Olefin-oxetane compound, method for synthesizing said olefin-oxetane compound and use thereof

Abstract

The purpose is to provide a novel olefin-oxetane compound, a method for synthesizing the olefin-oxetane compound, a resin composition containing the olefin-oxetane compound and a cured product thereof. The olefin oxetane compound is represented by chemical formula (I). (In the formula, R are the same or different and represent a hydrogen atom or a C1-3 alkyl group. The wavy lines represent a trans form, a cis form, or a mixture thereof.)

Description

Olefin-oxetane compound, method for synthesizing said olefin-oxetane compound and use thereof

[0001] The present invention relates to a novel olefin-oxetane compound, a method for synthesizing the olefin-oxetane compound, and its use.

[0002] Oxetane compounds have attracted attention in recent years as photocurable and thermocurable monomers, and resin compositions containing them as components shrink little upon curing, and the cured products (resins) thereof are excellent in toughness, mechanical properties, heat resistance, electrical properties, water resistance, weather resistance, transparency, etc. Because of these excellent characteristics, resin 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] Commercially available oxetane compounds such as 3-hydroxymethyloxetane are generally highly volatile, and there is a risk that the volatilization of the components during thermal curing may cause deviations in the compounding ratio or contamination of equipment.

[0004] Patent Document 1 describes an invention relating to an active energy ray-curable resin composition containing an oxetane compound that can be used in paints, coating materials, adhesives, lenses, etc. It is characterized by the use of a 1,3-propanediol bisoxetane derivative, and discloses that the composition has excellent heat resistance, flame retardancy, mechanical properties, and curability under high humidity conditions.

[0005] Patent Document 2 describes an invention relating to a cationically polymerizable adhesive that can be used for various applications, including polarizing plates for liquid crystal displays, etc. The adhesive is characterized by the combined use of a polyfunctional oxetane compound, an alicyclic epoxy compound, and an aromatic glycidyl ether, and is disclosed to exhibit high adhesive strength to various protective films.

[0006] International Publication No. 2006 / 104167 Japanese Patent Application Laid-Open No. 2012-241053

[0007] An object of one aspect of the present invention is to provide a novel olefin-oxetane compound having excellent volatility resistance, a method for synthesizing the olefin-oxetane compound, a resin composition containing the olefin-oxetane compound, and a cured product thereof.

[0008] One aspect of the present invention is an olefin-oxetane compound represented by formula (I):

[0009] (In the formula, R may be the same or different and represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. The wavy line represents a trans isomer, a cis isomer, or a mixture thereof.)

[0010] The olefin-oxetane compound according to one embodiment of the present invention has an oxetane ring in its molecule, and is therefore expected to be useful as a resin material. Furthermore, the olefin-oxetane compound according to one embodiment of the present invention has excellent volatility resistance, and can prevent deviations in the compounding ratio and equipment contamination due to volatilization of the components contained therein during thermal curing. Furthermore, the olefin-oxetane compound according to one embodiment of the present invention can be used to synthesize various novel compounds by utilizing the carbon-carbon double bond and oxetane ring in its molecule.

[0011] 1 is an IR spectrum chart of the colorless transparent liquid obtained in Example 1.

[0012] An olefin-oxetane compound according to one embodiment of the present invention is represented by general formula (I): The olefin-oxetane compound represented by chemical formula (I) has a structure in which two olefins are symmetrically arranged with respect to one oxetane ring having an ethyl group, and the oxetane ring and the two olefin groups are bonded via a connector each having an ether bond.

[0013] (In the formula, R may be the same or different and represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. The wavy line represents a trans isomer, a cis isomer, or a mixture thereof.)

[0014] In the above chemical formula (I), R may be the same or different and represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. The alkyl group may be linear or branched. Specific examples include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. From the standpoint of easy availability of raw materials and simplification of the synthesis process, it is preferable that R are the same and represent a hydrogen atom or a methyl group.

[0015] Examples of the olefin-oxetane compound represented by chemical formula (I) include compounds represented by chemical formulas (I-1) to (I-15).

