Olefin-oxetane compound, synthesis method of the olefin-oxetane compound and use of the same

Abstract

To provide a new olefin-oxetane compound, a synthesis method of the olefin-oxetane compound, a resin composition containing the olefin-oxetane compound, and a cured product of the same.SOLUTION: An olefin-oxetane compound is represented by chemical formula (I). In the formula, R is the same or different, and represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. The wavy lines represent a trans isomer, a cis isomer or a mixture thereof.SELECTED DRAWING: None

Description

Technical Field

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

Background Art

[0002] Oxetane compounds have attracted attention in recent years as monomers capable of photocuring and thermocuring. Resin compositions containing these as components have small shrinkage during curing, and the cured products (resins) are excellent in toughness, mechanical properties, heat resistance, electrical properties, water resistance, weather resistance, transparency, etc. Due to such excellent characteristics, resin compositions containing oxetane compounds are being promoted for use as raw materials for coating materials, paints, inks, adhesive materials, pressure-sensitive adhesive materials, films, pastes, optical materials, encapsulating materials, resist materials, etc.

[0003] Commercially available oxetane compounds such as 3-hydroxymethyloxetane generally have high volatility, and there is a risk of deviation in the mixing ratio due to volatilization of the contained components and equipment contamination during thermosetting.

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

[0005] Patent Document 2 describes an invention related to a cationically polymerizable adhesive that can be used for various applications such as polarizing plates for liquid crystal displays. It is characterized by using a polyfunctional oxetane compound, an alicyclic epoxy compound, and an aromatic glycidyl ether in combination, and it is disclosed that it exhibits high adhesive strength to various protective films.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0007] An object 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.

Means for Solving the Problems

[0008] As a result of intensive studies to solve the above problems, the present inventors have found that an olefin - oxetane compound obtained by reacting a bifunctional olefin compound having a certain kind of hydroxy group with an oxetane compound having a certain kind of leaving group can achieve the intended purpose, and thus have completed the present invention.

[0009] That is, the first invention is an olefin - oxetane compound represented by chemical formula (I).

[0010]

Chem.

[0011] 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).

[0012] [Chemical formula] (In the formula, R and the wavy line are the same as described above.)

[0013] [Chemical formula] (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).)

[0014] The third invention is a resin composition containing the olefin-oxetane compound of the first invention.

[0015] The fourth invention is a cured product obtained by curing the resin composition of the third invention. [Advantages of the Invention]

[0016] Since the olefin-oxetane compound of the present invention has an oxetane ring in the molecule, it is expected to be used as a resin material. In addition, the olefin-oxetane compound of the present invention is excellent in volatility resistance and can prevent deviation of the blending ratio and equipment contamination due to volatilization of the components during thermosetting. And the olefin-oxetane compound of the present invention can be used for the synthesis of various novel compounds by utilizing the carbon-carbon double bond and oxetane ring in the molecule. [Brief Description of the Drawings]

[0017]

Figure 1

[0018] The olefin-oxetane compound according to the present invention is represented by the general formula (I). The olefin-oxetane compound represented by the chemical formula (I) has a structure in which two olefins are symmetrically arranged with respect to one oxetane ring having an ethyl group, and each of the oxetane ring and the two olefin groups is bonded via a linker having one ether bond.

[0019]

Chemical formula

[0020] In the above chemical formula (I), R represents the same or different hydrogen atom or an alkyl group having 1 to 3 carbon atoms. The alkyl group may be linear or branched. Specifically, a methyl group, an ethyl group, an n-propyl group, and an isopropyl group can be mentioned. From the viewpoint of easy availability of raw materials and simplification of the synthesis process, it is preferable that R is the same and is a hydrogen atom or a methyl group.

[0021] Examples of the olefin-oxetane compound represented by the chemical formula (I) include compounds represented by the chemical formula (I-1) to the chemical formula (I-15).

[0022]

Chemical formula

[0023] From the viewpoint of easy availability of raw materials and simplification of the synthesis process, the olefin-oxetane compound represented by the chemical formula (I) is preferably an olefin-oxetane compound represented by the chemical formula (I-1) to the chemical formula (I-15), and more preferably an olefin-oxetane compound represented by the chemical formula (I-1). The olefin-oxetane compound represented by the chemical formula (I) may be alone or a mixture of two or more.

[0024] <Synthesis method of olefin-oxetane compound represented by chemical formula (I)> 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), an olefin-oxetane compound represented by chemical formula (I) can be synthesized (see reaction scheme (A)).

[0025]

Chemical formula

[0026] In chemical formula (III), X is a leaving group and represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a mesyloxy group (OMs), a tosyloxy group (OTs), or a trifluoromethanesulfonyloxy group (OTf). Also, in chemical formula (II), R and the wavy line are synonymous with R and the wavy line in chemical formula (I).

[0027] 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.

[0028] Examples of the bifunctional olefin compound having a hydroxy group represented by the above chemical formula (II) include compounds represented by chemical formulas (II-1) to (II-15). The bifunctional olefin compounds may be used alone or in combination of two kinds.

[0029]

Chemical formula

[0030] The bifunctional olefin compound having a hydroxy group represented by the above chemical formula (II) can be synthesized, for example, by the method described in Chinese Patent Publication No. 102267878. In the synthesis of the bifunctional olefin compound, raw materials derived from biomass can also be used. From the viewpoint of reducing environmental load, it is preferable to use the bifunctional olefin compound synthesized from raw materials derived from biomass. Specifically, the bifunctional olefin compound derived from biomass can be synthesized by using 2-chloromethyloxirane (epichlorohydrin) derived from biomass and an olefin compound having a terminal hydroxy group derived from biomass as raw materials.

[0031] The oxetane compound having a leaving group represented by the above chemical formula (III) can be synthesized, for example, by the method described in JP-A-2007-332294. In the synthesis of the oxetane compound, raw materials derived from biomass can also be used. From the viewpoint of reducing environmental load, it is preferable to use the oxetane compound synthesized from raw materials derived from biomass. By using a bifunctional olefin compound having a hydroxy group represented by chemical formula (II) derived from biomass and / or an oxetane compound having a leaving group represented by chemical formula (III) derived from biomass as raw materials, an olefin-oxetane compound represented by chemical formula (I) derived from biomass can be synthesized.

