Curable composition, curable ink composition, curable inkjet ink composition, and use thereof

Abstract

To provide a curable composition, a curable ink composition, and a curable inkjet ink composition that concomitantly have low viscosity, low volatility, and curing properties, and also provide a method for using the compositions.SOLUTION: A curable composition contains an epoxy-oxetane compound indicated by chemical formula (I). In the formula, n assumes the same or different values and represents an integer of 2-5.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a curable composition, a curable ink composition, a curable inkjet ink composition, and methods of using them. [Background technology]

[0002] Oxetane compounds have attracted attention in recent years as photocurable and thermocurable monomers. Curable compositions containing these compounds as components shrink little when cured, and the cured products (resins) have excellent toughness, mechanical properties, heat resistance, electrical properties, water resistance, weather resistance, transparency, etc. Because of these excellent characteristics, curable compositions containing oxetane compounds are increasingly being used as raw materials for coating materials, paints, inks, adhesive materials, pressure-sensitive adhesive materials, films, pastes, optical materials, sealing materials, resist materials, and the like.

[0003] The prior art related to the present invention will be described below with reference to the literature. The invention described in Patent Document 1 relates to an epoxyoxacyclobutane compound and a polymer thereof. This document describes, as examples of epoxyoxacyclobutane compounds, 3,3-di(2,3-epoxypropoxymethyl)oxacyclobutane (see chemical formula (Ref-5)) and its methyl-substituted derivative, 3,3-di(2,3-epoxy-2-methylpropoxymethyl)oxacyclobutane (see chemical formula (Ref-1)).

[0004] [ka]

[0005] [ka]

[0006] The invention described in Patent Document 2 relates to an actinic radiation-curable ink-jet ink and a printed matter. This document describes compounds represented by chemical formulas (Ref-2) to (Ref-4) as examples of non-acrylic cationically polymerizable compounds having an oxirane ring (epoxy group) and an oxetane ring in the same molecule.

[0007] [ka]

[0008] [ka]

[0009] [ka]

[0010] Patent Documents 3 to 5 also describe the compounds represented by the above chemical formulas (Ref-2) to (Ref-4) or their analogous compounds.

[0011] Curable compositions used as curable ink compositions or curable inkjet ink compositions are required to have a high level of properties, including low viscosity to enable ink ejection, low volatility to prevent ink drying due to evaporation, and excellent curability by heat or light (fast curing speed). Curable compositions containing chemical formulas (Ref-1) to (Ref-5) do not have a high level of these properties, and have problems with viscosity (ejectability), volatility, or curability (curing speed). [Prior art documents] [Patent documents]

[0012] [Patent Document 1] U.S. Pat. No. 3,457,193 [Patent Document 2] JP 2005-002191 A [Patent Document 3] JP 2007-270070 A [Patent Document 4] JP 2010-111713 A [Patent Document 5] JP 2011-208089 A Summary of the Invention [Problem to be solved by the invention]

[0013] An object of the present invention is to provide a curable composition, a curable ink composition, and a curable inkjet ink composition that combine low viscosity, low volatility, and curability, and to provide a method for using these compositions. [Means for solving the problem]

[0014] The present inventors have recognized that the desired object can be achieved by employing a curable composition containing an epoxy oxetane compound represented by chemical formula (I) as the curable composition, curable ink composition, and curable inkjet ink composition, and have thus completed the present invention.

[0015] That is, the first invention is a curable composition containing an epoxy-oxetane compound represented by chemical formula (I). [ka] (In the formula, n is the same or different and represents an integer of 2 to 5.)

[0016] In addition, a cationic polymerization initiator may be contained.

[0017] A second invention is a curable ink composition containing a curable composition.

[0018] A third aspect of the present invention is a curable inkjet ink composition comprising a curable ink composition.

[0019] A fourth invention relates to a cured product obtained by curing at least one of the curable composition of the first invention, the curable ink composition of the second invention, and the curable inkjet ink composition of the third invention.

[0020] A fifth invention is a curable composition for encapsulating optical elements, comprising at least one of the curable composition of the first invention, the curable ink composition of the second invention, and the curable inkjet ink composition of the third invention.

[0021] It may also be used for sealing an organic electroluminescence element.

[0022] A sixth invention is an adhesive for optical members, comprising at least one of the curable composition of the first invention, the curable ink composition of the second invention, and the curable inkjet ink composition of the third invention.

[0023] A seventh invention is a curable composition for stereolithography containing at least one of the curable composition of the first invention, the curable ink composition of the second invention, and the curable inkjet ink composition of the third invention.

[0024] An eighth invention is a curable composition for nanoimprints containing at least any one of the curable composition of the first invention, the curable ink composition of the second invention, and the curable inkjet ink composition of the third invention. Effect of the Invention

[0025] The curable composition, curable ink composition, and curable inkjet ink composition containing the epoxy oxetane compound represented by chemical formula (I) can be a curable composition that has low viscosity and excellent ejection properties, low volatility and excellent maintenance properties, and further has excellent curing properties (fast curing speed). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0026] The curable compound of the present invention contains an epoxy-oxetane compound represented by chemical formula (I). The epoxy-oxetane compound represented by chemical formula (I) has a structure in which two epoxy groups are each bonded to an oxetane ring via a connector having one ether bond.

[0027] [ka]

[0028] In the above chemical formula (I), n is the same or different and represents an integer of 2 to 5. From the viewpoint of easy availability of raw materials and simplification of the synthesis process, n is preferably the same and an integer of 2 to 5, more preferably an integer of 2 to 4, further preferably an integer of 2 to 3, and particularly preferably 2.

[0029] Examples of the epoxy-oxetane compound represented by chemical formula (I) include compounds represented by chemical formulas (I-1) to (I-4).

[0030] [ka]

[0031] From the viewpoints of easy availability of raw materials and simplification of the synthesis process, 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-3), more preferably an epoxy oxetane compound represented by chemical formula (I-1) or chemical formula (I-2), and further preferably an epoxy oxetane compound represented by chemical formula (I-1). These may be used alone or in combination of two or more kinds.

