Curable composition, curable ink composition, curable ink composition for inkjet, and uses thereof

Abstract

Provided are a curable composition, a curable ink composition, and a curable ink composition for inkjet, each of which has low viscosity, low volatility, and curability. And methods of using these compositions are provided. The curable composition contains an epoxy / oxetane compound represented by chemical formula (I). In the formula, n is the same or different and represents an integer of 2-5.

Description

Technical Field

[0001] This invention relates to curable compositions, curable ink compositions, curable inkjet ink compositions, and methods of using them. Background Technology

[0002] Oxycyclic butane compounds have attracted attention in recent years as monomers capable of both photocuring and thermocuring. Curable compositions containing oxycyclic butane compounds exhibit less shrinkage during curing, and their cured products (resins) also demonstrate excellent toughness, mechanical properties, heat resistance, electrical properties, water resistance, weather resistance, and transparency.

[0003] Due to these excellent characteristics, curable compositions containing oxobutane compounds are widely used as raw materials for coating materials, paints, inks, adhesives, bonding materials, various films, pastes, optical materials, sealing materials, corrosion-resistant materials, etc.

[0004] The prior art related to this invention is described below with reference to relevant literature.

[0005] The invention described in Patent Document 1 relates to an epoxy-oxocyclic butane compound and its polymer.

[0006] In this document, 3,3-bis(2,3-epoxypropyloxymethyl)oxetane (see chemical formula (Ref-5)) and 3,3-bis(2,3-epoxy-2-methylpropyloxymethyl)oxetane (see chemical formula (Ref-1)) as examples of epoxyoxetane compounds are described.

[0007] [Chemistry 1]: .

[0008] [Chemistry 2]: .

[0009] The invention described in Patent Document 2 relates to an active energy ray curable inkjet ink and its printed matter.

[0010] In this document, compounds with chemical formulas (Ref-2) to (Ref-4) are described as examples of non-acrylic cationic polymerizable compounds having an oxoethoxy ring (epoxy group) and an oxazetene ring within the same molecule.

[0011] [Chemistry 3]: .

[0012] [Chemistry 4]: .

[0013] [Chemistry 5]: .

[0014] In addition, compounds represented by the above chemical formulas (Ref-2) to (Ref-4) or their related compounds are also described in Patent Documents 3 to 5.

[0015] Curable compositions used as curable ink compositions and curable inkjet ink compositions are required to possess the following characteristics at a high level: low viscosity for ink ejection; low volatility to prevent ink drying caused by evaporation; and excellent curability initiated by heat or light (fast curing speed). However, curable compositions containing compounds shown in chemical formulas (Ref-1) to (Ref-5) cannot simultaneously possess these characteristics at a high level, and therefore problems remain in terms of viscosity (ejectability), volatility, or curability (curing speed).

[0016] [Existing Technical Documents]

[0017] (Patent Documents)

[0018] Patent Document 1: U.S. Patent No. 3,457,193, Specification Patent Document 2: Japanese Patent Application Publication No. 2005-002191, Patent Document 3: Japanese Patent Application Publication No. 2007-270070, Patent Document 4: Japanese Patent Application Publication No. 2010-111713, Patent document 5: Japanese Patent Application Publication No. 2011-208089. Summary of the Invention

[0019] (The problem that the invention aims to solve)

[0020] One 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. Another object of the present invention is to provide methods of using these compositions.

[0021] (Technical means used to solve the problem)

[0022] One aspect of the present invention is a curable composition containing an epoxy-oxobutane compound represented by chemical formula (I).

[0023] [Chemistry 6]: .

[0024] (In the formula, n can be the same or different and represents an integer from 2 to 5.)

[0025] (Invention effect)

[0026] Curable compositions containing epoxy-oxetane compounds as shown in formula (I) have low viscosity and excellent sprayability, low volatility and excellent maintainability, and consequently excellent curability (fast curing speed). Detailed Implementation

[0027] The following describes one aspect of the present invention. However, the present invention is not limited to the various embodiments and examples shown below, and various modifications can be made within the scope of the inventive concept described in its entirety. Embodiments obtained by appropriately combining the technical means disclosed in different embodiments and examples are also included within 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 description of a numerical range as "A to B" means "above A and below B" including the values ​​of both endpoints.

[0028] One aspect of the present invention provides a curable compound comprising an epoxy-oxetane compound as shown in formula (I). The epoxy-oxetane compound as shown in formula (I) has the following structure: each of the two epoxy groups is bonded to oxetane via a linker having an ether bond.

[0029] [Chemistry 7]: , In the above chemical formula (I), n can be the same or different and represents an integer from 2 to 5. From the viewpoint of easy availability of raw materials and simplification of the synthesis process, it is preferable that n is the same and is an integer from 2 to 5, more preferably an integer from 2 to 4, even more preferably an integer from 2 to 3, and particularly preferably 2.

[0030] Examples of epoxide-oxetane compounds represented by chemical formula (I) include compounds represented by chemical formulas (I-1) to (I-4).

[0031] [Chemistry 8]: , Regarding the epoxy-oxetane compounds represented by formula (I), from the viewpoint of easy availability of raw materials and simplification of the synthesis process, they are preferably epoxy-oxetane compounds represented by formulas (I-1) to (I-3), more preferably epoxy-oxetane compounds represented by formulas (I-1) or (I-2), and even more preferably epoxy-oxetane compounds represented by formula (I-1). They can be used alone or in combination of two or more.

[0032] <Synthetic methods of epoxy-oxacyclobutane compounds shown in chemical formula (I)>

[0033] The oxetane compound with leaving group shown in formula (II) is reacted with the alkene compound with hydroxyl group shown in formula (III) to generate the alkene-oxetane compound shown in formula (Ia). The double bond of the compound is then epoxidized to synthesize the epoxy-oxetane compound shown in formula (I) (see reaction scheme (A)).

[0034] [Chemistry 9]: .

[0035] Reaction scheme (A)

[0036] 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 methanesulfonyloxy group (OMs), a toluenesulfonyloxy group (OTs), or a trifluoromethanesulfonyloxy group (OTf). Furthermore, the definition of n in chemical formulas (III) and (Ia) is the same as that in chemical formula (I).

[0037] Examples of oxetane compounds having leaving groups include 3,3-bis(chloromethyl)oxetane and 3,3-bis(bromomethyl)oxetane, with 3,3-bis(bromomethyl)oxetane being preferred.

