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

Abstract

Provided are a curable composition, a curable ink composition, and a curable inkjet ink composition that concomitantly have low viscosity, low volatility, and curing properties. Also provided is a method for using said compositions. The 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.

Description

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

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

[0002] Oxetane compounds have attracted attention in recent years as photocurable and thermocurable monomers, and curable compositions containing them as components shrink little upon curing, and the resulting cured products (resins) are excellent in toughness, mechanical properties, heat resistance, electrical properties, water resistance, weather resistance, transparency, etc. Due to 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, etc.

[0003] Prior art related to the present invention will be described below with reference to related 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]

[0005]

[0006] The invention described in Patent Document 2 relates to an actinic radiation-curable inkjet ink and 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]

[0008]

[0009]

[0010] Furthermore, Patent Documents 3 to 5 also describe 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 the ink from drying out due to evaporation, and excellent curability by heat or light (fast curing rate). Curable compositions containing chemical formulas (Ref-1) to (Ref-5) do not have a high level of these properties, and have had problems with viscosity (ejectability), volatility, or curability (curing rate).

[0012] US Patent No. 3,457,193 Specification Japanese Patent Application Publication No. 2005-002191 Japanese Patent Application Publication No. 2007-270070 Japanese Patent Application Publication No. 2010-111713 Japanese Patent Application Publication No. 2011-208089

[0013] An object of one aspect 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 methods of using these compositions.

[0014] One aspect of the present invention is a curable composition containing an epoxy oxetane compound represented by formula (I). (In the formula, n may be the same or different and represents an integer of 2 to 5.)

[0015] A curable composition containing the epoxy-oxetane compound represented by chemical formula (I) can be a curable composition that has low viscosity and excellent dischargeability, low volatility and excellent maintainability, and further has excellent curability (high curing rate).

[0016] One aspect of the present invention will be described below. The present invention is not limited to the following embodiments and examples, and various modifications are possible within the scope of the claims. Embodiments obtained by appropriately combining the technical means disclosed in different embodiments and examples are also included in the technical scope of the present invention. Furthermore, new technical features can be formed by combining the technical means disclosed in each embodiment. In addition, in this specification, the term "A to B" indicating a numerical range means "greater than or equal to A and less than or equal to B," including both end values.

[0017] A curable compound according to one embodiment 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 bonded to an oxetane ring via a connector having one ether bond.

[0018]

[0019] In the above chemical formula (I), n may be 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, even more preferably an integer of 2 or 3, and particularly preferably 2.

[0020] Examples of the epoxy oxetane compound represented by chemical formula (I) include compounds represented by chemical formulas (I-1) to (I-4).

[0021]

[0022] 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 even more preferably an epoxy oxetane compound represented by chemical formula (I-1). These may be used alone or in combination of two or more kinds.

[0023] <Method for synthesizing the 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, thereby synthesizing the epoxy-oxetane compound represented by chemical formula (I) (see reaction scheme (A)).

[0024]

[0025] In chemical formula (II), X represents a leaving group, and 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).

[0026] Examples of the oxetane compound having a leaving group include 3,3-bis(chloromethyl)oxetane and 3,3-bis(bromomethyl)oxetane, with 3,3-bis(bromomethyl)oxetane being preferred.

[0027] 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 or more. The amount (charge amount) of the olefin compound used is preferably an appropriate ratio in the range of 2 to 20 times the molar amount (charge amount) of the oxetane compound having a leaving group used.

[0028]

[0029] 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, an epoxy-oxetane compound represented by the chemical formula (I-1) or an epoxy-oxetane compound represented by the chemical formula (I-2) can be obtained, respectively.

[0030] The olefin-oxetane compound represented by chemical formula (Ia) can be synthesized in the presence of a base (i), and a catalyst (ii) for promoting the reaction may be used. A reaction solvent (iii) may also be used as long as it does not inhibit the reaction. In addition, the reaction for epoxidizing the double bond of the compound can employ a general epoxidation (oxidation) method, such as a method using a peracid, a method using hydrogen peroxide with sodium tungstate as a catalyst, or a method using hydrogen peroxide together with a base in an acetonitrile-alcohol solvent.