[0016]

[0017] From the viewpoints of easy availability of raw materials and simplification of the synthesis process, the olefin-oxetane compound represented by chemical formula (I) is preferably an olefin-oxetane compound represented by chemical formula (I-1) to chemical formula (I-15), and more preferably an olefin-oxetane compound represented by chemical formula (I-1). The olefin-oxetane compound represented by chemical formula (I) may be a single compound or a mixture of two or more compounds.

[0018] <Method for synthesizing an olefin-oxetane compound represented by chemical formula (I)> The olefin-oxetane compound represented by chemical formula (I) can be synthesized by reacting a bifunctional olefin compound having a hydroxy group represented by chemical formula (II) with an oxetane compound having a leaving group represented by chemical formula (III) (see reaction scheme (A)).

[0019]

[0020] In chemical formula (III), X is a leaving group and represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a mesyloxy group (OMs), a tosyloxy group (OTs), or a trifluoromethanesulfonyloxy group (OTf). In addition, in chemical formula (II), R and the wavy line have the same meanings as R and the wavy line in chemical formula (I).

[0021] Examples of the oxetane compound having a leaving group represented by the above chemical formula (III) include 3-ethyl-3-methanesulfonyloxymethyloxetane, 3-bromomethyl-3-ethyloxetane, and the like.

[0022] Examples of the bifunctional olefin compound having a hydroxy group represented by the chemical formula (II) include compounds represented by the chemical formulas (II-1) to (II-15). The bifunctional olefin compounds may be used alone or in combination of two kinds.

[0023]

[0024] The bifunctional olefin compound having a hydroxy group represented by the chemical formula (II) can be synthesized, for example, by the method described in Chinese Patent Publication No. 102267878. Biomass-derived raw materials can also be used to synthesize the bifunctional olefin compound, and from the viewpoint of reducing the environmental load, it is preferable to use the bifunctional olefin compound synthesized from biomass-derived raw materials. Specifically, the biomass-derived bifunctional olefin compound can be synthesized by using biomass-derived 2-chloromethyloxirane (epichlorohydrin) and a biomass-derived olefin compound having a terminal hydroxy group as raw materials.

[0025] The oxetane compound having a leaving group represented by chemical formula (III) can be synthesized, for example, by the method described in JP 2007-332294 A. Biomass-derived raw materials can also be used for synthesizing the oxetane compound, and from the viewpoint of reducing the environmental burden, it is preferable to use the oxetane compound synthesized from biomass-derived raw materials. By using a biomass-derived bifunctional olefin compound having a hydroxy group represented by chemical formula (II) and / or a biomass-derived oxetane compound having a leaving group represented by chemical formula (III) as raw materials, a biomass-derived olefin-oxetane compound represented by chemical formula (I) can be synthesized.

[0026] The amount (charge amount) of the bifunctional olefin compound having a hydroxy group represented by the chemical formula (II) is preferably an appropriate ratio in the range of 0.8 to 2 times the molar amount of the oxetane compound having a leaving group represented by the chemical formula (III).

[0027] In addition, when the bifunctional olefin compound represented by the chemical formula (II-1) or the bifunctional olefin compound represented by the chemical formula (II-2) is used alone in the reaction as the bifunctional olefin compound, an olefin-oxetane compound represented by the chemical formula (I-1) or an olefin-oxetane compound represented by the chemical formula (I-2) can be obtained, respectively.

[0028] The olefin-oxetane compound represented by formula (I) can be synthesized in the presence of a base (i), a catalyst (ii) for accelerating the reaction, and a reaction solvent (iii) may be used as long as it does not inhibit the reaction.

[0029] Examples of the base (i) include hydrides, hydroxides, carbonates, hydrogencarbonates, alkoxides, and organic amine compounds of alkali metals or alkaline earth metals. Examples 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 the base used (charge amount) is preferably an appropriate ratio in the range of 1.1 to 20 times the molar amount of the oxetane compound having a leaving group used (charge amount).

[0030] 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.

[0031] 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.

[0032] 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.