[0038] Examples of alkene compounds containing hydroxyl groups include those shown in chemical formulas (III-1) to (III-4). These alkene compounds can be used alone or in combination.

[0039] Regarding the amount of this olefin compound used (added amount), it is preferable to use an appropriate ratio in the range of 2 to 20 moles relative to the amount of oxobutane compound with a depleted group used (added amount).

[0040] [Chemistry 10]: , Here, if the olefin compound represented by chemical formula (III-1) and the olefin compound represented by chemical formula (III-2) are used separately as the olefin compound for the reaction, the epoxy-oxetane compound represented by chemical formula (I-1) and the epoxy-oxetane compound represented by chemical formula (I-2) can be obtained respectively.

[0041] The olefin-oxetane compound represented by chemical formula (Ia) can be synthesized in the presence of a base (i) or a catalyst (ii) to promote the reaction. Additionally, a reaction solvent (iii) can be used as long as it does not hinder the reaction.

[0042] In addition, in the reaction of epoxidizing the double bond of the compound, general epoxidation (oxidation) methods can be used, such as using peracid, using sodium tungstate as a catalyst and using hydrogen peroxide, or using hydrogen peroxide with a base in an acetonitrile-alcohol solvent.

[0043] Examples of the bases (i) mentioned above include hydrides, hydroxides, carbonates, bicarbonates, alkoxides, or organic amine compounds of alkali metals or alkaline earth metals.

[0044] Examples of such bases (i) include sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium alkoxide, potassium alkoxide (e.g., potassium tert-butoxy), triethylamine, etc.

[0045] Regarding the amount of base used (added amount), it is generally preferred to use an appropriate ratio in the range of 2 to 20 moles relative to the amount of oxobutane compound with a detached group.

[0046] Examples of catalysts (ii) mentioned above include quaternary ammonium salts and quaternary phosphorus salts.

[0047] Examples of quaternary ammonium salts include halides (fluorides, chlorides, bromides, iodides) of tetrabutylammonium, tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrahexylammonium, tetraoctylammonium, tetradecylammonium, hexadecyltriethylammonium, dodecyltrimethylammonium, trioctylmethylammonium, octyltriethylammonium, benzyltrimethylammonium, benzyltriethylammonium, benzyltributylammonium, benzyldimethyloctadecylammonium, and phenyltrimethylammonium.

[0048] Examples of quaternary phosphonium salts include halides (fluorides, chlorides, bromides, iodides) of tetrabutylphosphonium, tetramethylphosphonium, tetraethylphosphonium, tetrapropylphosphonium, tetrahexylphosphonium, tetradecylphosphonium, tetraoctylphosphonium, triethyloctadecylphosphonium, trioctylethylphosphonium, hexadecyltriethylphosphonium, tetraphenylphosphonium, and methyltriphenylphosphonium.

[0049] These substances can be combined to be used as catalysts (ii).

[0050] Regarding the amount of catalyst (ii) used (added amount), it is preferable to use an appropriate ratio in the range of 0.0001 to 1.0 moles relative to the amount of oxobutane compound with the depletion group used (added amount).

[0051] As the solvent (iii) for the above reaction, there are no particular limitations as long as it does not hinder the reaction. Examples 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), dimethyl sulfoxide (DMSO), and hexamethylphosphoric triamine (HMPA). One or more of these solvents may be used in appropriate amounts.

[0052] The reaction temperature for synthesizing the olefin-oxetane compound shown in formula (Ia) is preferably set in the range of 0 to 150°C, and more preferably in the range of 20 to 120°C. Furthermore, the reaction time can be appropriately set according to the set reaction temperature, but is preferably set in the range of 1 to 48 hours.

[0053] After the reaction is complete, the olefin-oxetane compound, which is the precursor of the target compound, can be separated from the resulting reaction solution by means such as solvent extraction.

[0054] Furthermore, depending on the requirements, it can be refined by means of washing with water, activated carbon treatment, silica gel chromatography, etc.

[0055] In the epoxidation reaction of olefin-oxetane compounds using the above-mentioned peracids, persulfate-based reagents such as Oxone, peracetic acid, and m-chloroperbenzoic acid (3-chloroperbenzoic acid) can be used. Regarding the amount of peracid used (added), a suitable ratio in the range of 1.0 to 5.0 moles is preferably used relative to the double bonds present in the olefin-oxetane compound.

[0056] In this epoxidation reaction, there are no particular restrictions on the reaction solvent as long as it does not hinder the reaction. Examples include: alcohols such as water, methanol, ethanol, and 2-propanol; aliphatic hydrocarbons such as hexane and heptane; ketones such as acetone and 2-butanone; esters such as ethyl acetate and butyl acetate; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as methylene chloride (dichloromethane), chloroform, carbon tetrachloride, trifluorochloromethane, 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-methylpyrrolidone, and hexamethylphosphoric triamine; and sulfoxides such as dimethyl sulfoxide (DMSO). One or more of these reaction solvents can be used in appropriate amounts.

[0057] The reaction temperature for this epoxidation reaction is typically in the range of -10 to 150°C, preferably in the range of 0 to 100°C. The reaction time can be appropriately set according to the reaction temperature, but is typically set in the range of 1 to 24 hours, preferably in the range of 1 to 6 hours.

[0058] After the reaction is complete, the target compound, such as the epoxy-oxetane compound shown in chemical formula (I), can be separated from the resulting reaction solution by means such as solvent extraction.

[0059] Furthermore, depending on the requirements, it can be refined by means of washing with water, activated carbon treatment, silica gel chromatography, etc.

[0060] In the reaction of epoxidizing an olefin-oxetane compound using sodium tungstate as a catalyst and hydrogen peroxide, the amount of hydrogen peroxide used can be 1.0 to 5.0 moles relative to the double bonds present in the olefin-oxetane compound. Furthermore, regarding the amount of sodium tungstate used (added), a suitable proportion in the range of 0.001 to 0.5 moles relative to the double bonds present in the olefin-oxetane compound is preferably adopted.

[0061] In this epoxidation reaction, there are no particular restrictions as long as the reaction is not hindered; for example, the same reaction solvent as in the case of epoxidation using peracid described above can be used.