[0032] <Synthesis method of epoxy-oxetane compound represented by chemical formula (I)> An oxetane compound having a leaving group represented by chemical formula (II) is reacted with an olefin compound having a hydroxyl 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 an epoxy-oxetane compound represented by chemical formula (I) (see reaction scheme (A)).

[0033] [ka]

[0034] In chemical formula (II), X is a leaving group, which may be the same or different 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). In chemical formulas (III) and (Ia), n has the same meaning as n in chemical formula (I).

[0035] Examples of the oxetane compound having a leaving group include 3,3-bis(chloromethyl)oxetane, 3,3-bis(bromomethyl)oxetane, and the like, with 3,3-bis(bromomethyl)oxetane being preferred.

[0036] Examples of the olefin compound having a hydroxyl group include compounds represented by chemical formulas (III-1) to (III-4). The olefin compounds may be used alone or in combination of two kinds. The amount (charge amount) of the olefin compound used is preferably an appropriate ratio within a range of 2 to 20 times the amount (charge amount) of the oxetane compound having a leaving group used.

[0037] [ka]

[0038] In addition, when the olefin compound represented by the chemical formula (III-1) or the olefin compound represented by the chemical formula (III-2) is used alone in the reaction, the epoxy-oxetane compound represented by the chemical formula (I-1) or the epoxy-oxetane compound represented by the chemical formula (I-2) can be obtained, respectively.

[0039] The olefin-oxetane compound represented by formula (Ia) can be synthesized in the presence of a base (i), a catalyst (ii) to promote the reaction, and a reaction solvent (iii) that does not inhibit the reaction. In addition, in the reaction for epoxidizing the double bond of the compound, a general epoxidation (oxidation) method can be adopted, for example, a method using a peracid, a method using hydrogen peroxide in the presence of sodium tungstate as a catalyst, a method using hydrogen peroxide together with a base in an acetonitrile-alcohol solvent, etc.

[0040] The base (i) may be a hydride, hydroxide, carbonate, hydrogencarbonate, alkoxide or organic amine compound of an alkali metal or alkaline earth metal. Examples include sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium alkoxide, potassium alkoxide (eg, potassium t-butoxide, etc.), triethylamine, and the like. The amount of base used (charged amount) is preferably an appropriate ratio usually within a range of 2 to 20 times the amount of oxetane compound used (charged amount) having a leaving group.

[0041] The catalyst (ii) includes quaternary ammonium salts, quaternary phosphonium salts, and the like. Examples of quaternary ammonium salts include salts of tetrabutylammonium, tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrahexylammonium, tetraoctylammonium, tetradecylammonium, hexadecyltriethylammonium, dodecyltrimethylammonium, trioctylmethylammonium, octyltriethylammonium, benzyltrimethylammonium, benzyltriethylammonium, benzyltributylammonium, benzyldimethyloctadecylammonium, and phenyltrimethylammonium halides (fluorides, chlorides, bromides, iodides), and the like.

[0042] Examples of quaternary phosphonium salts include salts of tetrabutylphosphonium, tetramethylphosphonium, tetraethylphosphonium, tetrapropylphosphonium, tetrahexylphosphonium, tetradecylphosphonium, tetraoctylphosphonium, triethyloctadecylphosphonium, trioctylethylphosphonium, hexadecyltriethylphosphonium, tetraphenylphosphonium, and methyltriphenylphosphonium halides (fluorides, chlorides, bromides, iodides), and the like.

[0043] Combinations of these materials may also be used as catalyst (ii). The amount (charged amount) of the catalyst (ii) used is preferably an appropriate ratio within a range of 0.0001 to 1.0 times the amount (charged amount) of the oxetane compound having a leaving group used.

[0044] The reaction solvent (iii) is not particularly limited as long as it does not inhibit the reaction, and examples thereof include water, methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol monomethyl ether, tetrahydrofuran, diethyl ether, dioxane, dimethoxyethane, polyethylene glycol (PEG-400), ethyl acetate, propyl acetate, butyl acetate, acetonitrile, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, N,N-dimethylformamide (DMF), dimethylacetamide (DMA), dimethylsulfoxide (DMSO), hexamethylphosphoric acid triamide (HMPA), and the like. One or more of these may be used in combination in an appropriate amount.

[0045] The reaction temperature in synthesizing the olefin-oxetane compound represented by the chemical formula (Ia) is preferably set in the range of 0 to 150° C., more preferably in the range of 20 to 120° C. The reaction time is appropriately set according to the set reaction temperature, but is preferably set in the range of 1 to 48 hours.

[0046] After the reaction is completed, the olefin-oxetane compound, which is the precursor of the target product, can be separated and extracted from the resulting reaction solution by, for example, solvent extraction. If necessary, the product can be further purified by washing with water or the like, treatment with activated carbon, silica gel chromatography, or the like.

[0047] In the reaction of epoxidizing an olefin-oxetane compound using the peracid, a peracid such as an oxone reagent, peracetic acid, metachloroperbenzoic acid (3-chloroperbenzoic acid) or the like can be used. The amount of peracid used (charged amount) is preferably an appropriate ratio within the range of 1.0 to 5.0 times the molar amount of the double bond of the olefin-oxetane compound.

[0048] In this epoxidation reaction, the reaction solvent is not particularly limited as long as it does not inhibit the reaction, but examples thereof include water, alcohols such as 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 hexamethylphosphorotriamide, and sulfoxides such as dimethyl sulfoxide (DMSO). These reaction solvents are used in appropriate amounts, either alone or in combination of two or more.

[0049] The reaction temperature in this epoxidation reaction is usually set in the range of −10 to 150° C., and preferably in the range of 0 to 100° C. The reaction time is appropriately set depending on the reaction temperature, and is usually set in the range of 1 to 24 hours, and preferably in the range of 1 to 6 hours.

