloromethane.

[0103] Regarding the content of the latent curing accelerator composed of the reaction product of a compound having one or more isocyanate groups in the molecule and a compound having at least one of a primary amino group and a secondary amino group in the molecule in the curable composition of the present invention, it is preferably 1 to 10 parts by weight with respect to 100 parts by weight of the epoxy-oxetane compound.

[0104] The curable composition of the present invention further, as long as it does not inhibit the effects of the present invention, pigments (titanium white, cyanine blue, watching red, bengala, carbon black, aniline black, manganese blue, iron black, ultramarine blue, hansa red, chrome yellow, chrome green, etc.), Inorganic fillers (such as calcium carbonate, kaolin, clay, talc, mica, barium sulfate, lithopone, gypsum, zinc stearate, perlite, quartz, fused silica, spherical silica powder such as spherical silica, spherical alumina, crushed alumina, oxides such as magnesium oxide, beryllium oxide, titanium oxide, nitrides such as boron nitride, silicon nitride, aluminum nitride, carbides such as silicon carbide, hydroxides such as aluminum hydroxide, magnesium hydroxide, metals and alloys such as copper, silver, iron, aluminum, nickel, titanium, carbon-based materials such as diamond, carbon, etc.), Thermoplastic resins and thermosetting resins (homopolymers such as various high-density, medium-density, and low-density polyethylene, polypropylene, polybutene, polypentene, ethylene-propylene copolymer, polyamide resins such as nylon-6, nylon-6,6, vinyl chloride resins, nitrocellulose resins, vinylidene chloride resins, acrylamide resins, styrene resins, vinyl ester resins, polyester resins, phenolic resins (phenolic compounds), silicone resins, fluorine resins, various elastomer resins such as acrylic rubber, urethane rubber, graft copolymers such as methyl methacrylate-butadiene-styrene graft copolymer and acrylonitrile-butadiene-styrene graft copolymer, etc.), Reinforcing agents (such as glass fiber, carbon fiber, etc.), Dripping inhibitors (such as hydrogenated castor oil, fine particle anhydrous silicic acid, etc.), Matting agents (such as fine powder silica, paraffin wax, etc.), Abrasive agents (such as zinc stearate, etc.), Internal mold release agents (fatty acids such as stearic acid, fatty acid metal salts of calcium stearate, fatty acid amides such as stearic acid amide, fatty acid esters, polyolefin wax, paraffin wax, etc.), It may contain additives (modifiers) such as surfactants, leveling agents, defoaming agents, viscosity-adjusting diluents (organic solvents), coupling agents, fragrances, flame retardants, etc.

[0105] In the preparation of the curable composition of the present invention, there are no particular restrictions on the preparation method, and it is prepared by weighing out the above-described respective components in predetermined amounts and stirring and mixing them. For example, after preliminary mixing, it can be prepared by mixing or melt-kneading using a roll kneader, a kneader, an extruder, or the like. If necessary, an organic solvent (viscosity-adjusting diluent) may be used.

[0106] The curable composition of the present invention polymerizes (cures) upon irradiation with ultraviolet rays or heating to give a cured product. Examples of the ultraviolet irradiation means include methods using light sources such as chemical lamps, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, and metal halide lamps. Regarding the irradiation intensity and irradiation time of ultraviolet rays, they are appropriately set in consideration of the desired irradiation intensity or desired irradiation time, and also in consideration of the composition and shape (thickness) of the curable composition to be irradiated. Examples of the heating means include methods such as hot air circulation, infrared heating, and high-frequency heating. Further, as the curing apparatus, a closed curing furnace, a tunnel furnace capable of continuous curing, or the like can be used. Regarding the heating (curing) temperature and heating (curing) time, similar to the case of ultraviolet irradiation, they may be appropriately set in consideration of the composition and shape (thickness) of the curable composition to be irradiated.

[0107] Since the curable composition of the present invention has a low viscosity, it can be used as a curable ink composition. Further, the curable composition of the present invention has a low viscosity and excellent dischargeability. Therefore, it is also suitable as a curable ink composition for inkjet. By applying the curable ink composition for inkjet to a predetermined object using the inkjet method and curing it, it is used in the production of various components and members described below. In the inkjet method, since a resin film can be formed at high speed and uniformly over a wide area, there are advantages such as improvement in product accuracy of various components and members described below and reduction in manufacturing cost.