[0062] Furthermore, the reaction temperature for this epoxidation reaction is the same as that for the epoxidation using peracid described above, typically ranging from -10 to 150°C, and preferably from 0 to 100°C. The reaction time can be appropriately set according to the reaction temperature, but is typically set within the range of 1 to 24 hours, and preferably within the range of 1 to 6 hours.

[0063] After the reaction is complete, similar to the case of epoxidation using peracid described above, the epoxy-oxetane compounds shown in formula (I) can be separated from the resulting reaction solution by means such as solvent extraction. Additionally, the separated epoxy-oxetane compounds shown in formula (I) can be purified as needed.

[0064] In the above reaction of epoxidizing olefin oxetane compounds with hydrogen peroxide in an acetonitrile-alcohol solvent and a base, the amount of hydrogen peroxide used (added) is preferably an appropriate ratio in the range of 1.0 to 5.0 moles relative to the double bonds present in the olefin oxetane compound.

[0065] In addition, the amount of acetonitrile used (added) is preferably an appropriate ratio in the range of 0.5 to 5.0 moles relative to the olefin oxetane compound.

[0066] The amount of alcohol used (added) is preferably an appropriate proportion in the range of 10 to 80% by weight before the addition of hydrogen peroxide. In addition, it is preferable to use an alkali to set the pH in the range of 7 to 13.

[0067] The alcohol used for this epoxidation is preferably a saturated alcohol with 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). One or more of these alcohols may be used in appropriate amounts.

[0068] Examples of bases used for this epoxidation include hydroxides, carbonates or bicarbonates of alkali metals or alkaline earth metals, or organic amine compounds. Sodium hydroxide, potassium hydroxide, potassium carbonate, and potassium bicarbonate are preferred, and one or more of them may be used in appropriate amounts.

[0069] Furthermore, the reaction temperature for this epoxidation is the same as that for the epoxidation using peracid described above, typically set in the range of -10 to 150°C, preferably in the range of 0 to 100°C. The reaction time can be appropriately set according to the reaction temperature, but is typically set in the range of 1 to 48 hours, preferably in the range of 1 to 6 hours.

[0070] After the reaction is complete, similar to the case of epoxidation using peracid described above, the epoxy-oxetane compounds shown in formula (I) can be separated from the resulting reaction solution by means such as solvent extraction. Additionally, the separated epoxy-oxetane compounds shown in formula (I) can be purified as needed.

[0071]

[0072] The epoxy-oxobutane compounds shown in chemical formula (I) exhibit excellent curing properties.

[0073] That is, by curing a curable composition containing an epoxy-oxetane compound of chemical formula (I) (hereinafter sometimes referred to as "first curable compound"), a cured product (resin) that is expected to exhibit excellent properties can be obtained.

[0074] Here, in the curable composition of one aspect of the present invention, the first curable compound and other curable compounds different therefrom (hereinafter, sometimes referred to as the "second curable compound") may also be used together.

[0075] During the curing (polymerization) of the curable composition of one aspect of the present invention, a cured product formed by copolymerizing the first curable compound and the second curable compound can be obtained by coexisting the first curable compound with a second curable compound that is different from it.

[0076] Here, the second curable compound includes both polymeric monomers and polymeric oligomers (semi-cured products) having a structure formed by the polymerization of polymeric monomers.

[0077] Examples of such polymerizable monomers include well-known epoxy compounds (note: sometimes also called epoxy resins), oxetane compounds, epoxy-oxetane compounds (containing oxoethene rings and oxetane rings within the molecule), acrylate compounds (sometimes called acrylic resins), etc.

[0078] As an epoxy compound, any compound that has an oxoethene ring (epoxy group / glycidyl group) in its molecule can be used without particular restrictions. Examples include: Polyglycidyl ethers are obtained by reacting polyphenols such as bisphenol A, bisphenol F, bisphenol AD, catechol, and resorcinol, or polyols such as glycerol and polyethylene glycol with epichlorohydrin. Glycidyl ether esters are obtained by reacting hydroxycarboxylic acids such as p-hydroxybenzoic acid and β-hydroxynaphthoic acid with epichlorohydrin; Polyglycidyl esters are obtained by reacting polycarboxylic acids such as phthalic acid and terephthalic acid with epichlorohydrin. Glycidyl urea compounds with two or more epoxy groups in the molecule, such as 1,3,4,6-tetraglycidyl urea. Alicyclic epoxy compounds such as 3′,4′-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate; Nitrogen-containing cyclic epoxy compounds such as triglycidyl isocyanurate and hydantoin-type epoxy compounds; Epoxy-modified organopolysiloxane compounds, such as epoxidized phenolic varnish resins, epoxidized cresol varnish resins, epoxidized polyolefins, cyclic aliphatic epoxy resins, urethane-modified epoxy resins, and epoxy-modified organopolysiloxane compounds obtained by hydrosilylation addition reactions of organic compounds having carbon-carbon double bonds and glycidyl groups with silicon compounds having SiH groups (e.g., epoxy-modified organopolysiloxane compounds disclosed in Japanese Patent Application Publication Nos. 2004-99751 and 2006-282988), etc., can also be used in combination.