[0033] 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, tetrahydrofuran, diethyl ether, dioxane, 4-methyltetrahydropyran, dimethoxyethane, ethyl acetate, propyl acetate, butyl acetate, propylene glycol monomethyl ether acetate (PGMEA), acetonitrile, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, N,N-dimethylformamide (DMF), dimethylacetamide (DMA), dimethyl sulfoxide (DMSO), and hexamethylphosphoric triamide (HMPA). One or more solvents selected from these may be used in combination in appropriate amounts.

[0034] The reaction temperature when synthesizing the olefin-oxetane compound represented by chemical formula (I) 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.

[0035] 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.

[0036] Furthermore, an epoxy-oxetane compound can be obtained by epoxidizing the double bond of the olefin-oxetane compound represented by chemical formula (I). In the reaction for epoxidizing the double bond of the olefin-oxetane compound, a general epoxidation (oxidation) method can be used, such as a method using a peracid, a method using hydrogen peroxide in the presence of sodium tungstate as a catalyst, or a method using hydrogen peroxide together with a base in an acetonitrile-alcohol solvent.

[0037] 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.

[0038] 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.

[0039] 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 48 hours, preferably in the range of 1 to 24 hours.

[0040] After the reaction is complete, the epoxy-oxetane compound can be separated and extracted from the resulting reaction solution by, for example, solvent extraction, etc. If necessary, it can be further purified by washing with water, treatment with activated carbon, silica gel chromatography, etc.

[0041] 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.

[0042] 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.

[0043] 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 48 hours, preferably in the range of 1 to 24 hours.

[0044] After the reaction is complete, the epoxy-oxetane compound can be separated and extracted from the resulting reaction mixture by, for example, solvent extraction, as in the case of the epoxidation using a peracid described above. It may also be purified, if necessary.

[0045] 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.

[0046] 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.

[0047] 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.

[0048] 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 24 hours.

[0049] After the reaction is complete, the epoxy-oxetane compound can be separated and extracted from the resulting reaction mixture by, for example, solvent extraction, as in the case of the epoxidation using a peracid described above. It may also be purified, if necessary.

[0050] <Regarding the Resin Composition According to One Aspect of the Present Invention> The olefin-oxetane compound represented by chemical formula (I) is expected to be used as a resin material. That is, a resin composition containing the olefin-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 resin 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").

[0051] When the resin composition according to one aspect of the present invention is cured (polymerized), a cured product in which the first curable compound and the second curable compound are copolymerized can be obtained 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.

[0052] 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 (note: sometimes called acrylic resins).

[0053] 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.

[0054] 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.

[0055] The epoxy-oxetane compound can be any compound having an oxirane ring (same as above) and an oxetane ring (same as above) in the molecule.

[0056] 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.

[0057] In the resin 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 used in combination (different types of polymerizable monomers may be used in combination), and as the polymerizable oligomer, different types of polymerizable oligomers may be used in combination.

[0058] Regarding the ratio of the content of the first curable compound to the content of the second curable compound in the resin composition according to one embodiment 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).

[0059] Methods for curing (polymerizing) the resin 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, etc., 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 resin composition. Photocuring may also be combined with thermal curing to improve production efficiency and the properties of the cured product.

[0060] 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.

[0061] The content of the cationic photopolymerization initiator in the resin 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.

[0062] 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).

[0063] The content of the photoradical polymerization initiator in the resin 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.

[0064] When photocuring the resin 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.

[0065] On the other hand, when thermally curing the resin composition according to 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 adopted, and this can be contained in the resin composition.

[0066] 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.

[0067] The content of the thermal cationic polymerization initiator in the resin 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.

[0068] In the present invention, the cationic polymerization initiator refers to the above-mentioned photo-cationic polymerization initiator and / or thermal-cationic polymerization initiator.