[0108] The curable ink composition and the curable ink composition for inkjet are preferably measured using a differential thermal thermogravimetric analyzer under the conditions of a sample weight of 10 mg, a temperature increase condition of 10 °C / min, and a nitrogen flow (200 mL / min) from the perspective of volatility, and the 5% weight loss temperature (°C) is 185 °C or higher, more preferably 190 °C or higher.

[0109] The curable ink composition for inkjet preferably has a viscosity measured at 25 °C using a dynamic viscoelasticity measuring device (manufactured by UBM, "Rheosol-G5000") of 5 mPa·s or more and 150 mPa·s or less, more preferably 10 mPa·s or more and 80 mPa·s or less, and even more preferably 10 mPa·s or more and 40 mPa·s or less. In addition, when applying by the inkjet method, the curable ink composition for inkjet may be heated to lower the viscosity and then applied.

[0110] Also, the curable ink composition for inkjet preferably has a surface tension measured with a dynamic wettability tester at 25 °C of 15 mN / m or more and 35 mN / m or less, more preferably 20 mN / m or more and 30 mN / m or less.

[0111] Preferable examples of the curable ink composition for inkjet include curable compositions for optical element encapsulation used as encapsulants for optical elements such as organic electroluminescence (hereinafter referred to as organic EL) elements and organic thin film solar cell elements, adhesives for optical members used for bonding optical lenses, etc., curable compositions for stereolithography used in the production of various parts and members by 3D printers, curable compositions for nanoimprinting used in the formation of ultra-fine circuit patterns of semiconductors, and the like.

[0112] As an example, the curable composition of the present invention is used as a curable composition for optical element encapsulation. As a method for manufacturing an optical element, there is a method including a step of applying the curable composition for optical element encapsulation to at least one of two substrates by an inkjet method, a step of curing the applied curable composition for optical element encapsulation by light irradiation and / or heating, and a step of bonding the two substrates together.

[0113] In the step of applying the curable composition for optical element encapsulation to at least one of two substrates, the curable composition for optical element encapsulation may be applied to the entire surface of the substrate or may be applied to a part of the substrate. For example, when manufacturing an organic EL element as an optical element, the shape of the sealing agent portion formed by applying the curable composition for optical element encapsulation is not particularly limited as long as it can protect the laminate having the organic light-emitting material layer sandwiched between the two substrates from the outside air. That is, it may be a shape that completely covers the laminate, or may be a pattern shape that closes the peripheral portion of the laminate.

[0114] The step of curing the curable composition for optical element encapsulation by light irradiation and / or heating may be performed before the step of bonding the two substrates together, or may be performed after the step of bonding the two substrates together. When the step of curing the curable composition for optical element encapsulation by light irradiation and / or heating is performed before the step of bonding the two substrates together, it may be bonded within the pot life (for example, 1 minute) until the curing reaction proceeds and adhesion becomes impossible after light irradiation and / or heating.

[0115] Also, in the step of curing the applied curable composition for optical element encapsulation by light irradiation and / or heating, it may be performed by the above-described ultraviolet irradiation means and / or heating means.

[0116] The curable composition of the present invention has no particular limitation in its use, and is applicable to products (parts and members) in various fields where the material may be a resin, and can be used as a raw material for materials in the fields of electric and electronic, optical, architectural, civil engineering, automotive and aircraft, medical, and other daily and miscellaneous goods.