[0079] As an oxetane compound, any compound containing an oxetane ring (oxetane butyl / oxetane alkyl) within its molecule can be used without particular restriction. Examples include: 3-Ethyl-3-hydroxymethyloxetane, 3-(methyl)allyloxymethyl-3-ethyloxetane, (3-Ethyl-3-oxetanebutylmethoxy)methylbenzene, 4-Fluoro-[1-(3-ethyl-3-oxetanebutylmethoxy)methyl]benzene, 4-Methoxy-[1-(3-ethyl-3-oxecyclobutylmethoxy)methyl]benzene, [1-(3-ethyl-3-oxetanebutylmethoxy)ethyl]phenyl ether, Isobutoxymethyl (3-ethyl-3-oxetanebutylmethyl) ether, Isoborneol oxyethyl (3-ethyl-3-oxetanebutylmethyl) ether, Isoborneol (3-ethyl-3-oxetanebutylmethyl) ether, 2-Ethylhexyl(3-ethyl-3-oxetanebutylmethyl) ether, Ethyl diethylene glycol (3-ethyl-3-oxetanebutylmethyl) ether, Dicyclopentadiene (3-ethyl-3-oxetanebutylmethyl) ether, Dicyclopentenyloxyethyl(3-ethyl-3-oxetanebutylmethyl) ether, Dicyclopentenyl (3-ethyl-3-oxetanebutylmethyl) ether, Tetrahydrofurfuryl(3-ethyl-3-oxetanebutylmethyl) ether, 2-Hydroxyethyl (3-ethyl-3-oxetanebutylmethyl) ether, 2-Hydroxypropyl (3-ethyl-3-oxetanebutylmethyl) ether, Butoxyethyl (3-ethyl-3-oxetanebutylmethyl) ether, Borneol (3-ethyl-3-oxetanebutylmethyl) ether, 3,7-bis(3-oxetane)-5-oxononane, 3,3′-[1,3-(2-methylene)propanediylbis(oxomethylene)]bis-(3-ethyloxetane), 1,4-Bis[(3-ethyl-3-oxetanebutylmethoxy)methyl]benzene, 1,2-Bis[(3-ethyl-3-oxetane-butylmethoxy)methyl]ethane, 1,3-Bis[(3-ethyl-3-oxetanebutylmethoxy)methyl]propane, Ethylene glycol bis(3-ethyl-3-oxetanebutylmethyl) ether, Dicyclopentenyl bis(3-ethyl-3-oxetanebutylmethyl) ether, Triethylene glycol bis(3-ethyl-3-oxetanebutylmethyl) ether, Tetraethylene glycol bis(3-ethyl-3-oxetanebutylmethyl) ether, Tricyclodecanediyldimethylene (3-ethyl-3-oxetanebutylmethyl) ether, Trimethylolpropane tris(3-ethyl-3-oxetanebutylmethyl) ether, 1,4-Bis(3-ethyl-3-oxetanebutylmethoxy)butane, 1,6-bis(3-ethyl-3-oxetanebutylmethoxy)hexane, Pentaerythritol tris(3-ethyl-3-oxetanebutylmethyl) ether, Pentaerythritol tetra(3-ethyl-3-oxetanebutylmethyl) ether, Polyethylene glycol bis(3-ethyl-3-oxetanebutylmethyl) ether, Dipentaerythritol hexa(3-ethyl-3-oxetanebutylmethyl) ether, Dipentaerythritol penta(3-ethyl-3-oxetanebutylmethyl) ether, Dipentaerythritol tetra(3-ethyl-3-oxetanebutylmethyl) ether, Caprolactone-modified dipentaerythritol hexa(3-ethyl-3-oxetanebutylmethyl) ether Caprolactone-modified dipentaerythritol penta(3-ethyl-3-oxetanebutylmethyl) ether Di(trimethylolpropane)tetra(3-ethyl-3-oxetanebutylmethyl) ether, EO-modified bisphenol A bis(3-ethyl-3-oxetanebutylmethyl) ether, PO modified bisphenol A bis(3-ethyl-3-oxetanebutylmethyl) ether, EO-modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanebutylmethyl) ether, PO-modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanebutylmethyl) ether EO-modified bisphenol F (3-ethyl-3-oxetanebutylmethyl) ether, etc.

[0080] As epoxy-oxetane compounds, any compound having an oxetane ring (also known as above) and an oxetane ring (also known as above) within its molecule can be used without particular restriction, such as the compounds described in Patent Documents 1 to 5. The epoxy-oxetane compounds described in these documents are incorporated herein by reference.

[0081] Examples of acrylate compounds include: allyl methacrylate, vinyl methacrylate, dicyclopentenyl methacrylate, dicyclopentenyl oxyethyl methacrylate, modified allyl glycidyl ether (Denacol Acrylate DA111 (trade name)) manufactured by Nagase ChemteX Co., Ltd., urethane methacrylates, epoxy methacrylates, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, di(trimethylolpropane) tetramethacrylate, dipentaerythritol hexamethacrylate, di(methacrylate) butylene glycol, di(methacrylate) nonylene glycol, polypropylene glycol methacrylates, bisphenol A dimethacrylate, tri-2-(meth)acryloyloxyethyl isocyanurate, and polyorganosiloxanes containing (meth)acrylate groups.

[0082] In one aspect of the curable composition of the present invention, the aforementioned polymeric monomers and polymeric oligomers can be used in combination as a second curable compound, and the polymeric monomers exemplified above (different types of polymeric monomers can be used in combination) can also be used as polymeric monomers. Regarding polymeric oligomers, different types of polymeric oligomers can also be used in combination.

[0083] Regarding the ratio between the content of the first curable compound and the content of the second curable compound in the curable composition of one aspect of the present invention, the content of the second curable compound is preferably in the range of 0 to 1000 times the amount (weight ratio) of the first curable compound, and more preferably in the range of 0.01 to 100 times the amount (weight ratio).

[0084] As a method for curing (polymerizing) the curable composition of one aspect of the present invention, methods of photocuring and thermal curing can be cited.

[0085] Methods of photopolymerization include irradiation with active energy rays and the use of photopolymerization initiators. Active energy rays include light, radiation, electromagnetic waves, or electron beams, with light, especially ultraviolet light, being representative examples.

[0086] As photopolymerization initiators, photocationic polymerization initiators can be used, and photoradical polymerization initiators can also be used in combination as needed; these need to be present in the curable composition. Here, for photocuring, in order to improve production efficiency and the properties of the cured product, a thermosetting method can also be used.

[0087] As a photocationic polymerization initiator, it can be any commonly used photocationic polymerization initiator without special restrictions, such as onium salts and organometallic complexes.

[0088] Examples of onium salts include diazonium salts, sulfonium salts, and iodonium salts; examples of organometallic complexes include iron-aromatic complexes, titanocene complexes, and arylsilanol-aluminum complexes.

[0089] Commercially available industrial chemicals used as photocationic polymerization initiators include, for example, "Optomer SP-150" and "Optomer SP-170" manufactured by ADEKA Corporation, "CPI-100P" manufactured by Sun Apro Corporation, "UVE-1014" manufactured by General Electronics, and "CD-1012" manufactured by Sartomer.

[0090] Regarding counterionic initiators for photocationic polymerization, SbF6 can be cited as an example. - AsF6 - B(C6F5)4 - PF6 - wait.

[0091] Regarding the content of the photocationic polymerization initiator in the curable composition of one aspect of the present invention, it is preferably 0.001 to 20% by weight, and more preferably 0.01 to 10% by weight.