[0069] The resin 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, fused silica, silica powders such as spherical silica, spherical alumina, crushed alumina, oxides such as magnesium oxide, beryllium oxide, titanium oxide, nitrides such as boron nitride, silicon nitride, aluminum nitride, carbides such as silicon carbide, hydroxides such as aluminum hydroxide, magnesium hydroxide, metals and alloys such as copper, silver, iron, aluminum, nickel, titanium, carbon-based materials such as diamond, carbon, etc.), Thermoplastic resins and thermosetting resins (homopolymers such as various high-density, medium-density, and low-density 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.

[0070] The resin composition according to one embodiment of the present invention can be prepared by any method, including weighing out predetermined amounts of the aforementioned components and stirring and mixing them. For example, the resin composition can be prepared by premixing the components and then mixing or melt-kneading them using a roll mixer, kneader, extruder, or the like. If necessary, an organic solvent (a viscosity-adjusting diluent) may be used.

[0071] The resin 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 ultraviolet 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 ultraviolet 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 resin composition to be irradiated. Examples of heating methods include hot air circulation, infrared heating, and high-frequency heating. Furthermore, a sealed curing oven or a tunnel oven capable of continuous curing can be used as a curing device. The heating (curing) temperature and heating (curing) time can be appropriately set taking into account the composition and shape (thickness) of the resin composition to be irradiated, as in the case of ultraviolet irradiation.

[0072] A resin composition according to one embodiment of the present invention can be used as a curable ink composition, and can also be used as an inkjet curable ink composition. The inkjet curable ink composition is applied to a predetermined object using an inkjet method and cured, and is 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 has advantages such as improved product precision for the various parts and components, as described below, as well as reduced manufacturing costs.

[0073] 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 of 200 mL / min.

[0074] The inkjet curable ink composition preferably has a viscosity of 5 mPa·s or more and 150 mPa·s or less, more preferably 10 mPa·s or more and 80 mPa·s or less, and even more preferably 10 mPa·s or more and 40 mPa·s or less, as measured at 25°C using a dynamic viscoelasticity measuring device (Rheosol-G5000, manufactured by UBM). The inkjet curable ink composition may be heated during application by the inkjet method to reduce the viscosity before application.

[0075] 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.

[0076] Suitable examples of the inkjet curable 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.

[0077] As an example, a method for producing an optical element using a resin composition according to one embodiment of the present invention as a curable composition for encapsulating an optical element includes the steps of applying the curable composition for encapsulating an optical element to at least one of two substrates by an inkjet method, curing the applied curable composition for encapsulating an optical element by light irradiation and / or heating, and laminating the two substrates together.

[0078] 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.

[0079] 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.

[0080] 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.

[0081] The resin composition according to one embodiment of the present invention is not particularly limited in its use, 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.

[0082] 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, pressure-sensitive adhesive, sealing material, sealant (sealing material), sealing sheet, insulating material, thermally conductive material, hot melt material, paint, potting agent, etc., but more specific examples include: sealing materials (sealants) for printed wiring boards and electronic components such as interlayer insulating film and wiring coating film, sealing materials (sealants) for image display devices, sealing sheets for image display devices, sealing materials (sealants) for organic EL display elements, sealing sheets for organic EL display elements, and layer-forming materials; 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; optical component forming materials such as lenses, holograms, optical waveguides, optical circuits, optical circuit components, and antireflection films; Coating agents such as surface protective films for semiconductor elements and organic thin-film elements (for example, organic electroluminescence elements and organic thin-film solar cell elements), hard coating agents, antifouling films and antireflection films, etc. Further examples include materials for organic electronic 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 sealants, solar cell sealants, insulating films for semiconductors, coverlay films for protecting flexible printed circuits, and coating agents for wiring coating.

[0083] Examples of materials in the optical field include lenses, prisms, films, core materials for optical fibers, cladding materials, abrasion-resistant coating agents for plastic lenses, materials for stereolithography, optical waveguides, filters, image display materials, lens arrays, sealants and reflector materials for optical semiconductor elements, light guide plates, light diffusers, diffraction elements, and optical adhesives. For example, lenses and prisms are not particularly limited as long as they utilize refraction on their surfaces. They can also be used as: materials for lenses in camera modules, LiDAR modules, and still cameras; adhesives for finder prisms, target prisms, finder covers, light-receiving sensor units, photographic lenses, and projection lenses for projection televisions; optical fiber materials for the periphery of optical switches and optical connectors in optical communication systems; sealants and adhesives for optical passive components, optical circuit components, and the periphery of optoelectronic integrated circuits; and the like. Examples of bonding locations in a camera module include between an image sensor (imaging element) such as a CMOS or CCD and a substrate, between a cut filter and a substrate, between a substrate and a housing, between a housing and a cut filter, and between a housing and a lens unit.