[0031] Examples of the base (i) include hydrides, hydroxides, carbonates, hydrogencarbonates, alkoxides, and organic amine compounds of alkali metals or alkaline earth metals. Examples of such bases (i) include sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium alkoxides, potassium alkoxides (e.g., potassium t-butoxide), and triethylamine. The amount of base used (charge amount) is preferably an appropriate ratio in the range of 2 to 20 times the molar amount of the oxetane compound having a leaving group used (charge amount).

[0032] Examples of the catalyst (ii) include quaternary ammonium salts, quaternary phosphonium salts, etc. 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), etc.

[0033] Examples of quaternary phosphonium salts include salts such as halides (fluorides, chlorides, bromides, iodides) of tetrabutylphosphonium, tetramethylphosphonium, tetraethylphosphonium, tetrapropylphosphonium, tetrahexylphosphonium, tetradecylphosphonium, tetraoctylphosphonium, triethyloctadecylphosphonium, trioctylethylphosphonium, hexadecyltriethylphosphonium, tetraphenylphosphonium, and methyltriphenylphosphonium.

[0034] These substances may be combined and used as catalyst (ii). The amount (charge amount) of catalyst (ii) used is preferably an appropriate ratio in the range of 0.0001 to 1.0 times the molar amount (charge amount) of the oxetane compound having a leaving group.

[0035] The reaction solvent (iii) is not particularly limited as long as it does not inhibit the reaction, and examples thereof include solvents such as 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), dimethyl sulfoxide (DMSO), and hexamethylphosphoric triamide (HMPA). One or more solvents selected from these may be used in appropriate amounts in combination.

[0036] The reaction temperature when 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. The reaction time is appropriately set depending on the set reaction temperature, but is preferably set in the range of 1 to 48 hours.

[0037] After the reaction is complete, 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, etc. If necessary, the product can be further purified by washing with water, treatment with activated carbon, silica gel chromatography, etc.

[0038] In the reaction of epoxidizing an olefin-oxetane compound using the peracid, peracids such as Oxone reagent, peracetic acid, metachloroperbenzoic acid (3-chloroperbenzoic acid), etc. The amount of peracid used (charged amount) is preferably an appropriate ratio in the range of 1.0 to 5.0 times the molar amount of the double bond in the olefin-oxetane compound.

[0039] In this epoxidation reaction, the reaction solvent is not particularly limited as long as it does not inhibit the reaction, and examples thereof 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 hexamethylphosphorotriamide, and sulfoxides such as dimethyl sulfoxide (DMSO). These reaction solvents can be used alone or in combination of two or more in appropriate amounts.

[0040] The reaction temperature in this epoxidation reaction is usually set 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 24 hours, preferably in the range of 1 to 6 hours.

[0041] After the reaction is completed, the target epoxy-oxetane compound represented by chemical formula (I) can be separated and extracted from the resulting reaction solution by, for example, solvent extraction, etc. If necessary, the compound can be further purified by washing with water, treatment with activated carbon, silica gel chromatography, etc.

[0042] In the reaction of epoxidizing an olefin-oxetane compound using hydrogen peroxide and 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 (charge amount) is preferably an appropriate ratio in the range of 0.001 to 0.5 times the double bond of the olefin-oxetane compound.

[0043] 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.

[0044] The reaction temperature in this epoxidation reaction is set to be generally in the range of −10 to 150° C., preferably in the range of 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 to be in the range of 1 to 24 hours, preferably in the range of 1 to 6 hours.

[0045] After the reaction is complete, the epoxy-oxetane compound represented by chemical formula (I) can be separated and extracted from the resulting reaction solution by, for example, solvent extraction, in the same manner as in the above-mentioned epoxidation using a peracid. If necessary, the separated epoxy-oxetane compound represented by chemical formula (I) may be purified.

[0046] In the reaction of epoxidizing an olefin-oxetane compound using hydrogen peroxide together with a base in an acetonitrile-alcohol solvent, the amount of hydrogen peroxide used (charge amount) is preferably an appropriate ratio within the range of 1.0 to 5.0 times the molar ratio of the double bond possessed by the olefin-oxetane compound. The amount of acetonitrile used (charge amount) is preferably an appropriate ratio within the range of 0.5 to 5.0 times the molar ratio of the olefin-oxetane compound. The amount of alcohol used (charge amount) is preferably an appropriate ratio within the range of 10 to 80% by weight before the addition of hydrogen peroxide. The pH is preferably set within the range of 7 to 13 using a base.