[0032] The amount (charged amount) of the bifunctional olefin compound having a hydroxy group represented by the above chemical formula (II) is preferably an appropriate ratio in the range of 0.8 to 2 times the molar amount relative to the amount (charged amount) of the oxetane compound having a leaving group represented by the above chemical formula (III).

[0033] In addition, when the bifunctional olefin compound represented by chemical formula (II-1) and the bifunctional olefin compound represented by chemical formula (II-2) are each used alone in the reaction as the bifunctional olefin compound, an olefin-oxetane compound represented by chemical formula (I-1) and an olefin-oxetane compound represented by chemical formula (I-2) can be obtained, respectively.

[0034] The olefin-oxetane compound represented by Chemical Formula (I) can be synthesized in the presence of base (i), and a catalyst (ii) for promoting the reaction may be used. Further, as long as the reaction is not inhibited, a reaction solvent (iii) may be used.

[0035] Examples of the base (i) include hydrides, hydroxides, carbonates, hydrogen carbonates, alkoxides of alkali metals or alkaline earth metals, or organic amine compounds. For example, sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium alkoxide, potassium alkoxide (e.g., t-butoxypotassium, etc.), triethylamine, etc. may be mentioned. The amount of the base used (charged amount) is preferably an appropriate ratio in the range of usually 1.1 to 20 times the molar amount of the amount of the oxetane compound having a leaving group used (charged amount).

[0036] Examples of the catalyst (ii) include quaternary ammonium salts, quaternary phosphonium salts, etc. Examples of the quaternary ammonium salt include salts such as halides (fluoride, chloride, bromide, iodide) of tetrabutylammonium, tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrahexylammonium, tetraoctylammonium, tetradecylammonium, hexadecyltriethylammonium, dodecyltrimethylammonium, trioctylmethylammonium, octyltriethylammonium, benzyltrimethylammonium, benzyltriethylammonium, benzyltributylammonium, benzyldimethyloctadecylammonium, phenyltrimethylammonium.

[0037] Examples of the quaternary phosphonium salts include salts such as halides (fluoride, chloride, bromide, iodide) of tetrabutylphosphonium, tetramethylphosphonium, tetraethylphosphonium, tetrapropylphosphonium, tetrahexylphosphonium, tetradecylphosphonium, tetraoctylphosphonium, triethyloctadecylphosphonium, trioctylethylphosphonium, hexadecyltriethylphosphonium, tetraphenylphosphonium, and methyltriphenylphosphonium.

[0038] These substances may be combined and used as catalyst (ii). The amount of catalyst (ii) used (charged amount) is preferably an appropriate ratio in the range of 0.0001 to 1.0 times the molar amount of the oxetane compound having a leaving group (charged amount).

[0039] The reaction solvent (iii) is not particularly limited as long as it does not inhibit the reaction. Examples 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 of these can be selected and combined, and an appropriate amount thereof can be used.

[0040] When synthesizing the olefin-oxetane compound represented by Chemical Formula (I), the reaction temperature is preferably set in the range of 0 to 150°C, more preferably in the range of 20 to 120°C. Also, the reaction time is appropriately set according to the set reaction temperature, but is preferably set in the range of 1 to 48 hours.

[0041] After the completion of this reaction, the olefin-oxetane compound, which is a precursor of the target product, can be separated and extracted from the resulting reaction solution by means such as solvent extraction. Furthermore, if necessary, it can be purified by means such as washing with water or the like, activated carbon treatment, silica gel chromatography.

[0042] In addition, an epoxy-oxetane compound can be obtained by epoxidizing the double bond of the olefin-oxetane compound represented by the chemical formula (I). In the reaction for epoxidizing the double bond of the olefin-oxetane compound, a general epoxidation (oxidation) method can be adopted. For example, methods using peracids, methods using hydrogen peroxide with sodium tungstate as a catalyst, methods using hydrogen peroxide together with a base in an acetonitrile-alcohol solvent, etc. can be mentioned.

[0043] In the reaction for epoxidizing the olefin-oxetane compound using the above-mentioned peracid, peracids such as oxone reagent, peracetic acid, and metachloroperbenzoic acid (3-chloroperbenzoic acid) can be used. The usage amount (charged amount) of the peracid is preferably an appropriate ratio in the range of 1.0 to 5.0 times the molar amount relative to the double bond of the olefin-oxetane compound.

[0044] In this epoxidation reaction, the reaction solvent is not particularly limited as long as it does not inhibit the reaction. For example, water, alcohols such as methanol, ethanol, 2-propanol, aliphatic hydrocarbons such as hexane, heptane, ketones such as acetone, 2-butanone, esters such as ethyl acetate, butyl acetate, aromatic hydrocarbons such as benzene, toluene, xylene, halogenated hydrocarbons such as methylene chloride (dichloromethane), chloroform, carbon tetrachloride, chlorotrifluoromethane, dichloroethane, chlorobenzene, dichlorobenzene, ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, dimethoxyethane, diethylene glycol dimethyl ether, amides such as formamide, N,N-dimethylformamide (DMF), dimethylacetamide (DMA), N-methyl-2-pyrrolidone, N-methylpyrrolidinone, hexamethylphosphoramide, sulfoxides such as dimethyl sulfoxide (DMSO), etc. can be mentioned. These reaction solvents can be used alone or in combination of two or more, and an appropriate amount is used as appropriate.

[0045] The reaction temperature in this epoxidation reaction is usually in the range of -10 to 150 °C, preferably set in the range of 0 to 100 °C. Also, the reaction time is appropriately set according to the reaction temperature, but usually it is set within the range of 1 to 48 hours, preferably within the range of 1 to 24 hours.

[0046] After the completion of this reaction, the epoxy-oxetane compound can be separated and taken out from the obtained reaction solution by means such as solvent extraction method. Furthermore, if necessary, it can be purified by means such as washing with water, etc., activated carbon treatment, silica gel chromatography, etc.