[0092] Examples of photoradical polymerization initiators include: Ketals with 16 to 17 carbon atoms (e.g., acetophenone dimethyl ketal, benzyl dimethyl ketal, etc.); Acetophenone compounds with 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-phenylpropane-1-one, diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropane-1-one, etc.); Benzophenone compounds with 13 to 21 carbon atoms (e.g., benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 4,4'-dimethylaminobenzophenone, etc.); benzoin compounds with 14 to 18 carbon atoms (e.g., benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, etc.); Anthraquinone compounds with 14 to 19 carbon atoms (e.g., 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-chloroanthraquinone, 2-pentylanthraquinone, etc.); Thioxanone compounds with 13 to 17 carbon atoms (e.g., 2,4-diethylthioxanone, 2-isopropylthioxanone, 2-chlorothioxanone, etc.); Acylphosphine oxide compounds with 22 to 28 carbon atoms (e.g., 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, etc.).

[0093] Regarding the content of the photoradical polymerization initiator in the curable composition of one aspect of the present invention, it is preferably 0.001 to 20% by weight, and more preferably 0.01 to 10% by weight.

[0094] In addition, when photocuring the curable composition of one aspect of the present invention, sensitizers such as pyrene, perylene, acridine orange, thioxanone, 2-chlorothioxanone, and benzoxanthin can be used.

[0095] On the other hand, when thermally curing the curable composition of one aspect of the present invention, a thermal polymerization initiator can be used. As the thermal polymerization initiator, a thermal cationic polymerization initiator can be used, which is contained in the curable composition.

[0096] As a thermo-cationic polymerization initiator, it can be any commonly used thermo-cationic polymerization initiator without any particular restrictions. Examples include various onium salts such as quaternary ammonium salts, phosphonium salts, and sulfonium salts, as well as organometallic complexes.

[0097] Regarding commercially available industrial chemicals that are onium salts, examples include "Adecaopton CP-66" and "Adecaopton CP-77" manufactured by ADEKA Co., Ltd., "SunAid SI-60L", "SunAid SI-80L" and "SunAid SI-100L" manufactured by Sanshin Chemical Industry Co., Ltd., and "CI series" manufactured by Nippon Soda Co., Ltd.

[0098] In addition, examples of organometallic complexes include alkoxysilane-aluminum complexes.

[0099] Regarding the content of the thermal cationic polymerization initiator in the curable composition of one aspect of the present invention, it is preferably 0.001 to 20% by weight, and more preferably 0.01 to 10% by weight.

[0100] Here, in one aspect of the invention, the cationic polymerization initiator refers to the aforementioned photocationic polymerization initiator and / or thermal cationic polymerization initiator.

[0101] Provided that the effect of the invention is not impaired, the curable composition involved in one aspect of the invention may further contain: Pigments (titanium white, cyan blue, watching red, iron oxide red, carbon black, aniline black, manganese blue, iron oxide black, ultramarine blue, Hansa red, chrome yellow, chrome green, etc.) Inorganic fillers (calcium carbonate, kaolin, clay, talc, mica, barium sulfate, zinc aluminate, gypsum, zinc stearate, perlite, quartz, quartz glass, fused silica, spherical silica, etc.; 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; carbon-based materials such as diamond and carbon). Thermoplastic and thermosetting resins (high-density, medium-density, and low-density homopolymers of polyethylene, polypropylene, polybutene, polypentene, etc.; ethylene-propylene copolymers; nylon-6, nylon-6, 6 and other polyamide resins; vinyl chloride resins; nitrocellulose resins; vinylidene chloride resins; acrylamide resins; styrene resins; vinyl ester resins; polyester resins; phenolic resins (phenolic compounds); silicone resins; fluorinated resins; acrylate rubber, urethane rubber and other elastomer resins; methyl methacrylate-butadiene-styrene graft copolymers, acrylonitrile-butadiene-styrene graft copolymers, etc., etc.) Reinforcing agents (glass fiber, carbon fiber, etc.) Anti-sagging agents (hydrogenated castor oil, micronized anhydrous silica, etc.) Matting agents (micronized silica, paraffin, etc.) Abrasives (zinc stearate, etc.) Internal release agents (such as stearic acid and other fatty acids, fatty acid metal salts such as calcium stearate, fatty acid amides such as stearamide, fatty acid esters, polyolefin waxes, paraffin waxes, etc.) Additives (modifiers) such as surfactants, leveling agents, defoamers, viscosity adjusters (organic solvents), coupling agents, fragrances, and flame retardants.

[0102] Regarding the preparation of the curable composition of one aspect of the present invention, there are no particular limitations on the preparation method. It can be prepared by weighing a specified amount of the above-mentioned components and mixing them. For example, after premixing, it can be prepared by mixing or melt mixing using a roller mill, kneader, or extruder. Organic solvents (viscosity adjusting diluents) can also be used as needed.

[0103] In one aspect of the invention, the curable composition is polymerized (cured) by ultraviolet irradiation or heating, thereby achieving a cured product.

[0104] As a means of ultraviolet irradiation, methods such as using chemical lamps, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, and metal halide lamps can be cited.

[0105] The intensity and duration of ultraviolet irradiation should be appropriately set based on consideration of the required irradiation intensity or duration, as well as the components and shape (thickness) of the curable composition to be irradiated.

[0106] Examples of heating methods include hot air circulation, infrared heating, and high-frequency heating. Additionally, examples of curing devices include closed curing ovens and tunnel ovens capable of continuous curing.

[0107] Regarding the heating (curing) temperature and heating (curing) time, similar to the case of ultraviolet irradiation, they can be appropriately set based on the components and shape (thickness) of the curable composition to be irradiated.

[0108] The curable composition of one aspect of the present invention has low volatility, thus exhibiting excellent maintainability. Therefore, the curable composition can be used as a curable ink composition. Furthermore, the curable composition has low viscosity, thus exhibiting excellent ejectibility. Therefore, it is also suitable for use as a curable ink composition for inkjet printing. The method of applying the inkjet curable ink composition to a specified object using an inkjet method and then curing it can be used in the manufacture of various parts or components described later. The inkjet method can form a resin film over a large area at high speed and uniformly, thus not only improving the product precision of various parts or components described later, but also offering advantages such as reduced manufacturing costs.