[0047] 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 may be used alone or in combination of two or more in appropriate amounts.

[0048] 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.

[0049] The reaction temperature for 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.

[0050] After the reaction is complete, the epoxy-oxetane compound represented by chemical formula (I) can be separated and extracted from the resulting reaction solution by, for example, solvent extraction, in the same manner as in the above-mentioned epoxidation using a peracid. If necessary, the separated epoxy-oxetane compound represented by chemical formula (I) may be purified.

[0051] <Regarding the Curable Composition According to One Aspect of the Present Invention> The epoxy-oxetane compound represented by chemical formula (I) exhibits excellent curing performance. That is, a curable composition containing the epoxy-oxetane compound represented by chemical formula (I) (hereinafter sometimes referred to as the "first curable compound") can be cured to obtain a cured product (resin) that is expected to exhibit excellent properties. Note that in the curable composition according to one aspect of the present invention, the first curable compound can also be used in combination with another curable compound (hereinafter sometimes referred to as the "second curable compound").

[0052] When the curable composition according to one aspect of the present invention is cured (polymerized), a cured product can be obtained in which the first curable compound and the second curable compound are copolymerized by adding a second curable compound separately from the first curable compound. The second curable compound includes both a polymerizable monomer and a polymerizable oligomer (semi-cured product) having a structure in which the polymerizable monomer is polymerized.

[0053] Examples of this polymerizable monomer include known epoxy compounds (note: 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).

[0054] 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, and examples thereof include: 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 epichlorohydrin with hydroxycarboxylic acids such as p-hydroxybenzoic acid and β-hydroxynaphthoic acid; polyglycidyl esters obtained by reacting epichlorohydrin with polycarboxylic acids such as phthalic acid and terephthalic acid; 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, alicyclic epoxy resins, and 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.

[0055] 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, and examples thereof include 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-methyleneyl)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, Examples include 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, and EO-modified bisphenol F(3-ethyl-3-oxetanylmethyl) ether.

[0056] The epoxy-oxetane compound can be any compound having an oxirane ring (ibid.) and an oxetane ring (ibid.) in the molecule, and examples thereof 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.

[0057] Examples of the acrylic compound 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.

[0058] In the curable composition according to one embodiment of the present invention, the second curable compound may be a combination of the polymerizable monomer and polymerizable oligomer described above, and as the polymerizable monomer, the polymerizable monomers exemplified above may be a combination (different types of polymerizable monomers may be a combination), and as the polymerizable oligomer, different types of polymerizable oligomers may be a combination.

[0059] Regarding the ratio of the content of the first curable compound to the content of the second curable compound in the curable composition according to one aspect 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).

[0060] Methods for curing (polymerizing) the curable composition according to one embodiment 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. Active energy rays include light, radiation, electromagnetic waves, electron beams, and the like, but typically refer to light, particularly ultraviolet rays. A photocationic polymerization initiator can be used as the photopolymerization initiator, and a photoradical polymerization initiator can be used in combination as needed, and these can be incorporated into the curable composition. Photocuring may also be combined with thermal curing to improve production efficiency and the properties of the cured product.

[0061] As the cationic photopolymerization initiator, any commonly used one can be used without any particular limitation, and examples thereof 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-allene complexes, titanocene complexes, and arylsilanol-aluminum complexes. Examples of industrial chemicals commercially available as cationic photopolymerization initiators include "OPTOMER SP-150 (trade name)" and "OPTOMER SP-170 (trade name)" manufactured by ADEKA Corporation, "CPI-100P (trade name)" manufactured by San-Apro, "UVE-1014 (trade name)" manufactured by General Electronics Corporation, and "CD-1012 (trade name)" manufactured by Sartomer. Examples of the counter anion of the cationic photopolymerization initiator include SbF ６ － , AsF ６ － , B(C ６ F ５ ) ４ － , P.F. ６ － etc.