[0047] In the reaction of epoxidizing an olefin-oxetane compound using hydrogen peroxide with the above-mentioned sodium tungstate as a catalyst, hydrogen peroxide is used in a proportion of 1.0 to 5.0 times the molar amount relative to the double bond of the olefin-oxetane compound. Also, the amount of sodium tungstate used (charged amount) is preferably an appropriate proportion within the range of 0.001 to 0.5 times the molar amount relative to the double bond of the olefin-oxetane compound.

[0048] In this epoxidation reaction, there are no particular restrictions as long as the reaction is not inhibited. For example, the same reaction solvent as in the case of epoxidation using the above-mentioned peracid can be used.

[0049] Also, in this epoxidation reaction, the reaction temperature is usually in the range of -10 to 150 °C, preferably set in the range of 0 to 100 °C, in the same manner as in the case of epoxidation using the above-mentioned peracid. The reaction time is appropriately set according to the reaction temperature, but is usually set within the range of 1 to 48 hours, preferably within the range of 1 to 24 hours.

[0050] After the reaction is completed, in the same manner as in the case of epoxidation with the above-mentioned peracid, the epoxy-oxetane compound can be separated and taken out from the obtained reaction solution by means such as solvent extraction. Also, it may be purified if necessary.

[0051] In the reaction of epoxidizing an olefin-oxetane compound using hydrogen peroxide together with a base in the above-mentioned acetonitrile-alcohol solvent, the amount of hydrogen peroxide used (charged amount) is preferably an appropriate proportion within the range of 1.0 to 5.0 times the molar amount relative to the double bond of the olefin-oxetane compound. Also, the amount of acetonitrile used (charged amount) is preferably an appropriate proportion within the range of 0.5 to 5.0 times the molar amount relative to the olefin-oxetane compound. The amount of alcohol (charged amount) is preferably set at an appropriate ratio within the range of 10 to 80% by weight in the state before the addition of hydrogen peroxide. Further, it is preferable to set the pH within the range of 7 to 13 using a base.

[0052] The alcohol used for this epoxidation is preferably a saturated alcohol having 1 to 4 carbon atoms. Examples thereof include methanol, ethanol, n-propanol, 2-propanol, n-butanol, sec-butanol (2-butanol), and isobutanol (2-methyl-1-propanol). These alcohols can be used alone or in combination of two or more, and an appropriate amount is used.

[0053] Examples of the base used for this epoxidation include hydroxides, carbonates or bicarbonates of alkali metals or alkaline earth metals, or organic amine compounds. It is preferable to use sodium hydroxide, potassium hydroxide, potassium carbonate, or potassium bicarbonate. These can be used alone or in combination of two or more, and an appropriate amount is used.

[0054] Also, the reaction temperature for this epoxidation is usually set within the range of -10 to 150°C, preferably 0 to 100°C, in the same manner as in the case of epoxidation using the peracid described above. The reaction time is appropriately set according to the reaction temperature, but is usually set within the range of 1 to 48 hours, preferably 1 to 24 hours.

[0055] After the completion of the reaction, in the same manner as in the case of epoxidation using the peracid described above, the epoxy-oxetane compound can be separated and taken out from the obtained reaction solution by means such as solvent extraction. Further, it may be purified if necessary.

[0056] <Regarding the resin composition of the present invention> The olefin-oxetane compound represented by Chemical Formula (I) is expected to be used as a resin material. That is, for a resin composition containing an olefin-oxetane compound represented by the chemical formula (I) (hereinafter sometimes referred to as "the first curable compound"), by curing, a cured product (resin) with excellent properties can be expected to be obtained. In the resin composition of the present invention, it is also possible to use in combination the first curable compound and another curable compound different therefrom (hereinafter sometimes referred to as "the second curable compound").

[0057] When the resin composition of the present invention is cured (polymerized), by coexisting the second curable compound separately from the first curable compound, a cured product in which the first curable compound and the second curable compound are copolymerized can be obtained. The second curable compound includes both a polymerizable monomer and a polymerizable oligomer (semicured product) having a structure in which the polymerizable monomer is polymerized.

[0058] Examples of this polymerizable monomer include known epoxy compounds (note: sometimes referred to as epoxy resins), oxetane compounds, epoxy-oxetane compounds (having an oxirane ring and an oxetane ring in the molecule), acrylic compounds (note: sometimes referred to as acrylic resins), and the like.

[0059] As the epoxy compound, any compound having an oxirane ring (epoxy group / glycidyl group) in the molecule can be used without particular limitation. For example, Polyglycidyl ethers obtained by reacting polyhydric phenols such as bisphenol A, bisphenol F, bisphenol AD, catechol, resorcinol, or polyhydric alcohols such as glycerin and polyethylene glycol with epichlorohydrin; Glycidyl ether esters obtained by reacting hydroxycarboxylic acids such as p-hydroxybenzoic acid and β-hydroxynaphthoic acid with epichlorohydrin; Polyglycidyl esters obtained by reacting polycarboxylic acids such as phthalic acid and terephthalic acid with epichlorohydrin; A glycidyl glycoluril compound having two or more epoxy groups in the molecule, such as 1,3,4,6-tetraglycidyl glycoluril; An alicyclic epoxy compound such as 3′,4′-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate; A nitrogen-containing cyclic epoxy compound such as triglycidyl isocyanurate and a hydantoin-type epoxy compound; Furthermore, in addition to an epoxidized phenol novolak resin, an epoxidized cresol novolak resin, an epoxidized polyolefin, a cycloaliphatic epoxy resin, and a urethane-modified epoxy resin, an epoxy-modified organopolysiloxane compound by a hydrosilylation addition reaction between an organic compound having a carbon-carbon double bond and a glycidyl group and a silicon compound having an SiH group (for example, an epoxy-modified organopolysiloxane compound disclosed in JP-A-2004-99751 and JP-A-2006-282988), etc. may be mentioned, and these may be used in combination.