[0050] After the reaction is completed, the target epoxy-oxetane compound represented by formula (I) can be separated and extracted from the resulting reaction solution by, for example, solvent extraction. If necessary, the product can be further purified by washing with water or the like, treatment with activated carbon, silica gel chromatography, or the like.

[0051] In the reaction of epoxidizing an olefin-oxetane compound with hydrogen peroxide using the sodium tungstate as a catalyst, hydrogen peroxide is used in a molar ratio of 1.0 to 5.0 times the double bond of the olefin-oxetane compound. The amount of sodium tungstate used (charged amount) is preferably an appropriate ratio within the range of 0.001 to 0.5 times the double bond of the olefin-oxetane compound.

[0052] The epoxidation reaction is not particularly limited as long as it does not inhibit the reaction, and for example, the same reaction solvents as those used in the above-mentioned epoxidation using a peracid can be used.

[0053] The reaction temperature in this epoxidation reaction is generally set in the range of −10 to 150° C., preferably 0 to 100° C., as in the case of the above-mentioned epoxidation using a peracid. The reaction time is appropriately set depending on the reaction temperature, but is generally set in the range of 1 to 24 hours, preferably 1 to 6 hours.

[0054] After the reaction is completed, the epoxy-oxetane compound represented by formula (I) can be separated and extracted from the reaction solution by, for example, solvent extraction, in the same manner as in the case of the epoxidation using peroxy acid. It may also be purified if necessary.

[0055] 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 an appropriate ratio within the range of 1.0 to 5.0 times the molar amount of the double bond possessed by the olefin-oxetane compound. The amount of acetonitrile used (charged amount) is preferably an appropriate ratio within a range of 0.5 to 5.0 times by mole relative to the olefin / oxetane compound. The amount of alcohol used (charged amount) is preferably an appropriate ratio within the range of 10 to 80% by weight before the addition of hydrogen peroxide. In addition, it is preferable to set the pH within the range of 7 to 13 using a base.

[0056] The alcohol used in this epoxidation is preferably a saturated alcohol having 1 to 4 carbon atoms, such as methanol, ethanol, n-propanol, 2-propanol, n-butanol, sec-butanol (2-butanol), and isobutanol (2-methyl-1-propanol). These alcohols are used alone or in combination of two or more in appropriate amounts.

[0057] The base used in this epoxidation includes hydroxides, carbonates or hydrogencarbonates of alkali metals or alkaline earth metals, or organic amine compounds. It is preferable to use sodium hydroxide, potassium hydroxide, potassium carbonate, or potassium hydrogencarbonate, and an appropriate amount of one or a combination of two or more types is used.

[0058] The reaction temperature of this epoxidation is set, as in the case of the above-mentioned epoxidation using a peracid, usually in the range of −10 to 150° C., preferably in the range of 0 to 100° C. The reaction time is appropriately set depending on the reaction temperature, but is usually set in the range of 1 to 48 hours, preferably in the range of 1 to 6 hours.

[0059] After the reaction is completed, the epoxy-oxetane compound represented by formula (I) can be separated and extracted from the reaction solution by, for example, solvent extraction, in the same manner as in the case of the epoxidation using peroxy acid. It may also be purified if necessary.

[0060] <About the curable composition of the present invention> The epoxy-oxetane compound represented by formula (I) exhibits excellent curing performance. That is, by curing a curable composition containing an epoxy-oxetane compound represented by chemical formula (I) (hereinafter sometimes referred to as the "first curable compound"), a cured product (resin) that is expected to exhibit excellent properties can be obtained. In addition, in the curable composition of the present invention, it is also possible to use the first curable compound in combination with another curable compound (hereinafter, sometimes referred to as the "second curable compound").

[0061] During curing (polymerization) of the curable composition of the present invention, by allowing a second curable compound to coexist in addition to the first curable compound, a cured product in which the first curable compound and the second curable compound are copolymerized can be obtained. The second curable compound includes both a polymerizable monomer and a polymerizable oligomer (semi-cured product) having a structure in which a polymerizable monomer is polymerized.

[0062] Examples of such polymerizable monomers include known epoxy compounds (sometimes called epoxy resins), oxetane compounds, epoxy-oxetane compounds (having an oxirane ring and an oxetane ring in the molecule), and acrylic compounds (sometimes called acrylic resins).

[0063] The epoxy compound can be used without any particular limitation as long as it has an oxirane ring (epoxy group / glycidyl group) in the molecule. For example, Polyglycidyl ethers obtained by reacting epichlorohydrin with polyhydric phenols such as bisphenol A, bisphenol F, bisphenol AD, catechol, and resorcinol, or polyhydric alcohols such as glycerin and polyethylene glycol; Glycidyl ether esters obtained by reacting hydroxycarboxylic acids such as p-hydroxybenzoic acid and β-hydroxynaphthoic acid with epichlorohydrin; Polyglycidyl esters obtained by reacting polycarboxylic acids such as phthalic acid and terephthalic acid with epichlorohydrin; Glycidyl glycoluril compounds having two or more epoxy groups in the molecule, such as 1,3,4,6-tetraglycidyl glycoluril; Alicyclic epoxy compounds such as 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate; Nitrogen-containing cyclic epoxy compounds such as triglycidyl isocyanurate and hydantoin-type epoxy compounds; Further examples include epoxidized phenol novolac resins, epoxidized cresol novolac resins, epoxidized polyolefins, cyclic aliphatic epoxy resins, urethane-modified epoxy resins, as well as epoxy-modified organopolysiloxane compounds obtained by a hydrosilylation addition reaction between an organic compound having a carbon-carbon double bond and a glycidyl group and a silicon compound having a SiH group (for example, the epoxy-modified organopolysiloxane compounds disclosed in JP-A-2004-99751 and JP-A-2006-282988), and these may be used in combination.