[0117] For example, examples of components, members, and materials in the electrical and electronic fields include copper-clad laminates, prepregs, copper-clad laminates, printed wiring boards, solder resist inks, anisotropic conductive films, anisotropic conductive pastes, interlayer insulating materials, adhesives, pressure-sensitive adhesives, sealing materials, encapsulants (encapsulation materials), encapsulation sheets, insulating materials, thermally conductive materials, hot melt materials, paints, potting agents, etc. More specifically, Encapsulation materials (encapsulants) for printed wiring boards and electronic components such as interlayer insulating films and wiring coating films, encapsulation materials (encapsulation materials) for image display devices, encapsulation sheets for image display devices, encapsulation materials (encapsulation materials) for organic EL display elements, encapsulation sheets for organic EL display elements, layer forming materials; Forming materials for display devices such as color filters, polarizing plates, display materials, resist materials, alignment films; Forming materials for semiconductor devices such as resist materials and buffer coat films; Forming materials for optical components such as lenses, holograms, optical waveguides, optical circuits, optical circuit components, and antireflection films; Coating agents such as surface protection films, hard coat agents, antifouling films, and antireflection films for semiconductor elements and organic thin film elements (for example, organic electroluminescence elements and organic thin film solar cell elements); etc. can be mentioned. In addition, materials for organic electronics elements such as organic EL elements, organic transistors, and solar cells, forming materials for rigid wiring boards and flexible printed wiring boards for semiconductor mounting, mounting materials for semiconductor mounting, adhesives for flexible printed wiring boards, encapsulants for semiconductors, encapsulants for solar cells, insulating films for semiconductors, coverlay films for protecting flexible printed circuits, coating agents for wiring coating, etc. can be mentioned.

[0118] Examples of materials in the optical field include lenses, prisms, films, core materials for optical fibers, cladding materials, abrasion-resistant coating agents for plastic lenses, materials for stereolithography, optical waveguides, filters, image display materials, lens arrays, encapsulating materials and reflector materials for optical semiconductor elements, light guide plates, light diffusing plates, diffractive elements, and optical adhesives, etc. For example, lenses and prisms are not particularly limited as long as they utilize refraction on the surface. Also, materials for lenses of camera modules, LiDAR modules, and steel cameras; adhesives for finder prisms, target prisms, finder covers, light-receiving sensor parts, photographing lenses, projection lenses of projection TVs, etc.; optical fiber materials around optical switches and around optical connectors in optical communication systems; encapsulating materials and adhesives around optical passive components, optical circuit components, optoelectronic integrated circuits, etc.; and can be used as such. Adhesive locations of camera modules include between image sensors (imaging elements) such as CMOS and CCD and substrates, between cut filters and substrates, between substrates and housings, between housings and cut filters, between housings and lens units, etc.

[0119] As lenses and prisms, spherical lenses whose surfaces are spherical, such as biconvex lenses, plano-convex lenses, and convex meniscus lenses, and concave lenses such as biconcave lenses, plano-concave lenses, and concave meniscus lenses; aspherical lenses having aspherical surfaces such as symmetric paraboloids, ellipsoids, hyperboloids, and higher-order surfaces (e.g., fourth-order surfaces), and aspherical lenses having free-form surfaces without a symmetry axis; cylindrical lenses such as bell-shaped and cylindrical surface lenses; toroidal lenses having a toroidal surface with different radii of curvature in the vertical and horizontal directions like the surface of a donut; An annular prism having a reflecting surface that inclines in the same way as the curve of a thick convex lens to change the traveling direction of light and a refracting surface that transmits light is arranged on a plane, and a plurality of these prisms are thin Fresnel lenses that continuously become smaller or larger as they approach the center; A diffractive lens having concentrically formed fine reliefs with a depth of about the wavelength of light; Examples of prisms having two or more optical planes and at least one set of planes being substantially non-parallel can be cited. Examples of films include reflective films that are formed by treating inorganic compounds such as MgF2 and SiO2 by vacuum deposition, sputtering, or CVD methods, or by coexisting a light absorber, and that transmit light in a desired wavelength range while reflecting light in an undesired wavelength range.

[0120] Examples of materials in the construction field include sealing materials, coating materials, and primers for joints of exterior materials such as various metal panels and siding boards; Sealing materials, adhesives, injection materials, vibration damping materials, sound insulation materials, conductive materials for electromagnetic wave shielding, and putty used between exterior materials, base materials, ceiling materials, and interior materials; Adhesives for bonding tiles and stones to exterior wall materials and base materials; Adhesives and adhesives for bonding wooden flooring materials, polymer material-based floor sheets, and floor tiles to various floors; Examples include injection materials for crack repair of various exterior and interior materials, etc.