[0060] As the oxetane compound, any compound having an oxetane ring (oxetanyl group / oxetane group) in the molecule can be used without particular limitation. For example, 3-ethyl-3-hydroxymethyloxetane, 3-(meth)allyloxymethyl-3-ethyloxetane, (3-ethyl-3-oxetanylmethoxy)methylbenzene, 4-fluoro-[1-(3-ethyl-3-oxetanylmethoxy)methyl]benzene, 4-methoxy-[1-(3-ethyl-3-oxetanylmethoxy)methyl]benzene, [1-(3-ethyl-3-oxetanylmethoxy)ethyl]phenyl ether, Isobutoxymethyl(3-ethyl-3-oxetanylmethyl)ether, Isobornyloxyethyl(3-ethyl-3-oxetanylmethyl)ether, Isobornyl(3-ethyl-3-oxetanylmethyl)ether, 2-Ethylhexyl (3-ethyl-3-oxetanilylmethyl) ether, Ethyl diethylene glycol (3-ethyl-3-oxetanilylmethyl) ether, Dicyclopentadiene (3-ethyl-3-oxetanilylmethyl) ether, Dicyclopentenyl oxyethyl (3-ethyl-3-oxetanilylmethyl) ether, Dicyclopentenyl (3-ethyl-3-oxetanilylmethyl) ether, Tetrahydrofurfuryl (3-ethyl-3-oxetanilylmethyl) ether, 2-Hydroxyethyl (3-ethyl-3-oxetanilylmethyl) ether, 2-Hydroxypropyl (3-ethyl-3-oxetanilylmethyl) ether, Butoxyethyl (3-ethyl-3-oxetanilylmethyl) ether, Borneol (3-ethyl-3-oxetanilylmethyl) ether, 3,7-Bis(3-oxetanyl)-5-oxa-nonane, 3,3′-[1,3-(2-Methylenyl)propanediylbis(oxymethylene)]bis-(3-ethyloxetane), 1,4-Bis[(3-ethyl-3-oxetanilylmethoxy)methyl]benzene, 1,2-Bis[(3-ethyl-3-oxetanilylmethoxy)methyl]ethane, 1,3-Bis[(3-ethyl-3-oxetanilylmethoxy)methyl]propane, Ethylene glycol bis(3-ethyl-3-oxetanilylmethyl) ether, Dicyclopentenyl bis(3-ethyl-3-oxetanilylmethyl) ether, Triethylene glycol bis(3-ethyl-3-oxetanilylmethyl) ether, Tetraethylene glycol bis(3-ethyl-3-oxetanilylmethyl) ether, Tricyclodecandiyldimethylene (3-ethyl-3-oxetanilylmethyl) ether, Trimethylolpropane tris(3-ethyl-3-oxetanemethyl) ether, 1,4-bis(3-ethyl-3-oxetanemethoxy)butane, 1,6-bis(3-ethyl-3-oxetanemethoxy)hexane, Pentaerythritol tris(3-ethyl-3-oxetanemethyl) ether, Pentaerythritol tetrakis(3-ethyl-3-oxetanemethyl) ether, Polyethylene glycol bis(3-ethyl-3-oxetanemethyl) ether, Dipentaerythritol hexakis(3-ethyl-3-oxetanemethyl) ether, Dipentaerythritol pentakis(3-ethyl-3-oxetanemethyl) ether, Dipentaerythritol tetrakis(3-ethyl-3-oxetanemethyl) ether, Caprolactone-modified dipentaerythritol hexakis(3-ethyl-3-oxetanemethyl) ether, Caprolactone-modified dipentaerythritol pentakis(3-ethyl-3-oxetanemethyl) ether, Ditrimethylolpropane tetrakis(3-ethyl-3-oxetanemethyl) ether, EO-modified bisphenol A bis(3-ethyl-3-oxetanemethyl) ether, PO-modified bisphenol A bis(3-ethyl-3-oxetanemethyl) ether, EO-modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanemethyl) ether, PO-modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanemethyl) ether, EO-modified bisphenol F (3-ethyl-3-oxetanemethyl) ether and the like can be mentioned.

[0061] As the epoxy-oxetane compound, any compound having an oxirane ring (the same as above) and an oxetane ring (the same as above) in the molecule can be used without particular limitation.

[0062] Examples of acrylic compounds include allyl (meth)acrylate, vinyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyl oxyethyl (meth)acrylate, modified allyl glycidyl ether (meth)acrylate (manufactured by Nagase ChemteX Corporation, "Denacol Acrylate DA111 (trade name)"), urethane (meth)acrylates, epoxy (meth)acrylates, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, butanediol di(meth)acrylate, nonanediol di(meth)acrylate, polypropylene glycol-based (meth)acrylate, bisphenol A di(meth)acrylate, tris(2-(meth)acryloyloxyethyl) isocyanurate, (meth)acrylate group-containing polyorganosiloxane, and the like.

[0063] In the resin composition of the present invention, as the second curable compound, the above-mentioned polymerizable monomer and polymerizable oligomer may be used in combination. As the polymerizable monomer, the polymerizable monomers exemplified above may be used in combination (different types of polymerizable monomers may be used in combination), and for the polymerizable oligomer, different types of polymerizable oligomers may be used in combination.

[0064] Regarding the ratio of the content of the first curable compound to the content of the second curable compound in the resin composition of the present invention, it is preferable that the content of the second curable compound is an appropriate ratio in the range of 0 to 1000 times the amount (weight ratio) of the content of the first curable compound, and more preferably an appropriate ratio in the range of 0.01 to 100 times the amount (weight ratio).

[0065] Examples of the method for curing (polymerizing) the resin composition of the present invention include methods of photocuring and thermocuring. Examples of the method of photo-curing include irradiating active energy rays and using a photoinitiator in combination. The active energy rays include light, radiation, electromagnetic waves, electron beams, etc., and typically represent light, particularly ultraviolet light. As the photoinitiator, a photo cationic polymerization initiator can be employed, and if necessary, a photo radical polymerization initiator can be used in combination, and these can be contained in the resin composition. In photo-curing, in order to improve production efficiency and the properties of the cured product, heat-curing means may be used in combination.