[0109] Regarding the 5% weight loss temperature (°C) obtained by measuring the curable ink composition and the inkjet curable ink composition using a differential thermogravimetric analyzer under conditions of 10 mg sample weight, 10 °C / min heating rate, and 200 ml / min nitrogen flow rate, from the viewpoint of volatility, it is preferably 185 °C or higher, and more preferably 190 °C or higher.

[0110] The viscosity of the curable inkjet ink composition, measured using a dynamic viscoelasticity measuring device (UBM Rheosol-G5000) at 25°C, 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. Here, when coating using an inkjet method, heating the curable inkjet ink composition can also reduce viscosity.

[0111] Furthermore, the surface tension obtained by measuring the curable ink composition for inkjet printing using a dynamic wettability tester at 25°C is preferably 15 mN / m or more and 35 mN / m or less, more preferably 20 mN / m or more and 30 mN / m or less.

[0112] Examples of preferred applications of curable inkjet ink compositions include curable compositions for sealing optical components, which are used as sealants for optical components such as organic electroluminescent (hereinafter referred to as organic EL) elements and organic thin-film solar cell elements; adhesives for optical components used for bonding optical lenses; curable compositions for photoforming used in manufacturing various parts and components using 3D printers; and curable compositions for nanoprinting used in forming semiconductor microcircuit patterns.

[0113] Regarding a method for manufacturing an optical element by using the curable composition of one aspect of the present invention as a curable composition for sealing optical elements, as an example, a method comprising the following steps can be cited: a step of coating the curable composition for sealing optical elements onto at least one of two substrates by inkjet printing; a step of curing the coated curable composition for sealing optical elements by light irradiation and / or heating; and a step of bonding the two substrates together.

[0114] In the process of coating at least one of two substrates with a curable composition for sealing optical elements, the composition can be applied to either the entire substrate or only a portion of it. For example, in the case of manufacturing an organic EL element as an optical element, the shape of the sealant portion coated with the curable composition is not particularly limited, as long as it can protect the laminate containing the organic light-emitting material layer sandwiched between the two substrates from the influence of external gases. That is, it can be a shape that completely covers the laminate or a pattern that closes the periphery of the laminate.

[0115] The process of curing the optical element sealing curing composition by light irradiation and / or heating can be performed either before or after the bonding process of the two substrates. If the process of curing the optical element sealing curing composition by light irradiation and / or heating is performed before the bonding process of the two substrates, then bonding can be performed within the available time (e.g., 1 minute) from the start of light irradiation and / or heating until the curing reaction reaches the point where re-bonding is no longer possible.

[0116] Furthermore, the process of curing the coated optical element sealing curable composition by light irradiation and / or heating can be carried out by the aforementioned ultraviolet irradiation and / or heating methods.

[0117] The curable composition of one aspect of the present invention has no particular limitation on its use and can be applied to products (parts, components) in various fields where the material is resin. It can be used as a material in the electrical, electronic, optical, construction, civil, automotive, aircraft, and medical fields, as well as a raw material for other daily necessities.

[0118] Examples of components, parts, and materials used in the electrical and electronic fields include, for instance, resin-coated copper foil, prepregs, copper-clad laminates, printed circuit boards, solder resist inks, anisotropic conductive films, anisotropic conductive pastes, interlayer insulating materials, adhesives, sealants, encapsulation materials, insulating materials, thermally conductive materials, hot-melt materials, coatings, and potting compounds. More specifically, examples include: Sealing materials and layer forming materials for printed circuit boards and electronic components, such as interlayer insulating films and wiring coatings; Materials used in the formation of display devices, such as color filters, polarizers, display materials, mask materials, and alignment films; Materials used in the formation of semiconductor devices, such as resist materials and buffer coatings; Materials used to form optical components such as lenses, holographic devices, light guides, optical paths, optical path components, and anti-reflective films.

[0119] In addition, examples include materials for organic electronic components such as organic EL elements, organic transistors, and solar cells; forming materials for rigid or flexible printed circuit boards for semiconductor mounting; assembly materials for semiconductor mounting; adhesives for flexible printed circuit boards; sealing materials for semiconductors; sealing materials for solar cells; insulating films for semiconductors; cover films for flexible printed circuit protection; and coatings for wiring.

[0120] Examples of materials used in the field of optics include lenses, prisms, thin films, fiber cores and cladding materials for optical fibers, and wear-resistant coatings for plastic lenses. For example, there are no particular limitations for lenses and prisms as long as they utilize the refraction of the surface layer.

[0121] Examples of lenses and prisms include: Spherical lenses whose surfaces are composed of 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. For example, lenses with aspherical surfaces such as symmetrical parabolic surfaces, symmetrical elliptical surfaces, symmetrical hyperboloids, or symmetrical multi-order surfaces (e.g., fourth-order surfaces), as well as aspherical lenses with free-form surfaces without an axis of symmetry; For example, cylindrical lenses such as semi-cylindrical lenses; A toroidal lens having a ring-shaped surface with different longitudinal and transverse radii of curvature, like the surface of a donut; A thin Fresnel lens is made by arranging multiple annular prisms, which have a reflecting surface that is tilted in the same way as the curve of a thick convex lens to change the direction of light travel, and a refractive surface that can transmit light, in such a way that these prisms are arranged in concentric circles in a plane and continuously shrink or expand as they approach the center. A diffraction lens is formed by arranging micro-reliefs with a depth of about the wavelength of light in concentric circles. A prism that has two or more optical planes and at least one pair of optical planes that are not substantially parallel, and serves as an optical element.

[0122] In addition, as a thin film, examples include reflective films that transmit light in the desired wavelength range and reflect light in the desired wavelength range by treating inorganic compounds such as MgF2 and SiO2 or by combining them with light absorbers through vacuum evaporation, sputtering, or CVD.

[0123] Examples of materials used in the construction industry include sealants, coverings, and primers for the joints of various metal panels, side panels, and other exterior cladding materials. Sealing materials, adhesives, fillers, vibration damping materials, sound insulation materials, conductive materials for electromagnetic wave shielding, and filler materials used between exterior materials, base materials, ceiling materials and interior materials; Adhesives used to bond ceramic tiles and stone to exterior wall materials and substrates; Adhesives and binders used to bond wood flooring, polymer flooring sheets, and floor tiles to various types of flooring; Filling materials for repairing cracks in various exterior and interior materials, etc.