[0121] Examples of materials in the civil engineering field include sealing materials, coating materials, primers, paints, putty materials, injection materials, spraying materials, and formwork materials for joints of various concrete products such as roads, bridges, tunnels, and breakwaters;

[0122] Examples of materials in the automotive and aircraft fields include structural materials, fiber-reinforced composite materials, adhesives for bodies and parts, sealing materials, coating materials, cushioning materials, vibration damping materials, sound insulation materials, and spraying materials; Adhesives, adhesives, coating materials, and foaming materials for automotive interiors; Examples include sealing materials, adhesives, and coating materials for steel plate joints, etc. In addition, as applications of a substrate having a coating layer made of a cured product of the curable composition of the present invention on its surface, examples include members of various industrial equipment such as transportation machines (automobiles, aircraft, etc.), electronic and electrical equipment, etc. (for example, sliding members such as cylinders, pistons, bearings, etc.).

[0123] Examples of materials in the medical field include artificial bones, dental impression materials, medical rubber materials, medical adhesives, medical device sealing materials, and the like.

[0124] Other examples include paints to be applied on substrates such as metals, resin films, glass, paper, wood, and the like.

Examples

[0125] Hereinafter, the present invention will be described in more detail using examples and comparative examples, but the present invention is not limited thereto. The main raw materials used are as follows. · Allyl glycidyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) · Allyl alcohol (manufactured by Fujifilm Wako Pure Chemical Corporation) · Potassium tert-butoxide (manufactured by Tokyo Chemical Industry Co., Ltd.) · 3-Ethyl-3-methanesulfonyloxymethyloxetane (synthesized according to the method described in JP-A-2007-332294). · Sodium hydroxide (manufactured by Fujifilm Wako Pure Chemical Corporation) · Meta-chloroperbenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) · 1,2,3-Glycidyloxypropane (manufactured by Anhui Xinyuan Technology Co., Ltd., trade name "XY633", a compound represented by chemical formula (IV)). · Glycerin (manufactured by Fujifilm Wako Pure Chemical Corporation) · 3-Ethyl-3-hydroxymethyloxetane (manufactured by Ube Industries, Ltd.) · Allyl chloride (manufactured by Fujifilm Wako Pure Chemical Corporation) · 2-Chloromethyloxirane (manufactured by Osaka Soda Co., Ltd.) · Allyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) · Sodium iodide (manufactured by Fujifilm Wako Pure Chemical Corporation) · Potassium iodide (manufactured by Fujifilm Wako Pure Chemical Corporation)

[0126] [Chemistry]

[0127] (C) Thermal cationic polymerization initiator · Dibenzylmethyl-p-hydroxyphenylsulfonium hexafluoroantimonate (manufactured by Sanshin Chemical Industry Co., Ltd., "Sun-Aid SI-100L (trade name)")

[0128] The measuring methods for viscosity, elastic modulus, loss tangent, flexural elastic modulus, and flexural strength, which are the evaluation tests adopted in the examples and comparative examples, are as follows.

[0129] [Measurement of viscosity] Regarding the epoxy·oxetane compounds (including epoxy compounds and oxetane compounds) used in the examples and comparative examples described later, the viscosity at 25°C was measured using a dynamic viscoelasticity measuring device (manufactured by UBM, "Rheosol-G5000"). It is determined that the smaller the viscosity value (lower viscosity), the better the workability during the preparation of the curable composition and when using the curable composition as an adhesive.

[0130] [Measurement of elastic modulus and loss tangent] Regarding the curable compositions prepared in the examples and comparative examples described later, they were cured under the conditions of 65°C / 2 hours and further heated and cured under the conditions of 150°C / 2 hours. For the obtained cured product (test piece: length 30 mm × width 10 mm × thickness 1 mm), the storage elastic modulus G′ (MPa) and loss tangent tanδ at 25°C were measured using a dynamic viscoelasticity measuring device (manufactured by UBM, "Rheosol-G5000") (frequency: 1 Hz). It is determined that the larger the value of this storage elastic modulus G′ (higher elasticity), the better the rigidity, and the smaller the value of the loss tangent tanδ, the fewer the structural defects in the cured product and the more uniform the three-dimensional network is formed.