[0066] As the photo cationic polymerization initiator, any commonly used one can be used without particular limitation, and examples include onium salts and organometallic complexes. Examples of onium salts include diazonium salts, sulfonium salts, and iodonium salts, and examples of organometallic complexes include iron-allyl complexes, titanocene complexes, and arylsilanol-aluminum complexes. Examples of industrial chemicals commercially available as photo cationic polymerization initiators include "Optomer SP-150 (trade name)" manufactured by ADEKA, "Optomer SP-170 (trade name)" of the same company, "CPI-100P (trade name)" manufactured by San-Apro, "UVE-1014 (trade name)" manufactured by General Electronics, "CD-1012 (trade name)" manufactured by Sartomer, etc. Examples of the counter anion of the photo cationic polymerization initiator include SbF6 - 、AsF6 - 、B(C6F5)4 - 、PF6 - and the like.

[0067] The content of the photo cationic polymerization initiator in the resin composition of the present invention is preferably in the range of 0.001 to 20% by weight, more preferably in the range of 0.01 to 10% by weight.

[0068] Examples of the photo radical polymerization initiator include ketal compounds having 16 to 17 carbon atoms (for example, acetophenone dimethyl ketal, benzyl dimethyl ketal, etc.), Acetophenone compounds having 8 to 18 carbon atoms (for example, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, etc.), Benzophenone compounds having 13 to 21 carbon atoms (for example, benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 4,4'-bis(methylamino)benzophenone, etc.), benzoin compounds having 14 to 18 carbon atoms (for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, etc.), Anthraquinone compounds having 14 to 19 carbon atoms (for example, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-chloroanthraquinone, 2-amylanthraquinone, etc.), Thioxanthone compounds having 13 to 17 carbon atoms (for example, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, etc.), Acylphosphine oxide compounds having 22 to 28 carbon atoms (for example, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, etc.) and the like can be mentioned.

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

[0070] In addition, when photocuring the resin composition of the present invention, for example, sensitizers such as pyrene, perylene, acridine orange, thioxanthone, 2-chlorothioxanthone, and penzo flavin can be used.

[0071] On the one hand, when thermosetting the resin composition 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 it may be contained in the resin composition.

[0072] As the thermal cationic polymerization initiator, any commonly used one can be used without particular limitation, and various onium salts such as quaternary ammonium salts, phosphonium salts and sulfonium salts, as well as organometallic complexes and the like can be exemplified. Examples of onium salts commercially available as industrial chemicals include "ADEKA OPTON CP-66 (trade name)" and "ADEKA OPTON CP-77 (trade name)" manufactured by ADEKA Corporation, "SUN-AID SI-60L (trade name)", "SUN-AID SI-80L (trade name)", "SUN-AID SI-100L (trade name)" manufactured by Sanshin Chemical Industry Co., Ltd., and "CI series (trade name)" manufactured by Nippon Soda Co., Ltd. Examples of organometallic complexes include alkoxysilane-aluminum complexes.

[0073] The content of the thermal cationic polymerization initiator in the resin composition of the present invention is preferably in the range of 0.001 to 20% by weight, and more preferably in the range of 0.01 to 10% by weight.

[0074] In the present invention, the cationic polymerization initiator refers to the above-mentioned photo cationic polymerization initiator and / or thermal cationic polymerization initiator.

[0075] The resin composition of the present invention further, as long as it does not inhibit the effects of the present invention, Pigments (titanium white, cyanine blue, watching red, bengala, carbon black, aniline black, manganese blue, iron black, ultramarine blue, hansa red, chrome yellow, chrome green, etc.), Inorganic fillers (such as calcium carbonate, kaolin, clay, talc, mica, barium sulfate, lithopone, gypsum, zinc stearate, perlite, quartz, quartz glass, fused silica, silica powder such as spherical silica, spherical alumina, crushed alumina, metal oxides such as magnesium oxide, beryllium oxide, titanium oxide, nitrides such as boron nitride, silicon nitride, aluminum nitride, carbides such as silicon carbide, hydroxides such as aluminum hydroxide, magnesium hydroxide, metals and alloys such as copper, silver, iron, aluminum, nickel, titanium, carbon-based materials such as diamond, carbon, etc.), Thermoplastic resins and thermosetting resins (homopolymers such as various high-density, medium-density, and low-density polyethylene, polypropylene, polybutene, polypentene, ethylene-propylene copolymer, polyamide resins such as nylon-6, nylon-6,6, vinyl chloride resins, nitrocellulose resins, vinylidene chloride resins, acrylamide resins, styrene resins, vinyl ester resins, polyester resins, phenolic resins (phenolic compounds), silicone resins, fluorine resins, various elastomer resins such as acrylic rubber, urethane rubber, graft copolymers such as methyl methacrylate-butadiene-styrene graft copolymer and acrylonitrile-butadiene-styrene graft copolymer, etc.), Reinforcing agents (such as glass fibers, carbon fibers, etc.), Dripping inhibitors (such as hydrogenated castor oil, fine particle anhydrous silicic acid, etc.), Matting agents (such as fine powder silica, paraffin wax, etc.), Abrasive agents (such as zinc stearate, etc.), Internal mold release agents (fatty acids such as stearic acid, fatty acid metal salts of calcium stearate, fatty acid amides such as stearic acid amide, fatty acid esters, polyolefin waxes, paraffin waxes, etc.), It may contain additives (modifiers) such as surfactants, leveling agents, defoaming agents, viscosity-adjusting diluents (organic solvents), coupling agents, fragrances, flame retardants, etc.

[0076] In the preparation of the resin composition of the present invention, there is no particular limitation on the preparation method, and it is prepared by weighing out the above-described respective components in predetermined amounts and stirring and mixing them. For example, after preliminary mixing, it can be prepared by mixing or melt-kneading using a roll kneader, a kneader, an extruder, or the like. If necessary, an organic solvent (viscosity-adjusting diluent) may be used.