[0064] The oxetane compound can be used without any particular limitation as long as it has an oxetane ring (oxetanyl group / oxetane group) in the molecule. 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-oxetanylmethyl) ether, Ethyl diethylene glycol (3-ethyl-3-oxetanylmethyl) ether, Dicyclopentadiene (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyl (3-ethyl-3-oxetanylmethyl) ether, tetrahydrofurfuryl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxyethyl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxypropyl (3-ethyl-3-oxetanylmethyl) ether, butoxyethyl (3-ethyl-3-oxetanylmethyl) ether, Bornyl (3-ethyl-3-oxetanylmethyl) ether, 3,7-bis(3-oxetanyl)-5-oxa-nonane, 3,3′-[1,3-(2-methylene)propanediylbis(oxymethylene)]bis-(3-ethyloxetane), 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, Ethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyl bis(3-ethyl-3-oxetanylmethyl) ether, triethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, Tricyclodecanediyldimethylene (3-ethyl-3-oxetanylmethyl) ether, Trimethylolpropane tris(3-ethyl-3-oxetanylmethyl) ether, 1,4-bis(3-ethyl-3-oxetanylmethoxy)butane, 1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane, Pentaerythritol tris(3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, Polyethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, Dipentaerythritol hexakis(3-ethyl-3-oxetanylmethyl) ether, Dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, Dipentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, Caprolactone modified dipentaerythritol hexakis(3-ethyl-3-oxetanylmethyl) ether, Caprolactone modified dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, Ditrimethylolpropane tetrakis(3-ethyl-3-oxetanylmethyl) ether, EO modified bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, PO modified bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, EO modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, PO modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, Examples include EO modified bisphenol F (3-ethyl-3-oxetanylmethyl) ether.

[0065] The epoxy-oxetane compound may be any compound having an oxirane ring (ibid.) and an oxetane ring (ibid.) in the molecule, and examples of such compounds include those described in the above-mentioned Patent Documents 1 to 5. The epoxy-oxetane compounds described in these documents are incorporated by reference into the disclosure of this specification.

[0066] Examples of acrylic compounds include allyl (meth)acrylate, vinyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, (meth)acrylic acid modified allyl glycidyl ether (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 (meth)acrylate, bisphenol A di(meth)acrylate, tris(2-(meth)acryloyloxyethyl)isocyanurate, and (meth)acrylate group-containing polyorganosiloxane.

[0067] In the curable composition of the present invention, the second curable compound may be a combination of the above-mentioned polymerizable monomer and polymerizable oligomer, the polymerizable monomer may be a combination of the above-mentioned polymerizable monomers (different types of polymerizable monomers may be a combination), and the polymerizable oligomer may be a combination of different types.

[0068] 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 (weight ratio) the content of the first curable compound, and more preferably an appropriate ratio in the range of 0.01 to 100 times (weight ratio).

[0069] Methods for curing (polymerizing) the curable composition of the present invention include photocuring and thermal curing. Examples of photocuring methods include a method of irradiating with active energy rays and a method of using a photopolymerization initiator in combination. The active energy rays include light, radiation, electromagnetic waves, electron beams, etc., but typically represent light, particularly ultraviolet rays. As the photopolymerization initiator, a photocationic polymerization initiator can be used, and if necessary, a photoradical polymerization initiator can be used in combination, and these can be contained in the curable composition. In addition, in order to improve production efficiency and properties of the cured product, a thermal curing method can be used in combination with the photocuring.

[0070] As the photocationic polymerization initiator, any commonly used one can be used without any particular limitation, and examples thereof include onium salts and organometallic complexes. Examples of the onium salts include diazonium salts, sulfonium salts and iodonium salts, and examples of the organometallic complexes include iron-arene complexes, titanocene complexes and arylsilanol-aluminum complexes. Examples of industrial chemicals commercially available as photocationic polymerization initiators include "OPTOMER SP-150 (product name)" and "OPTOMER SP-170 (product name)" manufactured by ADEKA Corporation, "CPI-100P (product name)" manufactured by San-Apro, "UVE-1014 (product name)" manufactured by General Electronics Corporation, and "CD-1012 (product name)" manufactured by Sartomer Corporation. The counter anion of the photocationic polymerization initiator is SbF6 - , AsF6 - , B(C6F5)4 - , PF6- etc.

[0071] The content of the cationic photopolymerization initiator in the curable composition of the present invention is preferably from 0.001 to 20% by weight, and more preferably from 0.01 to 10% by weight.

[0072] Examples of photoradical polymerization initiators include: Ketal compounds having 16 to 17 carbon atoms (e.g., acetophenone dimethyl ketal, benzyl dimethyl ketal, etc.), Acetophenone compounds having 8 to 18 carbon atoms (e.g., 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 (e.g., benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 4,4'-bismethylaminobenzophenone, etc.), benzoin compounds having 14 to 18 carbon atoms (e.g., benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, etc.), Anthraquinone compounds having 14 to 19 carbon atoms (e.g., 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-chloroanthraquinone, 2-amylanthraquinone, etc.), Thioxanthone compounds having 13 to 17 carbon atoms (e.g., 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, etc.), Examples of the acylphosphine oxide compounds include those 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.).

[0073] The content of the photoradical polymerization initiator in the curable composition of the present invention is preferably from 0.001 to 20% by weight, and more preferably from 0.01 to 10% by weight.

[0074] When the curable composition of the present invention is photocured, a sensitizer such as pyrene, perylene, acridine orange, thioxanthone, 2-chlorothioxanthone, or benzoflavin can be used.

[0075] 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 can be adopted, and this may be contained in the curable composition.

[0076] As the thermal cationic polymerization initiator, any commonly used one can be used without any particular limitation, and examples thereof include various onium salts such as quaternary ammonium salts, phosphonium salts and sulfonium salts, and organometallic complexes. Examples of onium salts commercially available as industrial chemicals include "ADEKAOPTON CP-66 (product name)" and "ADEKAOPTON CP-77 (product name)" manufactured by ADEKA Corporation, "SAN-AID SI-60L (product name)," "SAN-AID SI-80L (product name)," and "SAN-AID SI-100L (product name)" manufactured by Sanshin Chemical Industry Co., Ltd., and "CI Series (product name)" manufactured by Nippon Soda Co., Ltd. Examples of organometallic complexes include alkoxysilane-aluminum complexes.