[0131] [Measurement of Flexural Elastic Modulus and Flexural Strength] For the curable compositions prepared in the examples and comparative examples described below, they were cured under the conditions of 65 °C for 2 hours, and further cured by heating under the conditions of 150 °C for 2 hours. For the obtained cured products (test pieces: length 80 mm × width 25 mm × thickness 1 mm), the flexural elastic modulus (GPa) and flexural strength (MPa) were measured in accordance with JIS K7203. The larger the flexural elastic modulus (higher elasticity), the better the rigidity, and the larger the flexural strength, the better the mechanical strength is determined.

[0132] [Synthesis of Epoxy-Oxetane Compound Represented by Chemical Formula (I-1)] [Synthesis Example 1] A 5 L three-necked flask was charged with 2178 g (37500 mmol) of allyl alcohol and 308.58 g (2750 mmol) of potassium tert-butoxide, heated to 40 °C, and then 285.35 g (2500 mmol) of allyl glycidyl ether was added dropwise, and the mixture was stirred at 60 °C for 14 hours. Then, after cooling the reaction solution to 25 °C, the reaction solution was filtered to remove solids, and the filtrate was distilled off under reduced pressure. The obtained concentrated solution was purified by distillation to obtain 391.19 g of a bifunctional olefin compound having a hydroxyl group represented by chemical formula (II-1) as a colorless transparent liquid (yield: 91%).

[0133] [Chemical Formula]

[0134] [Synthesis Example 2] A 5 L four-necked flask was charged with 344.44 g (2000 mmol) of the colorless transparent liquid obtained in Synthesis Example 1, 1500 g of dimethyl sulfoxide, and 114.96 g (2874 mmol) of sodium hydroxide. After heating to 60 °C, 427.35 g (2200 mmol) of 3-ethyl-3-methanesulfonyloxymethyloxetane was added dropwise, and the mixture was stirred at 70 °C for 8 hours. Then, the reaction solution was cooled to 25 °C, the solid was removed by filtration, and the filtrate was extracted with 2000 mL of ethyl acetate. Subsequently, after washing with 2000 mL of water, the organic layer was concentrated under reduced pressure. The obtained concentrated solution was purified by distillation to obtain 336.92 g of an olefin-oxetane compound represented by Chemical Formula (Ia-1) as a colorless transparent liquid (yield: 62%).

[0135]

Chemical formula

[0136] [Synthesis Example 3] A 1 L three-necked flask was charged with 54.07 g (200.0 mmol) of the colorless transparent liquid obtained in Synthesis Example 2, 86.29 g (500.0 mmol) of m-chloroperbenzoic acid, and 500 g of chloroform, and the mixture was stirred at 30 °C for 12 hours. The reaction solution was filtered to remove the solid, washed with 500 mL of a 10 wt% aqueous potassium carbonate solution and 500 mL of water, and then the organic layer was concentrated under reduced pressure. The obtained concentrate was purified by silica gel column chromatography (ethyl acetate / hexane = 1 / 3 (volume ratio)) to obtain 26.49 g of a pale yellow transparent liquid (yield: 44%).

[0137] The 1 1H-NMR spectral data of this pale yellow transparent liquid were as follows. · 1 1H-NMR (CDCl3) δ: 4.46 (d, 2H), 4.37 (d, 2H), 3.79 (m, 2H), 3.74 (t, 2H), 3.61 (m, 5H), 3.41 (m, 2H), 3.13 (quin., 2H), 2.79 (t, 2H), 2.60 (m, 2H), 1.74 (q, 2H), 0.88 (t, 3H). The IR spectral data of this pale yellow transparent liquid was as shown in the chart of Figure 1. From these spectral data, the obtained pale yellow transparent liquid was identified as an epoxy-oxetane compound represented by Chemical Formula (I-1).