[0077] The resin composition of the present invention polymerizes (cures) by irradiation with ultraviolet rays or heating to give a cured product. Examples of the ultraviolet irradiation means include methods using light sources such as chemical lamps, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, and metal halide lamps. Regarding the irradiation intensity and irradiation time of ultraviolet rays, they are appropriately set in consideration of the desired irradiation intensity or desired irradiation time, and also in consideration of the composition and shape (thickness) of the resin composition to be irradiated. Examples of the heating means include methods such as hot air circulation, infrared heating, and high-frequency heating. As the curing device, a closed curing furnace, a tunnel furnace capable of continuous curing, or the like can be used. Regarding the heating (curing) temperature and heating (curing) time, as in the case of ultraviolet irradiation, they may be appropriately set in consideration of the composition and shape (thickness) of the resin composition to be irradiated.

[0078] The resin composition of the present invention can be used as a curable ink composition and can also be used as a curable ink composition for inkjet. By applying the curable ink composition for inkjet to a predetermined object using the inkjet method and curing it, it is used in the manufacture of various parts and members described below. In the inkjet method, since a resin film can be formed at high speed and uniformly and over a wide area, there are advantages such as improvement in product accuracy of various parts and members described below and reduction in manufacturing cost.

[0079] The curable ink composition and the curable ink composition for inkjet are preferably measured using a differential thermal thermogravimetric analyzer under the conditions of a sample weight of 10 mg, a temperature increase condition of 10 °C / min, and a nitrogen flow rate (200 mL / min) from the perspective of volatility, and the 5% weight loss temperature (°C) is 185 °C or higher, more preferably 190 °C or higher.

[0080] The curable ink composition for inkjet preferably has a viscosity measured at 25 °C using a dynamic viscoelasticity measuring device (manufactured by UBM, "Rheosol - G5000") of 5 mPa·s or more and 150 mPa·s or less, more preferably 10 mPa·s or more and 80 mPa·s or less, and even more preferably 10 mPa·s or more and 40 mPa·s or less. In addition, when applying by the inkjet method, the curable ink composition for inkjet may be heated to lower the viscosity and then applied.

[0081] Further, the curable ink composition for inkjet preferably has a surface tension measured with a dynamic wettability tester at 25 °C of 15 mN / m or more and 35 mN / m or less, more preferably 20 mN / m or more and 30 mN / m or less.

[0082] Preferable examples of the curable ink composition for inkjet include curable compositions for optical element sealing used as sealants for optical elements such as organic electroluminescence (hereinafter referred to as organic EL) elements and organic thin - film solar cell elements, adhesives for optical members used for bonding optical lenses, etc., curable compositions for stereolithography used in the production of various parts and members by 3D printers, curable compositions for nanoimprint used in the formation of ultra - fine circuit patterns of semiconductors, and the like.

[0083] As an example, when the resin composition of the present invention is used as a curable composition for sealing an optical element, as a method for manufacturing an optical element, there is a method including a step of applying the curable composition for sealing an optical element to at least one of two substrates by an inkjet method, a step of curing the applied curable composition for sealing an optical element by light irradiation and / or heating, and a step of bonding the two substrates together.

[0084] In the step of applying the curable composition for sealing an optical element to at least one of two substrates, the curable composition for sealing an optical element may be applied to the entire surface of the substrate or to a part of the substrate. For example, when manufacturing an organic EL element as an optical element, the shape of the sealing agent portion formed by applying the curable composition for sealing an optical element is not particularly limited as long as it can protect the laminate having the organic light-emitting material layer sandwiched between two substrates from the outside air. That is, it may be a shape that completely covers the laminate, or may be a pattern shape that closes the peripheral portion of the laminate.

[0085] The step of curing the curable composition for sealing an optical element by light irradiation and / or heating may be performed before the step of bonding the two substrates together, or may be performed after the step of bonding the two substrates together. When the step of curing the curable composition for sealing an optical element by light irradiation and / or heating is performed before the step of bonding the two substrates together, it may be bonded within the pot life (for example, 1 minute) until the curing reaction proceeds and adhesion becomes impossible after light irradiation and / or heating.

[0086] In addition, in the step of curing the applied curable composition for sealing an optical element by light irradiation and / or heating, it may be performed by the above-described ultraviolet irradiation means and / or heating means.

[0087] The resin composition of the present invention has no particular limitation in its use, and is applicable to products (parts and components) in various fields where the material may be resin, such as in the fields of electric and electronic, optical, architectural, civil engineering, automotive and aircraft, medical, and other raw materials for materials such as daily necessities and miscellaneous goods.

[0088] For example, examples of components, members, and materials in the electrical and electronic fields include copper-clad laminates, prepregs, copper-clad laminates, printed wiring boards, solder resist inks, anisotropic conductive films, anisotropic conductive pastes, interlayer insulating materials, adhesives, pressure-sensitive adhesives, sealing materials, encapsulants (encapsulation materials), encapsulation sheets, insulating materials, thermally conductive materials, hot melt materials, paints, potting agents, etc. More specifically, Sealing materials (encapsulants) for printed wiring boards and electronic components such as interlayer insulating films and wiring coating films, sealing materials (encapsulation materials) for image display devices, sealing sheets for image display devices, sealing materials (encapsulation materials) for organic EL display elements, sealing sheets for organic EL display elements, layer forming materials; Forming materials for display devices such as color filters, polarizing plates, display materials, resist materials, alignment films; Forming materials for semiconductor devices such as resist materials and buffer coat films; Forming materials for optical components such as lenses, holograms, optical waveguides, optical circuits, optical circuit components, and antireflection films; Coating agents such as surface protective films, hard coat agents, antifouling films, and antireflection films for semiconductor elements and organic thin film elements (for example, organic electroluminescence elements and organic thin film solar cell elements); etc. can be mentioned. In addition, materials for organic electronics elements such as organic EL elements, organic transistors, and solar cells, forming materials for rigid wiring boards and flexible printed wiring boards for semiconductor mounting, mounting materials for semiconductor mounting, adhesives for flexible printed wiring boards, encapsulants for semiconductors, encapsulants for solar cells, insulating films for semiconductors, coverlay films for protecting flexible printed circuits, coating agents for wiring coating, etc. can be mentioned.