[0077] The content of the thermal cationic polymerization initiator in the curable composition of the present invention is preferably from 0.001 to 20% by weight, and more preferably from 0.01 to 10% by weight.

[0078] In the present invention, the cationic polymerization initiator refers to the above-mentioned photocationic polymerization initiator and / or thermal cationic polymerization initiator.

[0079] The curable composition of the present invention further includes, as long as the effects of the present invention are not impaired, Pigments (titanium white, cyanine blue, watching red, red iron oxide, carbon black, aniline black, manganese blue, iron black, ultramarine blue, Hansa red, chrome yellow, chrome green, etc.), Inorganic fillers (calcium carbonate, kaolin, clay, talc, mica, barium sulfate, lithopone, gypsum, zinc stearate, perlite, quartz, quartz glass, fused silica, 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 materials such as diamond, carbon, etc.), Thermoplastic resins and thermosetting resins (homopolymers such as various high-density, medium-density and low-density polyethylenes, polypropylene, polybutene, polypentene, etc., ethylene-propylene copolymers, polyamide resins such as nylon-6 and 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-based resins, various elastomer resins such as acrylic rubber and urethane rubber, graft copolymers such as methyl methacrylate-butadiene-styrene graft copolymers and acrylonitrile-butadiene-styrene graft copolymers, etc.), Reinforcing agents (glass fiber, carbon fiber, etc.), Anti-sagging agents (hydrogenated castor oil, fine silica particles, etc.), Matting agents (fine silica, paraffin wax, etc.), Abrasives (zinc stearate, etc.), Internal mold release agents (fatty acids such as stearic acid, fatty acid metal salts such as calcium stearate, fatty acid amides such as stearic acid amide, fatty acid esters, polyolefin wax, paraffin wax, etc.), The composition may contain additives (modifiers) such as surfactants, leveling agents, antifoaming agents, viscosity adjusting diluents (organic solvents), coupling agents, fragrances, and flame retardants.

[0080] The curable composition of the present invention is prepared by any method, and is prepared by weighing out the above-mentioned components in a predetermined amount and mixing them by stirring. For example, after premixing, it can be prepared by mixing or melt-kneading using a roll mixer, kneader, extruder, etc. If necessary, an organic solvent (a diluent for adjusting viscosity) may be used.

[0081] The curable composition of the present invention polymerizes (cures) upon irradiation with ultraviolet light or heating to give a cured product. Examples of the ultraviolet ray irradiation means include a method using a light source such as a chemical lamp, a low pressure mercury lamp, a high pressure mercury lamp, an extra high pressure mercury lamp, a xenon lamp, or a metal halide lamp. The irradiation intensity and irradiation time of ultraviolet light are appropriately set taking into consideration the desired irradiation intensity or desired irradiation time, and also taking into consideration the composition and shape (thickness) of the curable composition to be irradiated. Examples of the heating means include hot air circulation, infrared heating, high frequency heating, etc. Also, as the curing device, a closed curing oven or a tunnel oven capable of continuous curing, etc. can be used. The heating (curing) temperature and heating (curing) time may be appropriately set in consideration of the composition and shape (thickness) of the curable composition to be irradiated, as in the case of ultraviolet irradiation.

[0082] The curable composition of the present invention has low volatility and excellent maintenance. Therefore, the curable composition can be used as a curable ink composition. Furthermore, the curable composition has low viscosity and excellent dischargeability. Therefore, it is also suitable as an inkjet curable ink composition. By applying the inkjet curable ink composition to a predetermined object and curing it using the inkjet method, it is used in the manufacture of various parts and members, etc., which will be described later. The inkjet method can form a resin film quickly, uniformly, and over a wide area, so it has advantages such as improved product accuracy of various parts and members, etc., which will be described later, as well as reduced manufacturing costs.

[0083] From the viewpoint of volatility, the curable ink composition and the curable ink composition for inkjet preferably have a 5% weight loss temperature (°C) of 185°C or higher, and more preferably 190°C or higher, as measured using a differential thermal thermogravimetry device under conditions of a sample weight of 10 mg, a heating condition of 10°C / min, and a nitrogen flow (200 ml / min).

[0084] The curable inkjet ink composition preferably has a viscosity 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, as measured at 25° C. using a dynamic viscoelasticity measuring device (manufactured by UBM, "Rheosol-G5000") The curable inkjet ink composition may be heated during application by the inkjet method to reduce the viscosity before application.

[0085] Furthermore, the curable inkjet ink composition preferably has a surface tension of 15 mN / m or more and 35 mN / m or less, and more preferably 20 mN / m or more and 30 mN / m or less, as measured at 25° C. using a dynamic wettability tester.

[0086] Suitable examples of the curable inkjet ink composition include curable compositions for encapsulating optical elements, which are used as encapsulants for optical elements such as organic electroluminescence (hereinafter referred to as organic EL) elements and organic thin-film solar cell elements, as well as adhesives for optical components, which are used for bonding optical lenses, etc., curable compositions for stereolithography, which are used in the manufacture of various parts and components by 3D printers, and curable compositions for nanoimprinting, which are used in the formation of ultrafine circuit patterns for semiconductors.

[0087] As an example, a method for producing an optical element using the curable composition of the present invention as a curable composition for encapsulating an optical element includes a step of applying the curable composition for encapsulating an optical element to at least one of two substrates by an inkjet method, a step of curing the applied curable composition for encapsulating an optical element by light irradiation and / or heating, and a step of bonding the two substrates together.