[0138]

Chemical Formula

[0139] <Synthesis of Oxetane Compound Represented by Chemical Formula (V)> 〔Synthesis Example 4〕 A 500 mL three-necked flask was charged with 18.42 g (200.0 mmol) of glycerin, 180.0 g of dimethyl sulfoxide, and 22.20 g (555.0 mmol) of sodium hydroxide. After heating to 60 °C, 104.90 g (540.0 mmol) of 3-ethyl-3-methanesulfonyloxymethyloxetane was added dropwise, and the mixture was stirred at 70 °C for 8 hours. Then, the reaction solution was cooled to 25 °C, the solid matter was removed by filtration, and the filtrate was extracted with 200 mL of ethyl acetate. Subsequently, after washing with 60 mL of water, the organic layer was concentrated under reduced pressure. The obtained concentrate was purified by silica gel column chromatography (ethyl acetate / hexane = 2 / 3 (volume ratio)) to obtain 8.50 g of a colorless transparent liquid (yield: 11%).

[0140] The 1 1H-NMR spectral data of this colorless transparent liquid was as follows. · 1 1H-NMR (CDCl3) δ: 4.44 (d, 6H), 4.35 (d, 6H), 3.72 (s, 2H), 3.66(quin., 1H), 3.57 (m, 6H), 3.55 (d, 2H), 1.74 (q, 6H), 0.88 (t, 9H). The IR spectral data of this colorless transparent liquid was as shown in the chart of Figure 2. From these spectral data, the obtained colorless transparent liquid was identified as an oxetane compound represented by chemical formula (V).

[0141] [Chemical formula]

[0142] [Synthesis of epoxy-oxetane compound represented by chemical formula (VIII)] [Synthesis Example 5] A 1-L three-necked flask was charged with 174.24 g (1500 mmol) of 3-ethyl-3-hydroxymethyloxetane and 8.00 g (200.0 mmol) of sodium hydroxide, heated to 45°C, and then 114.14 g (1000 mmol) of allyl glycidyl ether was added dropwise. The mixture was stirred at 50°C for 12 hours. Thereafter, the reaction solution was cooled to 25°C, extracted with 750 mL of chloroform, washed with 500 mL of water, and the organic layer was concentrated under reduced pressure to obtain 223.4 g of a compound represented by chemical formula (VI) as a pale yellow transparent liquid (yield: 97%).

[0143] [Chemical formula]

[0144] [Synthesis Example 6] A 2-L three-necked flask was charged with 184.73 g (750.0 mmol) of the pale yellow transparent liquid obtained in Synthesis Example 5, 750.00 g of dimethyl sulfoxide, 45.00 g (1125.0 mmol) of sodium hydroxide, and 5.62 g (37.5 mmol) of sodium iodide, heated to 50°C, and then 86.10 g (1125.0 mmol) of allyl chloride was added dropwise. The mixture was stirred at 50°C for 8 hours. Thereafter, the reaction solution was cooled to 25°C, the solid matter was removed by filtration, and the filtrate was extracted with 1500 mL of ethyl acetate. Subsequently, it was washed with 1500 mL of water, and the organic layer was concentrated under reduced pressure. The obtained concentrated solution was purified by distillation to obtain 121.67 g of a compound represented by chemical formula (VII) as a colorless transparent liquid (yield: 60%).

[0145] [Chemical formula]

[0146] [Synthesis Example 7] Into a 500 mL three-necked flask, 27.03 g (100.0 mmol) of the colorless transparent liquid obtained in Synthesis Example 6, 43.14 g (250.0 mmol) of metachloroperbenzoic acid, and 250 g of chloroform were charged, and the mixture was stirred at 30 °C for 12 hours. The reaction solution was filtered to remove solids, washed with 250 mL of a 10 wt% aqueous potassium carbonate solution and 250 mL of water, and then the organic layer was concentrated under reduced pressure. The obtained concentrate was purified by silica gel column chromatography (ethyl acetate / hexane = 1 / 3 (volume ratio)) to obtain 12.02 g of a pale yellow transparent liquid (yield: 40%).