[0062] The content of the cationic photopolymerization initiator in the curable composition according to one embodiment of the present invention is preferably 0.001 to 20% by weight, and more preferably 0.01 to 10% by weight.

[0063] Examples of the photoradical polymerization initiator 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, and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide).

[0064] The content of the photoradical polymerization initiator in the curable composition according to one embodiment of the present invention is preferably 0.001 to 20% by weight, and more preferably 0.01 to 10% by weight.

[0065] When photocuring the curable composition according to one aspect of the present invention, a sensitizer such as pyrene, perylene, acridine orange, thioxanthone, 2-chlorothioxanthone, or benzoflavin can be used.

[0066] On the other hand, when thermally curing the curable composition according to one embodiment of the present invention, 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.

[0067] The thermal cationic polymerization initiator can be any commonly used one without particular limitation, and examples thereof include various onium salts such as quaternary ammonium salts, phosphonium salts, and sulfonium salts, as well as organometallic complexes. Examples of onium salts commercially available as industrial chemicals include "ADEKAOPTON CP-66 (trade name)" and "ADEKAOPTON CP-77 (trade name)" manufactured by ADEKA Corporation, "SAN-AID SI-60L (trade name)," "SAN-AID SI-80L (trade name)," and "SAN-AID SI-100L (trade name)" manufactured by Sanshin Chemical Industry Co., Ltd., and "CI Series (trade name)" manufactured by Nippon Soda Co., Ltd. Furthermore, examples of organometallic complexes include alkoxysilane-aluminum complexes.

[0068] The content of the thermal cationic polymerization initiator in the curable composition according to one embodiment of the present invention is preferably 0.001 to 20% by weight, and more preferably 0.01 to 10% by weight.

[0069] In one embodiment of the present invention, the cationic polymerization initiator refers to the above-mentioned photocationic polymerization initiator and / or thermal cationic polymerization initiator.

[0070] The curable composition according to one embodiment of the present invention may further contain, 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, silica powders such as fused silica and spherical silica, oxides such as spherical alumina, crushed alumina, magnesium oxide, beryllium oxide, and titanium oxide, nitrides such as boron nitride, silicon nitride, and aluminum nitride, carbides such as silicon carbide, hydroxides such as aluminum hydroxide and magnesium hydroxide, metals and alloys such as copper, silver, iron, aluminum, nickel, and titanium, and carbon-based materials such as diamond and carbon). Thermoplastic resins and thermosetting resins (homopolymers such as various high-density, medium-density, and low-density polyethylenes, polypropylene, polybutene, and polypentene, ethylene-propylene copolymers, polyamide resins such as nylon-6 and nylon-6,6, vinyl chloride resins, nitrocellulose resins, vinylidene chloride resins, acrylamide resins, styrene resins, vinyl ester resins, polyester resins, phenolic resins (phenolic compounds), silicone resins, fluorine-based resins, various elastomer resins such as acrylic rubber and urethane rubber, graft copolymers such as methyl methacrylate-butadiene-styrene graft copolymers and acrylonitrile-butadiene-styrene graft copolymers), reinforcing agents (glass fiber, carbon fiber, etc.), anti-sagging agents (hydrogenated castor oil, fine particle silicic anhydride, etc.), matting agents (fine powder silica, paraffin wax, etc.), abrasives (zinc stearate, etc.), The composition may contain additives (modifiers) such as an internal mold release agent (a fatty acid such as stearic acid, a fatty acid metal salt of calcium stearate, a fatty acid amide such as stearic acid amide, a fatty acid ester, a polyolefin wax, a paraffin wax, etc.), a surfactant, a leveling agent, an antifoaming agent, a viscosity adjusting diluent (organic solvent), a coupling agent, a fragrance, a flame retardant, etc.

[0071] The curable composition according to one embodiment of the present invention can be prepared by any method without particular limitations, and can be prepared by weighing out predetermined amounts of the above-described components and stirring and mixing them. For example, the composition can be prepared by premixing, followed by mixing or melt-kneading using a roll mixer, kneader, extruder, or the like. If necessary, an organic solvent (a viscosity-adjusting diluent) may be used.