[0088] In the step of applying the sealant for optical elements to at least one of two substrates, the curable composition for sealing optical elements may be applied to the entire surface of the substrate, or may be applied to a part of the substrate. For example, when an organic EL element is manufactured as the optical element, the shape of the sealant portion formed by applying the curable composition for sealing optical elements is not particularly limited as long as it is a shape that can protect the laminate having the organic light-emitting material layer sandwiched between two substrates from the outside air. That is, it may be a shape that completely covers the laminate, or a pattern shape that closes the periphery of the laminate.

[0089] The step of curing the curable composition for encapsulating optical elements by light irradiation and / or heating may be performed before or after the step of laminating the two substrates. When the step of curing the curable composition for encapsulating optical elements by light irradiation and / or heating is performed before the step of laminating the two substrates, the substrates may be laminated within a usable time (e.g., 1 minute) from the time of light irradiation and / or heating until the curing reaction progresses and adhesion becomes impossible.

[0090] In addition, the step of curing the applied curable composition for encapsulating optical elements by light irradiation and / or heating may be performed by the above-mentioned ultraviolet ray irradiation means and / or heating means.

[0091] The curable composition of the present invention is not particularly limited in its application, and can be applied to products (parts and components) in various fields where the material may be resin, and can be used as a raw material for materials in the fields of electricity / electronics, optics, architecture, civil engineering, automobiles / aircraft, and medicine, as well as for other daily necessities and miscellaneous goods.

[0092] For example, examples of parts, components and materials in the electrical and electronic fields include resin-coated copper foil, prepreg, copper-clad laminates, printed wiring boards, solder resist ink, anisotropic conductive film, anisotropic conductive paste, interlayer insulating material, adhesive, sealant, encapsulant, insulating material, thermally conductive material, hot melt material, paint, potting agent, etc., more specifically, interlayer insulating film, wiring coating film and other printed wiring boards, encapsulating materials for electronic components, layer forming materials; Materials for forming display devices such as color filters, polarizing plates, display materials, resist materials, and alignment films; Materials for forming semiconductor devices, such as resist materials and buffer coating films; Examples of the material include materials for forming optical components such as lenses, holograms, optical waveguides, optical circuits, optical circuit components, and anti-reflection films. Other examples include materials for organic electronics elements such as organic EL elements, organic transistors, and solar cells, materials for forming rigid wiring boards and flexible printed wiring boards for semiconductor mounting, mounting materials for semiconductor mounting, adhesives for flexible printed wiring boards, semiconductor encapsulants, solar cell encapsulants, insulating films for semiconductors, coverlay films for protecting flexible printed circuits, and coating agents for covering wiring.

[0093] 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, etc. For example, lenses and prisms are not particularly limited as long as they utilize refraction on the surface.

[0094] Lenses and prisms include convex lenses such as biconvex lenses, plano-convex lenses, and convex meniscus lenses, and concave lenses such as biconcave lenses, plano-concave lenses, and concave meniscus lenses, and have spherical surfaces; Aspheric lenses, such as lenses having aspheric surfaces, such as symmetric paraboloids, ellipsoids, hyperboloids, and polymorphic surfaces (e.g. quartic surfaces), and lenses having freeform surfaces without an axis of symmetry; Cylindrical lenses are like semi-cylindrical lenses with a cylindrical surface; A toroidal lens, which has a toroidal surface with different radii of curvature in the longitudinal and transverse directions, like the surface of a doughnut; A thin Fresnel lens is a lens in which a number of concentric ring-shaped prisms, each of which has a reflective surface that changes the direction of light by inclining in the same way as the curve of a thick convex lens, and a refracting surface that transmits light, are arranged on a flat surface, and these multiple prisms become successively smaller or larger as they approach the center; A diffractive lens that has a minute relief with a depth of about the wavelength of light formed in a concentric pattern; Examples of such prisms include those having two or more optically flat surfaces, with at least one pair of surfaces being substantially non-parallel. Examples of films include reflective films that are made by treating inorganic compounds such as MgF2 and SiO2 using a vacuum deposition method, a sputtering method, or a CVD method, or by coexisting a light absorber, and that transmit light in a desired wavelength range while reflecting light in an undesired wavelength range.

[0095] Examples of materials in the construction field include sealants, coating materials, and primers for exterior materials such as various metal panels and siding boards; Sealing materials, adhesives, injection materials, vibration-damping materials, soundproofing materials, conductive materials for electromagnetic wave shielding, putty materials used between exterior materials, base materials, ceiling materials and interior materials; Adhesives for bonding tiles and stone to exterior walls and substrates; Adhesives and pressure sensitive adhesives for bonding wood flooring materials, polymeric floor sheets, and floor tiles to various floors; Examples include injection materials for repairing cracks in various exterior and interior materials.

[0096] Examples of materials in the civil engineering field include joint sealants, coating materials, primers, paints, putty materials, injection materials, spraying materials, and formwork for various concrete products such as roads, bridges, tunnels, and breakwaters.

[0097] Examples of materials in the automotive and aerospace fields include structural materials, adhesives for bodies and parts, sealing materials, coating materials, cushioning materials, vibration-damping materials, soundproofing materials, spraying materials; Adhesives, pressure sensitive adhesives, coatings and foams for automotive interiors; Examples include sealing materials for steel plate joints, adhesives, coating materials, etc.