[0147] For this pale yellow transparent liquid, 1 the 1H-NMR spectrum data was as follows. · 1 1H-NMR (CDCl3) δ: 4.46 (d, 2H), 4.36 (d, 2H), 3.91 (m, 1H), 3.76 (m, 2H), 3.60 (m, 7H), 3.41 (m, 1H), 3.15 (m, 2H), 2.78 (m, 2H), 2.61 (m, 2H), 1.74 (q, 2H), 0.89 (t, 3H). The IR spectrum data of this pale yellow transparent liquid was as shown in the chart of Figure 3. From these spectrum data, the obtained pale yellow transparent liquid was identified as an epoxy·oxetane compound represented by Chemical Formula (VIII).

[0148] [Chemical formula]

[0149] [Synthesis of an epoxy·oxetane compound represented by Chemical Formula (XI)] [Synthesis Example 8] A 1 L three-necked flask was charged with 278.78 g (2400.0 mmol) of 3-ethyl-3-hydroxymethyloxetane and 38.40 g (960.0 mmol) of sodium hydroxide. After heating to 47 °C, 74.02 g (800.0 mmol) of 2-chloromethyloxirane was added dropwise, and the mixture was stirred at 60 °C for 4 hours. Thereafter, the reaction solution was cooled to 25 °C, extracted with 900 mL of chloroform, washed with 500 mL of water, and the organic layer was concentrated under reduced pressure. By distillation and purification of the concentrated solution, 87.51 g of the compound represented by chemical formula (IX) was obtained as a colorless transparent liquid (yield: 38%).

[0150] [Chemical formula]

[0151] [Synthesis Example 9] A 300 mL three-necked flask was charged with 40.37 g (140.0 mmol) of the colorless transparent liquid obtained in Synthesis Example 8, 8.12 g (203.0 mmol) of sodium hydroxide, and 1.16 g (7.0 mmol) of potassium iodide. After heating to 67 °C, 13.93 g (182.0 mmol) of allyl chloride was added dropwise, and the mixture was stirred at 70 °C for 2 hours. Thereafter, the reaction solution was cooled to 25 °C, the solid matter was removed by filtration, and the filtrate was extracted with 80 mL of ethyl acetate. Subsequently, after washing with 40 mL of water, the organic layer was concentrated under reduced pressure to obtain 44.79 g of the compound represented by chemical formula (X) as a colorless transparent liquid (yield: 97%).

[0152] [Chemical formula]

[0153] [Synthesis Example 10] A 500 mL three-necked flask was charged with 42.70 g (130.0 mmol) of the colorless transparent liquid obtained in Synthesis Example 9, 22.43 g (130.0 mmol) of metachloroperbenzoic acid, and 300 g of chloroform, and stirred at 30 °C for 12 hours. Subsequently, the reaction solution was filtered to remove solids and washed with 150 mL of a 10 wt% aqueous potassium carbonate solution and 150 mL of water. The organic layer was concentrated under reduced pressure to obtain 38.44 g of a colorless transparent liquid (yield: 86%).

[0154] The 1 1H-NMR spectral data of this colorless transparent liquid was as follows. · 1 1H-NMR (CDCl3) δ: 4.44 (d, 4H), 4.35 (d, 4H), 3.89 (dd, 1H), 3.72 (quin., 1H), 3.56 (m, 9H), 3.12(quin, 1H), 2.77 (t, 1H), 2.60 (dd, 1H), 1.72 (q, 4H), 0.87 (t, 6H). The IR spectral data of this colorless transparent liquid was as shown in the chart of Figure 4. From these spectral data, the obtained colorless transparent liquid was identified as an epoxy-oxetane compound represented by chemical formula (XI).

[0155]

Chemical formula

[0156] 〔Synthesis Example 11〕 Into a 1 L three-necked eggplant flask, 49.26 g (200.0 mmol) of the pale yellow transparent liquid obtained in Synthesis Example 5, 200.00 g of dimethyl sulfoxide, 10.40 g (260.0 mmol) of sodium hydroxide, and 1.50 g (10.0 mmol) of sodium iodide were charged. After heating to 50 °C, 50.51 g (260.0 mmol) of 3-ethyl-3-methanesulfonyloxymethyloxetane was added dropwise, and the mixture was stirred at 50 °C for 8 hours. Then, the reaction solution was cooled to 25 °C, the solid matter was removed by filtration, and the filtrate was extracted with 400 mL of ethyl acetate. Subsequently, after washing with 400 mL of water, the organic layer was concentrated under reduced pressure. By subjecting the obtained concentrated solution to distillation purification, 26.32 g of the compound represented by Chemical Formula (XII) was obtained as a colorless transparent liquid (yield: 40%).