[0084] 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 polyhedral surfaces (for example, quartic surfaces), and lenses with free-form surfaces without an axis of symmetry; cylindrical lenses, such as semi-cylindrical cylindrical lenses; toroidal lenses, such as donut-shaped lenses with toroidal surfaces with different radii of curvature in the vertical and horizontal directions; 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 prisms becoming successively smaller or larger toward the center; and 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. ２and 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.

[0085] 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.

[0086] 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.

[0087] Examples of materials in the automotive and aircraft fields include structural materials, fiber-reinforced composites, 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 seams. Furthermore, examples of uses for substrates having a coating layer formed on their surfaces, which is made of a cured product of the resin composition according to one embodiment of the present invention, include components for various industrial equipment such as transportation vehicles (automobiles, aircraft, etc.) and electronic and electrical equipment (e.g., sliding components such as cylinders, pistons, and bearings).

[0088] Examples of materials in the medical field include artificial bones, dental impression materials, medical rubber materials, medical adhesives, and medical device sealing materials.

[0089] Other examples include paints that are applied to substrates such as metals, resin films, glass, paper, and wood.

[0090] [Summary] As a result of intensive research as described above, the present inventors have found that the desired object can be achieved by an olefin-oxetane compound obtained by reacting a bifunctional olefin compound having a certain type of hydroxy group with an oxetane compound having a certain type of leaving group, and have thus completed the present invention.

[0091] That is, the first invention is an olefin-oxetane compound represented by chemical formula (I).

[0092] (In the formula, R may be the same or different and represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. The wavy line represents a trans isomer, a cis isomer, or a mixture thereof.)

[0093] The second invention is a method for synthesizing the olefin-oxetane compound of the first invention, which comprises reacting a bifunctional olefin compound having a hydroxy group represented by chemical formula (II) with an oxetane compound having a leaving group represented by chemical formula (III).

[0094] (In the formula, R and the wavy line are the same as above.)

[0095] (In the formula, X 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).)

[0096] The third invention is a resin composition containing the olefin-oxetane compound of the first invention.

[0097] A fourth invention is a cured product obtained by curing the resin composition of the third invention.

[0098] The present invention will be described in more detail below using examples and comparative examples, but the present invention is not limited thereto. The main raw materials used are as follows: Allyl glycidyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) Allyl alcohol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) Potassium tert-butoxide (manufactured by Tokyo Chemical Industry Co., Ltd.) 3-ethyl-3-methanesulfonyloxymethyloxetane (synthesized in accordance with the method described in JP 2007-332294 A) Sodium hydroxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) Triethylamine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) 3,3-bis(bromomethyl)oxetane (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0099] The thermal cationic polymerization initiator used was as follows: Dibenzylmethyl-p-hydroxyphenylsulfonium hexafluoroantimonate (manufactured by Sanshin Chemical Industry Co., Ltd., trade name "Sanaid SI-100L")

[0100] The methods for measuring the 5% weight loss temperature, heat generation initiation temperature, heat generation peak temperature, and gel time, which are evaluation tests employed in the examples and comparative examples, are as follows.

[0101] [Measurement of 5% Weight Loss Temperature] The 5% weight loss temperature (Td5) was measured for the compounds of Example 1 and Synthesis Examples 2 and 3 described below. The measurement was performed using a differential scanning thermogravimetry analyzer ("STA7300" manufactured by Hitachi High-Tech Science Corporation) under the following conditions: sample weight 10 mg, heating rate 10°C / min, nitrogen flow (200 ml / min).