[0089] Examples of materials in the optical field include lenses, prisms, films, core materials for optical fibers, cladding materials, abrasion-resistant coating agents for plastic lenses, materials for stereolithography, optical waveguides, filters, image display materials, lens arrays, encapsulating materials and reflector materials for optical semiconductor elements, light guide plates, light diffusing plates, diffraction elements, and optical adhesives, etc. For example, lenses and prisms are not particularly limited as long as they utilize refraction on the surface. Also, materials for lenses of camera modules, LiDAR modules, and steel cameras; adhesives for finder prisms, target prisms, finder covers, light-receiving sensor parts, photographing lenses, projection lenses of projection TVs, etc.; optical fiber materials around optical switches and around optical connectors in optical communication systems; encapsulating materials and adhesives around optical passive components, optical circuit components, optoelectronic integrated circuits, etc.; and can be used as such. Examples of the bonding locations of camera modules include between image sensors (imaging elements) such as CMOS and CCD and substrates, between cut filters and substrates, between substrates and housings, between housings and cut filters, between housings and lens units, etc.

[0090] As lenses and prisms, spherical lenses with spherical surfaces such as biconvex lenses, plano-convex lenses, and convex meniscus lenses, and concave lenses such as biconcave lenses, plano-concave lenses, and concave meniscus lenses; aspherical lenses having aspherical surfaces such as symmetric paraboloids, ellipsoids, hyperboloids, and polynomial surfaces (e.g., quartic surfaces), and aspherical lenses having free-form surfaces without a symmetry axis; cylindrical lenses such as barrel-shaped and cylindrical surface lenses; toroidal lenses having toroidal surfaces with different radii of curvature in the vertical and horizontal directions like the surface of a donut; An annular prism having a reflecting surface that inclines in the same way as the curve of a thick convex lens to change the traveling direction of light and a refracting surface that transmits light, arranged on a plane, and a plurality of these prisms becoming continuously smaller or larger as they approach the center; a thin Fresnel lens; A diffractive lens formed with concentric fine reliefs having a depth of about the wavelength of light; Examples of prisms include those having two or more optical planes and at least one pair of planes being substantially non-parallel. Examples of films include reflective films that are formed by treating inorganic compounds such as MgF2 and SiO2 by vacuum deposition, sputtering, or CVD methods, or by coexisting a light absorber, and reflect light in an unwanted wavelength range while transmitting light in a desired wavelength range.

[0091] Examples of materials in the construction field include sealing materials, coating materials, and primers for joints of exterior materials such as various metal panels and siding boards; Sealing materials, adhesives, injection materials, vibration damping materials, soundproofing materials, conductive materials for electromagnetic wave shielding, and putty used between exterior materials, base materials, ceiling materials, and interior materials; Adhesives for adhering tiles and stones to exterior wall materials and base materials; Adhesives and adhesives for adhering wooden flooring materials, polymer material-based floor sheets, and floor tiles to various floors; Examples include injection materials for crack repair of various exterior and interior materials.

[0092] Examples of materials in the civil engineering field include sealing materials, coating materials, primers, paints, putty materials, injection materials, spraying materials, and formwork materials for joints of various concrete products such as roads, bridges, tunnels, and breakwaters.

[0093] Examples of materials in the automotive and aircraft fields include structural materials, fiber-reinforced composite materials, adhesives, sealing materials, coating materials, cushioning materials, vibration damping materials, soundproofing materials, and spraying materials for bodies and parts; Adhesives, adhesives, coating materials, and foaming materials for automotive interiors; Examples include sealing materials, adhesives, and coating materials for steel plate joints. In addition, as applications of a substrate having a coating layer made of a cured product of the resin composition of the present invention formed on its surface, for example, members of various industrial equipment such as transportation machines (automobiles, airplanes, etc.), electronic and electrical equipment, etc. (for example, sliding members such as cylinders, pistons, bearings, etc.) can be mentioned.

[0094] Examples of materials in the medical field include artificial bones, dental impression materials, medical rubber materials, medical adhesives, medical device sealing materials, etc.

[0095] Other examples include paints to be applied on substrates such as metals, resin films, glass, paper, wood, etc.

Examples

[0096] Hereinafter, the present invention will be described in more detail using examples and comparative examples, but the present invention is not limited thereto. The main raw materials used are as follows. · Allyl glycidyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) · Allyl alcohol (manufactured by Fujifilm Wako Pure Chemical Corporation) · Potassium tert-butoxide (manufactured by Tokyo Chemical Industry Co., Ltd.) · 3-Ethyl-3-methanesulfonyloxymethyloxetane (synthesized according to the method described in JP-A-2007-332294). · Sodium hydroxide (manufactured by Fujifilm Wako Pure Chemical Corporation) · Triethylamine (manufactured by Fujifilm Wako Pure Chemical Corporation) · 3,3-Bis(bromomethyl)oxetane (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0097] The thermal cationic polymerization initiators used are as follows. · Dibenzylmethyl-p-hydroxyphenylsulfonium hexafluoroantimonate (manufactured by Sanshin Chemical Industry Co., Ltd., trade name "Sun-Aid SI-100L")

[0098] The measurement methods for the 5% weight loss temperature, heat generation start temperature, heat generation peak temperature, and gel time, which are the evaluation tests adopted in the examples and comparative examples, are as follows.

[0099] [Measurement of 5% weight loss temperature] For the compounds of Example 1 and Synthesis Examples 2 and 3 described below, the 5% weight loss temperature (Td5) was measured. The measurement was carried out using a differential thermal thermogravimetric analyzer (manufactured by Hitachi High-Tech Science Corporation, "STA7300") under the conditions of a sample weight of 10 mg, a heating rate of 10 °C / min, and a nitrogen flow (200 ml / min).

[0100] [Heat generation start temperature and heat generation peak temperature] For the resin compositions prepared in Example 2 and Comparative Examples 1 and 2 described below, the heat generation start temperature and heat generation peak temperature were measured to evaluate the curability of the resin compositions. The measurement was carried out using a differential scanning calorimeter (manufactured by Hitachi High-Tech Science Corporation, "DSC7020") under the conditions of a temperature profile from -30 °C to 250 °C and a heating rate of 10 °C / min.