[0072] The curable composition according to one embodiment of the present invention is polymerized (cured) by irradiation with ultraviolet light or heating to give a cured product. Examples of UV irradiation methods 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. The UV irradiation intensity and irradiation time are appropriately set taking into account the desired irradiation intensity or desired irradiation time, as well as the composition and shape (thickness) of the curable composition to be irradiated. Examples of heating methods include hot air circulation, infrared heating, and high-frequency heating. Furthermore, curing devices such as sealed curing ovens and tunnel ovens capable of continuous curing can be used. The heating (curing) temperature and heating (curing) time can be appropriately set taking into account the composition and shape (thickness) of the curable composition to be irradiated, as in the case of UV irradiation.

[0073] The curable composition according to one embodiment of the present invention has low volatility and excellent maintenance properties. Therefore, the curable composition can be used as a curable ink composition. Furthermore, the curable composition has low viscosity and excellent ejection properties. Therefore, the curable composition is also suitable as an inkjet curable ink composition. By applying the inkjet curable ink composition to a predetermined object using an inkjet method and curing it, the composition can be used to manufacture various parts and components, as described below. The inkjet method can form a resin film quickly, uniformly, and over a wide area, which offers advantages such as improved product precision for the various parts and components, as described below, as well as reduced manufacturing costs.

[0074] From the viewpoint of volatility, the curable ink composition and the curable inkjet ink composition 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 temperature increase rate of 10°C / min, and a nitrogen flow (200 ml / min).

[0075] The viscosity of the curable inkjet ink composition, measured at 25°C using a dynamic viscoelasticity measuring device (Rheosol-G5000, manufactured by UBM), is preferably 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. Note that the curable inkjet ink composition may be heated during application by the inkjet method to reduce the viscosity before application.

[0076] 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.

[0077] 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, adhesives for optical members, which are used for bonding optical lenses, curable compositions for stereolithography, which are used in the manufacture of various parts and members using 3D printers, and curable compositions for nanoimprinting, which are used in the formation of ultrafine circuit patterns for semiconductors.

[0078] As an example, a method for producing an optical element using the curable composition according to one embodiment 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 heat, and a step of bonding the two substrates together.

[0079] In the step of applying the curable composition for encapsulating optical elements to at least one of two substrates, the curable composition for encapsulating 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 produced as the optical element, the shape of the sealant portion formed by applying the curable composition for encapsulating optical elements is not particularly limited as long as it is a shape that can protect a laminate having an 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.

[0080] The step of curing the curable composition for encapsulating optical elements by light irradiation and / or heating may be carried out before the step of laminating the two substrates together, or may be carried out after the step of laminating the two substrates together. When the step of curing the curable composition for encapsulating optical elements by light irradiation and / or heating is carried out before the step of laminating the two substrates together, the substrates may be laminated together within a usable time (for example, 1 minute) from the time of light irradiation and / or heating until the curing reaction progresses and the substrates can no longer be bonded.

[0081] Furthermore, the step of curing the applied curable composition for encapsulating optical elements by light irradiation and / or heating may be carried out by the ultraviolet ray irradiation means and / or heating means described above.

[0082] The curable composition according to one embodiment of the present invention is not particularly limited in its application, and can be applied to products (components and members) in various fields where resin may be used as the material, and can be used as a raw material for materials in the fields of electricity and electronics, optics, architecture, civil engineering, automobiles and aircraft, and medicine, as well as for other daily necessities and miscellaneous goods.

[0083] For example, examples of parts, members, and materials in the electrical and electronic fields include resin-coated copper foil, prepreg, copper-clad laminate, printed wiring board, solder resist ink, anisotropic conductive film, anisotropic conductive paste, interlayer insulating material, adhesive, sealant, encapsulant, insulating material, thermally conductive material, hot melt material, paint, potting agent, and the like. More specific examples include: encapsulating materials and layer-forming materials for printed wiring boards and electronic components, such as interlayer insulating films and wiring coating films; display device forming materials, such as color filters, polarizing plates, display materials, resist materials, and alignment films; semiconductor device forming materials, such as resist materials and buffer coat films; and optical component forming materials, such as lenses, holograms, optical waveguides, optical circuits, optical circuit components, and antireflection 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.

[0084] 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 their surfaces.