[0102] [Exothermic Onset Temperature and Exothermic Peak Temperature] The curability of the resin compositions prepared in Example 2 and Comparative Examples 1 and 2 described below was evaluated by measuring the exothermic onset temperature and the exothermic peak temperature. The measurements were performed using a differential scanning calorimeter (manufactured by Hitachi High-Tech Science Corporation, "DSC7020"), with a temperature profile from -30°C to 250°C, and a temperature rise rate of 10°C / min.

[0103] [Measurement of Gel Time] For the resin compositions prepared in Example 2 and Comparative Examples 1 and 2 described below, the gel time at 150°C was measured by the hot plate method (JIS C-2105) to evaluate the curability of the resin compositions.

[0104] Synthesis of Olefin-Oxetane Compound Represented by Chemical Formula (I-1) Synthesis Example 1 A 5 L three-neck flask was charged with 2,178 g (37,500 mmol) of allyl alcohol and 308.58 g (2,750 mmol) of potassium tert-butoxide, and the mixture was heated to 40°C. 285.35 g (2,500 mmol) of allyl glycidyl ether was then added dropwise, followed by stirring at 60°C for 14 hours. The reaction solution was then cooled to 25°C or below, filtered to remove solids, and the filtrate was evaporated under reduced pressure. The resulting concentrate was purified by distillation to obtain 391.19 g of a bifunctional olefin compound having a hydroxyl group represented by chemical formula (II-1) as a colorless, transparent liquid (yield: 91%).

[0105]

[0106] Example 1 A 5 L four-neck flask was charged with 344.44 g (2,000 mmol) of the colorless, transparent liquid obtained in Synthesis Example 1, 1,500 g of dimethyl sulfoxide, and 114.97 g (2,874 mmol) of sodium hydroxide. The mixture was heated to 60°C, and then 427.35 g (2,200 mmol) of 3-ethyl-3-methanesulfonyloxymethyloxetane was added dropwise thereto. The mixture was stirred at 70°C for 8 hours. The reaction solution was then cooled to 25°C or below, the solid matter was removed, and the filtrate was extracted with 2,000 mL of ethyl acetate. The extract was then washed with 2,000 mL of water, and the organic layer was concentrated under reduced pressure. The resulting concentrate was purified by distillation to obtain 336.92 g of a colorless, transparent liquid (yield: 62%).

[0107] This colorless and transparent liquid １ The H-NMR spectrum data was as follows: １ H-NMR (CDCl ３) δ: 5.90 (m, 2H), 5.27 (dd, 2H), 5.18 (dd, 2H), 4.47 (d, 2H), 4.37 (d, 2H), 4.00 (d, 4H), 3.75 (s, 2H), 3.66 (quin., 1H), 3.54 (m, 4H), 1.75 (q, 2H), 0.88 (t, 3H). The IR spectrum data of this colorless, transparent liquid was as shown in the chart in Figure 1. From these spectrum data, the obtained colorless, transparent liquid was identified as an olefin-oxetane compound represented by chemical formula (I-1).

[0108]

[0109] Synthesis Example 2: A 100 mL recovery flask was charged with 14.64 g (85.0 mmol) of the colorless, transparent liquid obtained in Synthesis Example 1 and 12.90 g (127.5 mmol) of triethylamine, and the mixture was stirred at room temperature. Next, 23.59 g (255.0 mmol) of epichlorohydrin was added dropwise, and the mixture was stirred at 75°C for 15 hours. Subsequently, 100 mL of chloroform and 50 mL of water were added to the reaction solution, followed by extraction and washing with water. The resulting organic layer was concentrated. The resulting concentrate was purified by silica gel column chromatography (hexane / ethyl acetate = 1 / 1 (volume ratio)), yielding 9.90 g of a colorless, transparent liquid (yield: 51%).

[0110] This colorless and transparent liquid １ The H-NMR spectrum data was as follows: １ H-NMR (CDCl ３ ) δ: 5.90 (m, 2H), 5.27 (dd, 2H), 5.18 (dd, 2H), 4.00 (m, 4H), 3.68 (d, 2H), 3.50 (m, 5H), 3.16 (m, 1H), 2.81 (t, 1H), 2.62 (dd, 1H). From this spectral data, the obtained colorless, transparent liquid was identified as an olefin-epoxy compound represented by chemical formula (IV).