[0157] [Chemical Formula]

[0158] [Synthesis Example 12] Into a 1 L three-necked eggplant flask, 26.28 g (80.0 mmol) of the colorless transparent liquid obtained in Synthesis Example 11, 16.57 g (96.0 mmol) of metachloroperbenzoic acid, and 500 g of chloroform were charged, and the mixture was stirred at 30 °C for 12 hours. The reaction solution was filtered to remove the solid matter, washed with 100 mL of a 10 wt% aqueous potassium carbonate solution and 100 mL of water, and then the organic layer was concentrated under reduced pressure. The obtained concentrate was purified by silica gel column chromatography (ethyl acetate / hexane = 2 / 3 (volume ratio)) to obtain 17.05 g of a pale yellow transparent liquid (yield: 62%).

[0159] The 1 1H-NMR spectral data of this pale yellow transparent liquid was as follows. · 11H-NMR (CDCl3) δ: 4.43 (d, 4H), 4.32 (d, 4H), 3.77 (dd, 1H), 3.72 (d, 2H), 3.56 (m, 7H), 3.39 (m, 1H), 3.12(quin., 1H), 2.78 (t, 1H), 2.59 (dd, 1H), 1.72 (q, 4H), 0.87 (t, 6H). The IR spectral data of this pale yellow transparent liquid was as shown in the chart of FIG. 5. From these spectral data, the obtained pale yellow transparent liquid was identified as an epoxy-oxetane compound represented by the chemical formula (XIII).

[0160] [Chemical formula]

[0161] <Evaluation of the cured product> [Example 1] 100 parts by weight of the epoxy-oxetane compound represented by the chemical formula (I-1) synthesized in Synthesis Example 3 and 0.2 parts by weight of a thermal cationic polymerization initiator were uniformly mixed to prepare a curable composition. When the above-described evaluation tests were conducted on this curable composition and the cured product obtained by curing the curable composition, the obtained test results were as shown in Table 1.

[0162] [Comparative Examples 1 to 5] In the same manner as in Example 1, curable compositions having the compositions shown in Table 1 were prepared, and the above-described evaluation tests were conducted on those curable compositions and the cured products obtained by curing the curable compositions. The obtained test results were as shown in Table 1.

[0163] [Table 1]

[0164] From Table 1, it was confirmed that the epoxy-oxetane compound contained in the curable composition of the present invention has an extremely low viscosity, and thus is excellent in workability during preparation and when used as a curable adhesive. In addition, since the cross-linking function of the curable composition of the present invention is exerted, a cured product is obtained by curing. Despite the low viscosity, the values of the storage elastic modulus G' and the flexural elastic modulus of the cured product are large, and the value of the flexural strength is large. Therefore, it was confirmed that the cured product has excellent mechanical strength. Since the cured product obtained by curing the curable composition of the present invention has a small loss tangent tanδ value, it is presumed that there are few structural defects in the cured product and a uniform three-dimensional network is formed.

Industrial Applicability

[0165] According to the curable composition of the present invention, a curable composition and its cured product having curability, low viscosity, and mechanical strength can be provided as compared with conventional curable compositions, and the industrial applicability of the present invention is great.

Claims

1. A curable composition comprising an epoxy oxetane compound represented by formula (I). 【Chemistry 1】 (In the formula, R may be the same or different and represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.)

2. The curable composition according to claim 1, which contains a cationic polymerization initiator.

3. A cured product obtained by curing the curable composition according to any one of claims 1 to 2.

4. An adhesive comprising the curable composition according to any one of claims 1 to 2.

5. A sealant comprising the curable composition according to any one of claims 1 to 2.

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