[0098] Examples of materials in the medical field include artificial bones, dental impression materials, medical rubber materials, medical adhesives, and medical device sealing materials. EXAMPLES

[0099] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these. The main raw materials used in the synthesis examples are as follows:

[0100] [Main raw materials, etc.] 3,3-Bis(bromomethyl)oxetane (Tokyo Chemical Industry Co., Ltd.) 3,3-Bis(hydroxymethyl)oxetane: Synthesized according to the method described in "Journal of Polymer Science: Part A Polymer Chemistry, Vol. 27, 3083-3112 (1989)". Epichlorohydrin (Osaka Soda Co., Ltd.) Benzyltrimethylammonium chloride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) Sodium hydroxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) 7-Octen-1-ol (Tokyo Chemical Industry Co., Ltd.) 3-Methyl-3-buten-1-ol (Tokyo Chemical Industry Co., Ltd.) Potassium t-butoxide (Tokyo Chemical Industry Co., Ltd.) 3-Chloroperbenzoic acid (Tokyo Chemical Industry Co., Ltd.) Potassium carbonate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) ·2-Buten-1-ol (Tokyo Chemical Industry Co., Ltd.) ·Toluene (Fujifilm Wako Pure Chemical Industries, Ltd.) Dichloromethane (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) N,N-Dimethylformamide (Fujifilm Wako Pure Chemical Industries, Ltd.) Hexane (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) Ethyl acetate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0101] The thermal cationic polymerization initiators (thermal acid generators) used in the evaluation tests are as follows. Dibenzylmethyl-p-hydroxyphenylsulfonium hexafluoroantimonate (manufactured by Sanshin Chemical Industry Co., Ltd., "San-Aid SI-100L (trade name)")

[0102] The evaluation tests (curability) employed in the examples and comparative examples are as follows. (a) Measurement of 5% weight loss temperature The 5% weight loss temperature was measured for the epoxy-oxetane compounds used in the examples and comparative examples using a differential thermal thermogravimetry device (STA7300, Hitachi High-Tech Science Corporation) under the following conditions: sample weight 10 mg, heating condition 10°C / min, nitrogen flow (200 ml / min). (b) Viscosity measurement The viscosity of the epoxy-oxetane compounds used in the examples and comparative examples was measured at 25°C using a dynamic viscoelasticity measuring device (manufactured by UBM, "Rheosol-G5000"). (c) Curability of curable composition Gel time measurements (hot plate method) were carried out at 120° C. using the curable compositions prepared in the examples and comparative examples described below. (d) Physical properties of the cured product The curable compositions prepared in the Examples and Comparative Examples described below were kneaded and degassed using a mixer ("Awatori Rentaro (product name)"), and then 15 g of each was poured into a formwork consisting of two release-treated glass plates (120 mm x 120 mm x 3 mm) sandwiched between them and fixed with clips, and then the formwork was placed in a ventilation oven and heated at 65°C for 2 hours, and then further heated at 150°C for 2 hours to cause curing. Subsequently, after cooling to room temperature, the cured product was taken out and cut into test pieces of 10 mm (length) × 10 mm (width) × 4 mm (thickness) using a cutter. The glass transition temperature (Tg) and coefficient of linear expansion (CTE) of these test pieces were measured using a thermomechanical analyzer (TMA: Hitachi High-Tech Science Corporation, "TMA7100") (flow gas: nitrogen, heating conditions: 5°C / min.).

[0103] [Synthesis Example 1] <Synthesis of epoxy-oxetane compound represented by chemical formula (IV)> A 10L separable flask was charged with 391.4g (3.31mol) of 3,3-bis(hydroxymethyl)oxetane, 2438.6g (26.36mol) of epichlorohydrin, and 12.8g of benzyltrimethylammonium chloride. The mixture was cooled to 10℃ with ice, and 3865.2g (46.38mol) of 48% aqueous sodium hydroxide solution was added dropwise and stirred for 14 hours. Dichloromethane was added to the reaction liquid, which was washed with water and the organic layer was concentrated. The resulting concentrate was purified by distillation to obtain 169.1g (0.73mol / yield 22.2%) of the epoxy-oxetane compound represented by the chemical formula (IV) as a colorless, transparent liquid.

[0104] [ka]

[0105] [Synthesis Example 2] <Synthesis of compound represented by chemical formula (Va)> In a 300 mL eggplant flask, 21.90 g (89.8 mmol) of 3,3-bis(bromomethyl)oxetane, 19.67 g (153.4 mmol) of 7-octen-1-ol, and 15.00 g of N,N-dimethylformamide were charged and cooled to 5°C with stirring. 17.50 g (156.0 mmol) of potassium t-butoxide was added in portions so that the temperature did not exceed 5°C. After stirring at 5°C for 1 hour, the temperature was raised to room temperature and stirred for 14 hours. Subsequently, toluene was added to the reaction liquid, which was washed with water. The resulting organic layer was concentrated, and the concentrate was purified by distillation to obtain 25.01 g (73.9 mmol / yield 82.1%) of a compound represented by chemical formula (Va) as a colorless, transparent liquid.

[0106] [ka]

[0107] [Synthesis Example 3] <Synthesis of epoxy-oxetane compound represented by chemical formula (V)> In a 1 L recovery flask, 24.98 g (73.8 mmol) of the compound represented by the chemical formula (Va) synthesized in Synthesis Example 2 and 73.80 g of dichloromethane were charged and cooled on ice to 5° C. Then, 45.48 g (184.5 mmol) of 70% by weight 3-chloroperbenzoic acid was added, the temperature was raised to 40° C., and the mixture was stirred for 20 hours. The reaction mixture was then filtered to remove solids, washed with an aqueous potassium carbonate solution and water, and the organic layer was concentrated. The concentrate was purified by silica gel column chromatography (ethyl acetate / hexane = 1 / 3 (volume ratio)) to obtain 9.89 g (26.7 mmol / yield 36.2%) of the epoxy-oxetane compound represented by formula (V) as a colorless, transparent liquid.

[0108] [ka]

[0109] [Synthesis Example 4] <Synthesis of the compound represented by chemical formula (VI)> In a 3L eggplant flask, 73.18g (300.0mmol) of 3,3-bis(bromomethyl)oxetane, 59.43g (690.0mmol) of 3-methyl-3-buten-1-ol, and 60.00g of N,N-dimethylformamide were charged and cooled to 5°C with stirring. 70.69g (630.0mmol) of t-butoxypotassium was added in portions so that the temperature did not exceed 5°C. After stirring at 5°C for 1 hour, the temperature was raised to room temperature and stirred for 14 hours. Subsequently, toluene was added to the reaction liquid, washed with water, and the resulting organic layer was concentrated. This concentrate was purified by distillation to obtain 55.00g (216.2mmol / yield 72.1%) of a compound represented by chemical formula (VI) as a colorless, transparent liquid.