[0124] Examples of materials used in the field of civil engineering include sealants, coverings, primers, coatings, fillers, grouts, spraying materials, and molding materials for joints in various concrete products such as roads, bridges, tunnels, and breakwaters.

[0125] Examples of materials used in the automotive and aerospace industries include:

[0126] Structural materials, adhesives for main body and components, sealants, covering materials, cushioning materials, vibration damping materials, sound insulation materials, and spray coatings; Adhesives, adhesives, covering materials, and foam materials used in automotive interiors; Sealing materials, adhesives, and covering materials used for steel plate joints.

[0127] Examples of materials used in the medical field include artificial bone, dental impression materials, medical rubber materials, medical adhesives, and medical device sealants.

[0128] 〔Summarize〕

[0129] As described above, the inventors discovered that by using a curable composition containing an epoxy-oxetane compound as shown in formula (I) as the aforementioned curable composition, curable ink composition, and curable inkjet ink composition, the intended purpose can be achieved, thereby completing the present invention.

[0130] That is, the first invention is a curable composition containing an epoxy-oxobutane compound as shown in chemical formula (I).

[0131] [Chemistry 11]: , In the formula, n can be the same or different and represents an integer from 2 to 5.

[0132] In addition, the curable composition of the first invention may also contain a cationic polymerization initiator.

[0133] The second invention is a curable ink composition containing a curable composition.

[0134] The third invention is a curable inkjet ink composition containing a curable ink composition.

[0135] The 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.

[0136] The fifth invention is a curable composition for sealing 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.

[0137] In addition, the curable composition for sealing optical elements of the fifth invention can also be used to seal organic electroluminescent elements.

[0138] The sixth invention is an adhesive for optical components, 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.

[0139] The seventh invention is a curable composition for optical modeling, 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.

[0140] The eighth invention is a curable composition for nanoprinting, 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.

[0141] [Example]

[0142] The present invention will be described in more detail below by way of examples and comparative examples, but the present invention is not limited thereto.

[0143] Here, the main raw materials used in the synthesis example are as follows.

[0144] [Main ingredients, etc.]

[0145] ·3,3-Di(bromomethyl)oxetane (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0146] ·3,3-bis(hydroxymethyl)oxetane: was synthesized according to the method described in "Journal of Polymer Science, Part APolymer Chemistry, Vol.27, 3083-3112 (1989)".

[0147] Epichlorohydrin (manufactured by Osaka Soda Co., Ltd.)

[0148] • Benzyltrimethylammonium chloride (manufactured by Fujifilm and Kazumitsu Chemical Co., Ltd.)

[0149] • Sodium hydroxide (manufactured by Fujifilm and Wako Pure Chemical Industries Co., Ltd.)

[0150] · 7-Octen-1-ol (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0151] · 3-Methyl-3-buten-1-ol (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0152] Potassium tert-butoxy (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0153] ·3-Chloroperbenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0154] Potassium carbonate (manufactured by Fujifilm and Wako Pure Chemical Industries, Ltd.)

[0155] ·2-Buten-1-ol (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0156] Toluene (manufactured by Fujifilm and Wako Pure Chemical Industries, Ltd.)

[0157] • Dichloromethane (manufactured by Fujifilm and Wako Pure Chemical Industries, Ltd.)

[0158] N,N-Dimethylformamide (manufactured by Fujifilm and Wako Pure Chemical Industries, Ltd.)

[0159] • Hexane (manufactured by Fujifilm and Wako Pure Chemical Industries, Ltd.)

[0160] • Ethyl acetate (manufactured by Fujifilm and Wako Pure Chemical Industries, Ltd.)

[0161] The thermal cationic polymerization initiator (thermal acid-producing agent) used in the evaluation test is as follows.

[0162] • Dibenzylmethyl-p-hydroxyphenylsulfonium hexafluoroantimonate (manufactured by Sanshin Chemical Industry Co., Ltd., "SunAidSI-100L (trade name)")

[0163] The evaluation tests (curing properties) used in the examples and comparative examples are as follows.

[0164] (a) Determination of temperature at 5% weight loss

[0165] The 5% weight loss temperature of the epoxy-oxetane compounds used in the examples and comparative examples was determined. The determination was performed using a differential thermogravimetric analyzer (STA7300, manufactured by Hitachi High-Tech Science Co., Ltd.) under the following conditions: sample weight 10 mg, heating rate 10 °C / min, and nitrogen flow rate 200 ml / min.

[0166] (b) Viscosity determination

[0167] The viscosity of the epoxy-oxobutane compounds used in the examples and comparative examples at 25°C was measured using a dynamic viscoelasticity measuring device (UBM Rheosol-G5000).

[0168] (c) Curing properties of the curable composition

[0169] The gel time of the curable compositions prepared in the examples and comparative examples described later was determined at 120°C using the hot plate method.

[0170] (d) Physical properties of cured products

[0171] Using a mixing apparatus (“Defoaming Retaro (trade name)”), the curable compositions prepared in the following examples and comparative examples were mixed and defoamed. Then, 15g portions of the mixture were injected into molds obtained by clamping two glass plates (120mm×120mm×3mm) after demolding treatment with a U-shaped spacer made of 4mm thick silicone rubber between the molded plates and fixing them with clamps. The molds were then placed in an oven with a forced-air drying process and heated at 65°C for 2 hours, and then heated at 150°C for 2 hours to cure them.

[0172] Next, cool to room temperature, then remove the cured material and use a cutting machine to prepare it into test pieces measuring 10mm (length) × 10mm (width) × 4mm (thickness). Here, in this instruction manual, room temperature refers to 15–25°C.

[0173] For these test pieces, the glass transition temperature (Tg) and coefficient of linear expansion (CTE) were determined using a thermomechanical analysis apparatus (TMA; "TMA7100" manufactured by Hitachi High-Tech Science Co., Ltd.) (the gas flow was nitrogen, and the heating rate was 5°C / min).

[0174] [Synthesis example 1]

[0175] <Synthesis of epoxide-oxacyclobutane compounds represented by chemical formula (IV)>

[0176] 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 were added to a 10 L detachable flask and cooled to 10 °C. Then, 3865.2 g (46.38 mol) of 48% sodium hydroxide aqueous solution was added dropwise, and the mixture was stirred for 14 hours. Dichloromethane was added to the reaction solution, followed by washing with water, and the organic layer was concentrated. The concentrate was purified by distillation to give 169.1 g (0.73 mol; yield 22.2%) of a colorless, transparent liquid, representing an epoxy-oxetane compound as shown in formula (IV).