[0085] Lenses and prisms include: spherical lenses with spherical surfaces, such as convex lenses like biconvex lenses, plano-convex lenses, and convex meniscus lenses, and concave lenses like biconcave lenses, plano-concave lenses, and concave meniscus lenses; aspherical lenses, such as lenses with aspherical surfaces like symmetrical paraboloids, ellipsoids, hyperboloids, and multi-dimensional curved surfaces (for example, quartic surfaces), and lenses with free-form surfaces without an axis of symmetry; cylindrical lenses, such as semi-cylindrical lenses; toroidal lenses, such as those with a toroidal surface with different radii of curvature in the vertical and horizontal directions like the surface of a doughnut; thin Fresnel lenses, in which ring-shaped prisms, each with a reflective surface that changes the direction of light and a refracting surface that transmits light, are arranged concentrically on a plane, with the multiple prisms becoming successively smaller or larger toward the center; diffractive lenses, in which a fine relief with a depth on the order of the wavelength of light is formed concentrically; A prism having two or more optically flat surfaces, at least one pair of surfaces of which is substantially non-parallel, is also included. ２ and SiO ２ Examples of such reflective films include those prepared by treating inorganic compounds such as those mentioned above by vacuum deposition, sputtering, or CVD, or by allowing a light absorber to coexist therewith, thereby transmitting light in a desired wavelength range while reflecting light in an undesired wavelength range.

[0086] Examples of materials in the construction field include joint sealants, coating materials, and primers for exterior materials such as various metal panels and siding boards; sealants, adhesives, injection materials, vibration-damping materials, soundproofing materials, conductive materials for electromagnetic wave shielding, and putty materials used between exterior materials, base materials, ceiling materials, and interior materials; adhesives for bonding tiles and stone to exterior wall materials and base materials; adhesives and pressure-sensitive adhesives for bonding wood flooring materials, polymer material floor sheets, and floor tiles to various floors; and injection materials for repairing cracks in various exterior and interior materials.

[0087] Examples of materials used in the civil engineering field include joint sealants, coating materials, primers, paints, putty materials, injection materials, spray materials, and formwork for various concrete products such as roads, bridges, tunnels, and breakwaters.

[0088] Examples of materials used in the automotive and aircraft fields include: structural materials, adhesives for bodies and parts, sealing materials, coating materials, cushioning materials, vibration-damping materials, soundproofing materials, and spray materials; adhesives, pressure-sensitive adhesives, coating materials, and foam materials for automotive interiors; and sealing materials, adhesives, and coating materials for steel plate joints.

[0089] Examples of materials in the medical field include artificial bones, dental impression materials, medical rubber materials, medical adhesives, and medical device sealing materials.

[0090] [Summary] As described above, 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 completed the present invention.

[0091] That is, the first invention is a curable composition containing an epoxy-oxetane compound represented by chemical formula (I). (In the formula, n may be the same or different and represents an integer of 2 to 5.)

[0092] The curable composition of the first invention may also contain a cationic polymerization initiator.

[0093] A second invention is a curable ink composition containing a curable composition.

[0094] A third invention is a curable inkjet ink composition containing a curable ink composition.

[0095] A fourth invention is 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.

[0096] 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.

[0097] The curable composition for encapsulating optical elements according to the fifth invention may be used for encapsulating organic electroluminescence elements.

[0098] A sixth invention is an adhesive for optical members, which contains 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.

[0099] 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.

[0100] An eighth invention is a curable composition for nanoimprints 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.

[0101] 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.

[0102] [Main raw materials, etc.] 3,3-bis(bromomethyl)oxetane (Tokyo Chemical Industry Co., Ltd.) 3,3-bis(hydroxymethyl)oxetane: Synthesized in accordance with the method described in "Journal of Polymer Science: Part A Polymer Chemistry, Vol. 27, 3083-3112 (1989)". Epichlorohydrin (Osaka Soda Co., Ltd.) Benzyltrimethylammonium chloride (Fujifilm Wako Pure Chemical Industries, Ltd.) Sodium hydroxide (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 (Fujifilm Wako Pure Chemical Industries, Ltd.) 2-buten-1-ol (Tokyo Chemical Industry Co., Ltd.) Toluene (Fujifilm Wako Pure Chemical Industries, Ltd.) Dichloromethane (Fujifilm Wako Pure Chemical Industries, Ltd.) N,N-dimethylformamide (Fujifilm Wako Pure Chemical Industries, Ltd.) Hexane (Fujifilm Wako Pure Chemical Industries, Ltd.) Ethyl acetate (Fujifilm Wako Pure Chemical Industries, Ltd.)