[0111]

[0112] Synthesis Example 3: A 1000 mL recovery flask was charged with 39.20 g (675.0 mmol) of allyl alcohol and 125.00 g of dimethylformamide, and the mixture was ice-cooled to 5°C with stirring. Next, 67.33 g (600.0 mmol) of potassium t-butoxide was added, and 60.98 g (250.0 mmol) of 3,3-bis(bromomethyl)oxetane was added dropwise. The mixture was then warmed to room temperature and stirred for 14 hours. Subsequently, 500 mL of toluene and 250 mL of water were added to the reaction solution, which was then washed with water. The resulting organic layer was concentrated. The concentrate was purified by distillation to obtain 31.08 g of a colorless, transparent liquid (yield: 63%).

[0113] This colorless and transparent liquid １ The H-NMR spectrum data was as follows: １ H-NMR (CDCl ３ ) δ: 5.91 (m, 2H), 5.29 (dd, 2H), 5.20 (dd, 2H), 4.48 (s, 4H), 4.02 (d, 4H), 3.66 (s, 4H). From this spectral data, the obtained colorless, transparent liquid was identified as an olefin-oxetane compound represented by chemical formula (V).

[0114]

[0115] <Evaluation of Resin Composition> [Example 2] A resin composition was prepared by uniformly mixing 100 parts by weight of the olefin-oxetane compound represented by chemical formula (I-1) synthesized in Example 1 and 0.2 parts by weight of a thermal cationic polymerization initiator. The above-mentioned evaluation tests were carried out on this resin composition and the compound of Example 1, and the obtained test results are shown in Table 1.

[0116] Comparative Examples 1 and 2 Resin compositions having the formulations shown in Table 1 were prepared in the same manner as in Example 2, and the above-described evaluation tests were carried out on these resin compositions and the compounds of Synthesis Examples 2 and 3. The test results obtained were as shown in Table 1.

[0117]

[0118] As shown in Table 1, the olefin-oxetane compound according to one embodiment of the present invention has a higher 5% weight loss temperature than the compounds of Synthesis Examples 2 and 3, demonstrating its excellent volatility resistance. This indicates that a resin composition containing the olefin-oxetane compound according to one embodiment of the present invention can suppress deviations in the blending ratio and equipment contamination due to volatilization of the contained components during thermal curing of the resin composition, thereby enabling the production of resin compositions and cured products of stable quality. Furthermore, it was confirmed that the resin composition containing the olefin-oxetane compound according to one embodiment of the present invention exhibited superior curability to the resin composition of Comparative Example 1 and equivalent curability to the resin composition of Comparative Example 2.

[0119] The novel olefin-oxetane compound according to one embodiment of the present invention has an oxetane ring in its molecule, and is therefore expected to be used as a resin material. Furthermore, the olefin-oxetane compound according to one embodiment of the present invention has excellent volatility resistance, and can prevent deviations in the blend ratio and equipment contamination due to volatilization of the components contained therein during thermal curing. Furthermore, the olefin-oxetane compound according to one embodiment of the present invention can be used to synthesize various novel compounds by utilizing the carbon-carbon double bond and oxetane ring contained in the molecule.

Claims

1. An olefin-oxetane compound represented by the chemical formula (I): (In the formula, R may be the same or different and represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. The wavy line represents a trans isomer, a cis isomer, or a mixture thereof.) 2. A method for synthesizing an olefin-oxetane compound according to claim 1, which comprises reacting a bifunctional olefin compound having a hydroxy group represented by chemical formula (II) with an oxetane compound having a leaving group represented by chemical formula (III). (In the formula, R and the wavy line are the same as above.) (In the formula, X 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).) 3. A resin composition containing the olefin-oxetane compound according to claim 1.

4. A cured product obtained by curing the resin composition according to claim 3.

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