[0177] [Chemistry 12]: , [Synthesis example 2] <Synthesis of compounds represented by chemical formula (Va)> In a 300 mL round-bottom 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 added and cooled to 5 °C with stirring. 17.50 g (156.0 mmol) of potassium tert-butoxy was added in fractions, ensuring the temperature did not exceed 5 °C. After stirring at 5 °C for 1 hour, the mixture was heated to room temperature and stirred for another 14 hours. Toluene was then added to the reaction mixture, followed by washing with water, and the resulting organic layer was concentrated. The concentrate was purified by distillation to give 25.01 g (73.9 mmol; yield 82.1%) of a colorless, transparent liquid as shown in formula (Va).

[0178] [Chemistry 13]: , [Synthesis example 3] <Synthesis of epoxy-oxacyclobutane compounds represented by chemical formula (V)> In a 1L flask, 24.98 g (73.8 mmol) of the compound synthesized in Synthesis Example 2 as shown in chemical formula (Va) and 73.80 g of dichloromethane were added and cooled to 5°C. Next, 45.48 g (184.5 mmol) of 70% by weight of 3-chloroperbenzoic acid was added, the temperature was raised to 40°C, and the mixture was stirred for 20 hours.

[0179] Next, the reaction solution was filtered to remove solids, then 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 (v / v)) to give 9.89 g (26.7 mmol; yield 36.2%) of a colorless, transparent liquid containing an epoxy-oxetane compound as shown in formula (V).

[0180] [Chemistry 14]: , [Synthesis example 4] <Synthesis of the compound shown in chemical formula (VI)> In a 3L flask, 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 added and cooled to 5°C with stirring. 70.69 g (630.0 mmol) of potassium tert-butoxy was added in fractions, ensuring the temperature did not exceed 5°C. After stirring at 5°C for 1 hour, the mixture was heated to room temperature and stirred for another 14 hours. Toluene was then added to the reaction mixture, followed by washing with water, and the resulting organic layer was concentrated. The concentrate was purified by distillation to give 55.00 g (216.2 mmol; yield 72.1%) of a colorless, transparent liquid as shown in formula (VI).

[0181] [Chemistry 15]: , [Synthesis example 5] <Synthesis of epoxide-oxobutane compounds represented by chemical formula (VII)> In a 3L flask, 25.44 g (100.0 mmol) of the compound synthesized in Synthetic Example 4 as shown in chemical formula (VI) and 500.00 g of dichloromethane were added and cooled to 5°C. Then, 49.30 g (220.0 mmol) of 70% by weight of 3-chloroperbenzoic acid was added, the mixture was heated to room temperature, and stirred for 2 hours.

[0182] Next, the reaction solution was filtered to remove solids, then 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 (v / v)) to give 8.76 g (30.6 mmol; yield 30.6%) of a colorless, transparent liquid as an epoxy-oxetane compound represented by chemical formula (VII).

[0183] [Chemistry 16]: , [Synthesis Example 6] <Synthesis of the compound represented by chemical formula (Ia-1)> In a 3L round-bottom flask, 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 were added and cooled to 5°C with stirring. 94.91 g (845.8 mmol) of potassium tert-butoxy was added in fractions, not exceeding 5°C. After stirring at 5°C for 1 hour, the mixture was heated to room temperature and stirred for another 14 hours. Toluene was then added to the reaction mixture, followed by washing with water, and the resulting organic layer was concentrated. The concentrate was purified by distillation to give 57.2 g (252.7 mmol; yield 71.7%) of a colorless, transparent liquid.

[0184] The colorless and transparent liquid 1 The H-NMR spectral data are as follows.

[0185] 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).

[0186] Based on the spectral data, it was determined that the colorless and transparent liquid was the compound represented by chemical formula (Ia-1).

[0187] [Chemistry 17]: , [Synthesis Example 7] <Synthesis of epoxy-oxacyclobutane compounds represented by chemical formula (I-1)> 57.20 g (252.7 mmol) of the compound synthesized in Synthetic Example 6 as shown in chemical formula (Ia-1) and 500.00 g of dichloromethane were added to a 2 L flask and cooled to 5 °C. Then, 130.72 g (530.4 mmol) of 70% by weight of 3-chloroperbenzoic acid was added, the mixture was heated to 25 °C, and stirred for 20 hours.

[0188] Next, the reaction solution was filtered to remove solids, then washed with potassium carbonate aqueous 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 give 22.80 g (88.3 mmol; yield 34.9%) of a colorless, transparent liquid.

[0189] The colorless and transparent liquid 1 The H-NMR spectral data are as follows.

[0190] 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).

[0191] Based on the spectral data, it was determined that the obtained colorless and transparent liquid was an epoxy-oxobutane compound represented by chemical formula (I-1).

[0192] [Chemistry 18]: , [Example 1] 100 parts by weight of the epoxy-oxobutane compound as shown in chemical formula (I-1) synthesized in Synthesis Example 7 were uniformly mixed with 0.2 parts by weight of a thermal cationic polymerization initiator to prepare a curable composition.

[0193] The test results obtained from the evaluation tests of this curing composition are shown in Table 1. Here, the measurements of the 5% weight loss temperature and viscosity are the individual physical property values ​​of the epoxy-oxetane compound.

[0194] [Comparative Examples 1-3]

[0195] Similar to Example 1, a curable composition having the formulation components shown in Table 1 was prepared, and the test results obtained from the evaluation test are shown in Table 1.

[0196] [Table 1]

[0197] [Industry availability]

[0198] According to one aspect of the present invention, a curable composition can be provided that combines low viscosity, low volatility and curability compared to conventional curable compositions, and the present invention has great potential for industrial application.

Claims

1. A curable composition comprising an epoxy-oxetane compound represented by the formula (I), ###0001### wherein n is the same or different and represents an integer of 2 to 5. ， 2. The curable composition according to claim 1, further comprising 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 any one of the curable composition 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 sealing an optical element comprising at least any one of the curable composition 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 sealing an optical element according to claim 6, which is used for sealing an organic electroluminescent element.

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

9. A curable composition for optical molding comprising at least any one of the curable composition 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 nanoimprinting comprising at least any one of the curable composition 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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