[0103] The thermal cationic polymerization initiators (thermal acid generators) used in the evaluation tests were as follows: Dibenzylmethyl-p-hydroxyphenylsulfonium hexafluoroantimonate (manufactured by Sanshin Chemical Industry Co., Ltd., "Sanaid SI-100L (trade name)")

[0104] 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 of the epoxy oxetane compounds used in the Examples and Comparative Examples was measured. The measurement was performed using a differential thermal thermogravimetry analyzer (STA7300, manufactured by Hitachi High-Tech Science Corporation) with a sample weight of 10 mg, a temperature increase rate of 10°C / min, and a nitrogen flow of 200 ml / min. (b) Measurement of Viscosity The viscosity of the epoxy oxetane compounds used in the Examples and Comparative Examples was measured at 25°C using a dynamic viscoelasticity analyzer (Rheosol-G5000, manufactured by UBM). (c) Curability of Curable Compositions Gel time measurements (hot plate method) were performed 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 mold frame consisting of two release-treated glass plates (120 mm x 120 mm x 3 mm) sandwiched between them and secured with clips, with a 4 mm thick U-shaped spacer made of silicone rubber. The mold frame was then placed in a ventilated oven and heated at 65°C for 2 hours, and then further heated at 150°C for 2 hours to cure. The cured product was then cooled to room temperature, removed, and a 10 mm (length) x 10 mm (width) x 4 mm (thickness) test piece was cut using a cutter. Note that, in this specification, room temperature refers to 15 to 25°C. The glass transition temperature (Tg) and the coefficient of linear expansion (CTE) of these test specimens were measured using a thermomechanical analyzer (TMA: Hitachi High-Tech Science Corporation, "TMA7100") (flow gas: nitrogen, heating condition: 5°C / min.).

[0105] Synthesis Example 1 Synthesis of Epoxy-Oxetane Compound Represented by Chemical Formula (IV) A 10-L separable flask was charged with 391.4 g (3.31 mol) of 3,3-bis(hydroxymethyl)oxetane, 2438.6 g (26.36 mol) of epichlorohydrin, and 12.8 g of benzyltrimethylammonium chloride. The mixture was ice-cooled to 10°C, and 3865.2 g (46.38 mol) of 48% aqueous sodium hydroxide solution was added dropwise and stirred for 14 hours. Dichloromethane was added to the reaction solution, which was then washed with water, and the organic layer was concentrated. The resulting concentrate was purified by distillation to obtain 169.1 g (0.73 mol / yield 22.2%) of the epoxy-oxetane compound represented by chemical formula (IV) as a colorless, transparent liquid.

[0106]

[0107] Synthesis Example 2 Synthesis of Compound Represented by Chemical Formula (Va) 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 placed in a 300 mL recovery flask and cooled to 5°C with stirring on ice. 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 mixture was warmed to room temperature and stirred for 14 hours. Subsequently, toluene was added to the reaction solution, and the mixture 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 the compound represented by chemical formula (Va) as a colorless, transparent liquid.

[0108]

[0109] Synthesis Example 3 Synthesis of Epoxy-Oxetane Compound Represented by Chemical Formula (V) 24.98 g (73.8 mmol) of the compound represented by chemical formula (Va) synthesized in Synthesis Example 2 and 73.80 g of dichloromethane were charged into a 1 L recovery flask and cooled to 5°C on ice. Next, 45.48 g (184.5 mmol) of 70 wt % 3-chloroperbenzoic acid was added, and the mixture was heated to 40°C and stirred for 20 hours. The reaction mixture was then filtered to remove solids, washed with aqueous potassium carbonate 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 chemical formula (V) as a colorless, transparent liquid.