[0101] [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.

[0102] [Synthesis of olefin-oxetane compound represented by chemical formula (I-1)] [Synthesis Example 1] Into a 5 L three-necked flask, 2178 g (37500 mmol) of allyl alcohol and 308.58 g (2750 mmol) of potassium tert-butoxide were charged. After heating to 40 °C, 285.35 g (2500 mmol) of allyl glycidyl ether was added dropwise, and the mixture was stirred at 60 °C for 14 hours. Then, after cooling the reaction solution to 25 °C, the reaction solution was filtered to remove solids, and the filtrate was distilled off under reduced pressure. By distillation and purification of the obtained concentrated solution, 391.19 g of a bifunctional olefin compound having a hydroxyl group represented by the chemical formula (II-1) was obtained as a colorless transparent liquid (yield: 91%).

[0103]

Chemical formula

[0104] 〔Example 1〕 Into a 5 L four-necked flask, 344.44 g (2000 mmol) of the colorless transparent liquid obtained in Synthesis Example 1, 1500 g of dimethyl sulfoxide, and 114.97 g (2874 mmol) of sodium hydroxide were charged. After heating to 60 °C, 427.35 g (2200 mmol) of 3-ethyl-3-methanesulfonyloxymethyloxetane was added dropwise, and the mixture was stirred at 70 °C for 8 hours. Then, the reaction solution was cooled to 25 °C, solids were removed by filtration, and the filtrate was extracted with 2000 mL of ethyl acetate. Subsequently, after washing with 2000 mL of water, the organic layer was concentrated under reduced pressure. By distillation and purification of the obtained concentrated solution, 336.92 g of a colorless transparent liquid was obtained (yield: 62%).

[0105] The 1 1H-NMR spectrum data of this colorless transparent liquid was as follows. · 1 1H-NMR (CDCl3) 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 of Figure 1. From these spectrum data, the obtained colorless transparent liquid was identified as an olefin-oxetane compound represented by Chemical Formula (I-1).

[0106]

Chemical Formula

[0107] 〔Synthesis Example 2〕 A 100 mL eggplant 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 stirred at room temperature. Subsequently, 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 this reaction solution, followed by extraction and washing with water, and the obtained organic layer was concentrated. The obtained concentrate was purified by silica gel column chromatography (hexane / ethyl acetate = 1 / 1 (volume ratio)) to obtain 9.90 g of a colorless transparent liquid (yield: 51%).

[0108] The 1 1H-NMR spectrum data of this colorless transparent liquid was as follows. · 1 1H-NMR (CDCl3) 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 spectrum data, the obtained colorless transparent liquid was identified as an olefin-epoxy compound represented by Chemical Formula (IV).

[0109]

Chemical Formula

[0110] [Synthesis Example 3] Into a 1000 mL eggplant flask, 39.20 g (675.0 mmol) of allyl alcohol and 125.00 g of dimethylformamide were charged, and the mixture was cooled to 5 °C with ice while 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. Then, the temperature was raised to room temperature and the mixture was stirred for 14 hours. Subsequently, 500 ml of toluene and 250 ml of water were added to the reaction solution for washing, and the obtained organic layer was concentrated. This concentrate was purified by distillation to obtain 31.08 g of a colorless transparent liquid (yield: 63%).

[0111] The 1 1H-NMR spectral data of this colorless transparent liquid was as follows. · 1 1H-NMR (CDCl3) 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).

[0112] [Chemical formula]

[0113] [Evaluation of the resin composition] [Example 2] 100 parts by weight of the olefin-oxetane compound represented by Chemical Formula (I-1) synthesized in Example 1 and 0.2 part by weight of a thermal cationic polymerization initiator were uniformly mixed to prepare a resin composition. When the above evaluation tests were conducted on this resin composition and the compound of Example 1, the obtained test results were as shown in Table 1.

[0114] [Comparative Examples 1-2] In the same manner as in Example 1, a resin composition having the composition shown in Table 1 was prepared, and the above-described evaluation tests were conducted on these resin compositions and the compounds of Synthesis Examples 2 and 3. As a result, the test results obtained were as shown in Table 1.

[0115] [Table 1]

[0116] From Table 1, it was confirmed that the olefin-oxetane compound of the present invention is excellent in volatility resistance because its 5% weight loss temperature is higher than that of the compounds of Synthesis Examples 2 and 3. Thereby, in the resin composition containing the olefin-oxetane compound of the present invention, it is possible to suppress the deviation of the compounding ratio and the equipment contamination due to the volatilization of the contained components during the thermosetting of the resin composition, and it is possible to obtain a resin composition and a cured product of stable quality. Further, it was confirmed that the resin composition containing the olefin-oxetane compound of the present invention exhibits better curability than the resin composition of Comparative Example 1 and exhibits curability equivalent to that of the resin composition of Comparative Example 2.

Industrial Applicability

[0117] Since the novel olefin-oxetane compound according to the present invention has an oxetane ring in the molecule, it is expected to be used as a resin material. Further, the olefin-oxetane compound of the present invention is excellent in volatility resistance and can prevent the deviation of the compounding ratio and the equipment contamination due to the volatilization of the contained components during thermosetting. And the olefin-oxetane compound of the present invention can be used for the synthesis of various novel compounds by utilizing the carbon-carbon double bond and the oxetane ring in the molecule.

Claims

1. An olefin - oxetane compound represented by Chemical Formula (I). 【Chemical Formula 1】 (In the formula, R is the same or different and represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. The wavy line represents that it is a trans - form, cis - form or a mixture thereof.)

2. A method for synthesizing the olefin - oxetane compound according to Claim 1, characterized 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). 【Chemical Formula 2】 (In the formula, R and the wavy line are the same as above.) 【Chemical Formula 3】 (In the formula, X represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a mesyloxy group (OMs), a tosyl - oxy 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.

Images