[0110] [ka]

[0111] [Synthesis Example 5] <Synthesis of epoxy-oxetane compound represented by chemical formula (VII)> In a 3 L recovery flask, 25.44 g (100.0 mmol) of the compound represented by chemical formula (VI) synthesized in Synthesis Example 4 and 500.00 g of dichloromethane were charged and cooled to 5° C. on ice. Next, 49.30 g (220.0 mmol) of 70% by weight 3-chloroperbenzoic acid was added, the temperature was raised to room temperature, and the mixture was stirred for 2 hours. The reaction mixture was then filtered to remove solids, washed with an aqueous potassium carbonate solution and water, and the organic layer was concentrated. The concentrate was purified by silica gel column chromatography (ethyl acetate / hexane = 1 / 5 (volume ratio)) to obtain 8.76 g (30.6 mmol / yield 30.6%) of the epoxy-oxetane compound represented by formula (VII) as a colorless, transparent liquid.

[0112] [ka]

[0113] [Synthesis Example 6] <Synthesis of compound represented by chemical formula (Ia-1)> In a 3L eggplant flask, 85.95g (352.4mmol) of 3,3-bis(bromomethyl)oxetane, 63.52g (880.8mmol) of 3-buten-1-ol, and 587.25g of N,N-dimethylformamide were charged and cooled to 5°C with stirring. 94.91g (845.8mmol) of t-butoxypotassium was added in portions so that the temperature did not exceed 5°C. After stirring at 5°C for 1 hour, the temperature was raised to room temperature and stirred for 14 hours. Subsequently, toluene was added to the reaction liquid, washed with water, and the resulting organic layer was concentrated. This concentrate was purified by distillation to obtain 57.2g (252.7mmol / yield 71.7%) of a colorless transparent liquid.

[0114] This colorless and transparent liquid 1 The H-NMR spectrum data was as follows: · 1 H-NMR (CDCl3) δ:5.77-5.80(m, 2H), 5.01-5.12(m, 4H), 4.46(s, 4H), 3.63(s, 4H), 3.52(t, 4H), 2.31-2.37(m, 4H).. From this spectral data, the obtained colorless transparent liquid was identified as a compound represented by chemical formula (Ia-1).

[0115] [ka]

[0116] [Synthesis Example 7] <Synthesis of epoxy-oxetane compound represented by chemical formula (I-1)> In a 2L recovery flask, 57.20 g (252.7 mmol) of the compound represented by the chemical formula (Ia-1) synthesized in Synthesis Example 6 and 500.00 g of dichloromethane were charged and cooled to 5° C. on ice. Next, 130.72 g (530.4 mmol) of 70% by weight 3-chloroperbenzoic acid was added, the temperature was raised to 25° C., and the mixture was stirred for 20 hours. The reaction mixture was then filtered to remove solids, washed with an aqueous potassium carbonate solution and water, and the organic layer was concentrated. The concentrate was purified by silica gel column chromatography (ethyl acetate / hexane = 2 / 3 (volume ratio)) to obtain 22.80 g (88.3 mmol / yield 34.9%) of a colorless, transparent liquid.

[0117] This colorless and transparent liquid 1 The H-NMR spectrum data was as follows: · 1 H-NMR (CDCl3) δ:4.48(s, 4H), 3.60-3.66(m, 8H), 3.02-3.07(m, 2H), 2.78-2.81(m, 2H), 2.47-2.51(m, 2H), 1.86-1.95(m, 2H), 1.69-1.77(m, 2H). From this spectral data, the obtained colorless transparent liquid was identified as an epoxy-oxetane compound represented by the chemical formula (I-1).

[0118] [ka]

[0119] Example 1 A curable composition was prepared by uniformly mixing 100 parts by weight of the epoxy oxetane compound represented by the chemical formula (I-1) synthesized in Synthesis Example 7 and 0.2 parts by weight of a thermal cationic polymerization initiator. This curable composition was subjected to evaluation tests, and the test results obtained are shown in Table 1. Note that, for the measurement of the 5% weight loss temperature and the measurement of the viscosity, the physical property values ​​of the epoxy-oxetane compound alone were measured.

[0120] [Comparative Examples 1 to 3] In the same manner as in Example 1, a curable composition having the blending composition shown in Table 1 was prepared and an evaluation test was carried out, and the test results obtained were as shown in Table 1.

[0121] [Table 1] [Industrial Applicability]

[0122] According to the curable composition of the present invention, it is possible to provide a curable composition which has low viscosity, low volatility, and curability, 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, n is the same or different and represents an integer of 2 to 5.)

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

3. A curable ink composition comprising the curable composition according to claim 2 .

4. A curable inkjet ink composition comprising the curable ink composition according to claim 3 .

5. A cured product obtained by curing at least one of the curable composition according to claim 1 or 2, the curable ink composition according to claim 3, and the curable inkjet ink composition according to claim 4.

6. A curable composition for encapsulating optical elements, comprising at least one of the curable composition according to claim 1 or 2, the curable ink composition according to claim 3, and the curable inkjet ink composition according to claim 4.

7. The curable composition for encapsulating optical elements according to claim 6, which is for encapsulating an organic electroluminescence element.

8. An adhesive for optical members, comprising at least one of the curable composition according to claim 1 or 2, the curable ink composition according to claim 3, and the curable inkjet ink composition according to claim 4.

9. A curable composition for stereolithography, comprising at least one of the curable composition according to claim 1 or 2, the curable ink composition according to claim 3, and the curable inkjet ink composition according to claim 4.

10. A curable composition for nanoimprints, comprising at least one of the curable composition according to claim 1 or 2, the curable ink composition according to claim 3, and the curable inkjet ink composition according to claim 4.

Images