[0110]

[0111] Synthesis Example 4 Synthesis of Compound Represented by Chemical Formula (VI) 73.18 g (300.0 mmol) of 3,3-bis(bromomethyl)oxetane, 59.43 g (690.0 mmol) of 3-methyl-3-buten-1-ol, and 60.00 g of N,N-dimethylformamide were placed in a 3-L recovery flask and cooled to 5°C with ice while stirring. 70.69 g (630.0 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 solution, and the mixture was washed with water. The resulting organic layer was concentrated, and the concentrate was purified by distillation to obtain 55.00 g (216.2 mmol / yield 72.1%) of the compound represented by chemical formula (VI) as a colorless, transparent liquid.

[0112]

[0113] Synthesis Example 5 Synthesis of Epoxy-Oxetane Compound Represented by Chemical Formula (VII) 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 into a 3-L recovery flask and cooled to 5°C on ice. Next, 49.30 g (220.0 mmol) of 70 wt % 3-chloroperbenzoic acid was added, and the mixture was warmed to room temperature and stirred for 2 hours. The reaction solution was then filtered to remove solids, washed with aqueous potassium carbonate 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 chemical formula (VII) as a colorless, transparent liquid.

[0114]

[0115] Synthesis Example 6 Synthesis of Compound Represented by Chemical Formula (Ia-1) A 3-L recovery flask was charged with 85.95 g (352.4 mmol) of 3,3-bis(bromomethyl)oxetane, 63.52 g (880.8 mmol) of 3-buten-1-ol, and 587.25 g of N,N-dimethylformamide, and the mixture was ice-cooled to 5°C with stirring. 94.91 g (845.8 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 mixture was warmed to room temperature and stirred for 14 hours. Subsequently, toluene was added to the reaction solution, and the mixture was washed with water. The resulting organic layer was concentrated, and the concentrate was purified by distillation to obtain 57.2 g (252.7 mmol / yield 71.7%) of a colorless, transparent liquid.

[0116] This colorless and transparent liquid １ The H-NMR spectrum data was as follows: １ H-NMR (CDCl ３ ) 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 the compound represented by chemical formula (Ia-1).

[0117]

[0118] Synthesis Example 7 Synthesis of Epoxy-Oxetane Compound Represented by Chemical Formula (I-1) 57.20 g (252.7 mmol) of the compound represented by chemical formula (Ia-1) synthesized in Synthesis Example 6 and 500.00 g of dichloromethane were charged into a 2-L recovery flask and cooled to 5°C on ice. Next, 130.72 g (530.4 mmol) of 70 wt% 3-chloroperbenzoic acid was added, and the mixture was heated to 25°C and stirred for 20 hours. The reaction mixture was then filtered to remove solids, washed with aqueous potassium carbonate 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.

[0119] This colorless and transparent liquid １ The H-NMR spectrum data was as follows: １ H-NMR (CDCl ３ ) 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 the epoxy oxetane compound represented by chemical formula (I-1).

[0120]

[0121] Example 1 A curable composition was prepared by uniformly mixing 100 parts by weight of the epoxy-oxetane compound represented by chemical formula (I-1) synthesized in Synthesis Example 7 and 0.2 parts by weight of a thermal cationic polymerization initiator. Evaluation tests were conducted on this curable composition, and the test results obtained are shown in Table 1. Note that the 5% weight loss temperature and viscosity were measured using the epoxy-oxetane compound alone as physical property values.

[0122] Comparative Examples 1 to 3 In the same manner as in Example 1, curable compositions having the formulations shown in Table 1 were prepared and subjected to evaluation tests. The test results obtained were as shown in Table 1.

[0123]

[0124] According to one aspect of the present invention, a curable composition that has low viscosity, low volatility, and curability, compared to conventional curable compositions, can be provided, and the industrial applicability of the present invention is great.

Claims

1. A curable composition containing an epoxy oxetane compound represented by formula (I): (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 ink-jet ink composition comprising the curable ink composition according to claim 3.

5. A cured product obtained by curing at least one of the curable compositions according to claims 1 and 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 compositions according to claims 1 and 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 used for encapsulating an organic electroluminescence element.

8. An adhesive for optical components 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 compositions according to claims 1 and 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 compositions according to claims 1 and 2, the curable ink composition according to claim 3, and the curable inkjet ink composition according to claim 4.

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