TW201245141A - Epoxy acrylate, acrylic curable composition, cured product and manufacturing processes therefor - Google Patents

Abstract

Provided are: an epoxy acrylate which exhibits excellent heat resistance and low thermal expansion and is useful for solder resist resins, electroless plating resist resins, hard coat materials, UV-curable coating materials, substitute materials for glass, color filters for liquid crystal displays, and so on; an acrylic composition; and a cured product. The epoxy acrylate is represented by general formula (1) [wherein Z is C1-6 alkyl; a is a number of 0 to 4; and n is an integer of 2 to 3]. The epoxy acrylate can be obtained by reacting an epoxycyclohexane compound with acrylic acid or methacrylic acid.

Description

201245141 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a novel epoxy acrylate which is excellent in high temperature resistance, fluidity, toughness, photosensitivity, chemical resistance, hardness, transparency, and weather resistance. Acrylic curable composition, cured product, and a method for producing the same. When the epoxy acrylate is polymerized by itself or copolymerized with a compound having various unsaturated bonds, high temperature resistance, toughness, chemical resistance, hardness, transparency, and weather resistance can be obtained. It is excellent in polymer materials and can be used in various applications such as coatings, laminates, and adhesives. Further, 'as a photocurable resin composition or a thermosetting resin composition' is also suitably used as a resin for solder-resist, or a resin for nonelectolytic plating resist, and hard. A protective film such as a hard coat material, a UV (ultraviolet) hardening paint, a glass substitute material, and a liquid crystal color filter. [Prior Art] The epoxy acrylate resin which is mainly obtained by the reaction of an epoxy compound and acrylic acid is widely used as a photosensitive material, a crosslinking agent, and the like, and various functional polymer materials. Since the resin has a hydroxyl group in the molecule, it is superior to solvent solubility and high temperature resistance (Non-Patent Document 1). In particular, 2-hydroxy-2-phenylethyl propyl acrylate which is an epoxy acrylate derived from epoxy ethyl benzene which is an epoxy group directly bonded to benzene is hardened. When the resin is compared with the general epoxy acrylate resin having glycidyl ether group-5-201245141, the molecular motion of the cured product is inhibited because the soft hydroxymethylene moiety is not held. Excellent high temperature resistance and low thermal expansion property can be expected. Further, high temperature resistance, moisture resistance, and chemical resistance can be obtained by copolymerization with a compound having various unsaturated bonds (Patent Document η, or crosslinking with a hydroxyl group such as isocyanate (Patent Document 2)) A polymer material excellent in chemical properties, etc. However, the role of 2-hydroxy-2-phenylethyl acrylate, which is the only disclosure of epoxy acrylate derived from epoxy ethyl benzene, is The reaction diluent or the cross-linking agent has not been noticed for the improvement of the epoxy acrylate itself for the purpose of improving the physical properties of the resin. Furthermore, the epoxy acrylate derived from epoxy ethylbenzene In the case of an aromatic compound, if it is to be applied to the field of optical parts, transparency and weather resistance may be insufficient. [Prior Art Document] [Patent Document 1] Japanese Patent Laid-Open No. 52 - Japanese Patent Publication No. 9-595 3 5 [Non-Patent Literature]] Polymer Chemistry, 1987, Vol. 25, No. 284, p. 850 [Invention] The purpose of the present invention is to provide It is superior to high temperature resistance, low thermal expansion, transparency, and weather resistance, and is a resin for solder resist, or a resin for electroless plating resist, a hard coating material, a UV hard coating, a glass substitute material, or a liquid crystal. An epoxy acrylate, a C -6 - 201245 141 composition, and a cured product which are useful as a color filter. In particular, an acrylic resin composition and a cured product which are useful as an optical material are provided. In the actual situation of the technology, in order to obtain better resistance to temperature, low thermal expansion, high refractive index, transparency, and weather resistance, it is a resin for solder resist or a resin for electroless plating resist. Hard acrylic coating materials, UV hardening coatings, glass substitute materials, liquid crystal color-sensitive sheets, and the like have been found to be intensive, and it has been found that epoxycyclohexane compounds and unsaturated resins are used as epoxy acrylates. When the epoxy acrylate obtained by the reaction of decanoic acid can solve the above-mentioned problem, the present invention is finally completed, that is, the present invention can be expressed by the following general formula (1). Epoxy acrylate.

0

X (wherein 'X represents a hydrogen atom or a methyl group. Z represents a C1 to C6 alkyl group' may be all the same or different. η represents a number from 2 to 3. a represents 〇 to 4). In the present invention, the epoxy acrylate represented by the above general formula (1) is contained as a main component, and the epoxy acrylate having the following general formula (2) is used as a subcomponent to contain an epoxy acrylate. . 201245141 【化2】

Ο

X

(3)

OH 1

X ο (4) Here, 'eight' is a group containing an ester bond represented by the formula (3), and B is a group containing an ester bond represented by the formula (3) or the formula (4). b represents an integer from 1 to 2. The Z, X, and a systems have the same meaning as the general formula (1). Further, the present invention relates to an acrylic curable composition comprising the above epoxy acrylate and a polymerization initiator. Further, the present invention relates to an acrylic resin cured product which is obtained by molding and curing the acrylic hardening composition. Further, the present invention relates to a process for producing the above epoxy acrylate, which comprises reacting an epoxycyclohexane compound represented by the general formula (5) with acrylic acid or methacrylic acid. -8- 201245141 【化3】

(5) (here, Z, a, and η' have the same meanings as in the general formula (i)). Further, the present invention is an acrylic curable composition or an acrylic cured product, which is characterized by the above acrylic The curable composition or the cured acrylic resin is used as an optical material. BEST MODE FOR CARRYING OUT THE INVENTION First, the epoxy acrylate of the present invention will be described. The epoxy acrylate of the present invention can be represented by the above general formula (1). Here, X represents a hydrogen atom or a methyl group. Ζ represents an alkyl group of C1 to C6, which may be all the same or different. η represents an integer of 2 to 3. a represents an integer from 〇 to 4. However, n + a will not exceed 6. The epoxy acrylate represented by the above general formula (1), such as an epoxycyclohexanoic acid compound represented by the above general formula (5) and an unsaturated carboxylic acid (containing acrylic acid, methacrylic acid, or both) The reaction can be carried out to carry out acrylation, that is, it can be produced. Therefore, the type of Z is derived from the structure of the epoxycyclohexane compound used as a raw material. From the easiness of obtaining an epoxycyclohexane compound or the characteristics of the obtained epoxy acrylate, -9-201245141 z The alkyl group of C to C6 is an integer of 〇 to 4, preferably 〇 to 1, and the epoxycyclohexane compound represented by the above general formula (5) may be substituted on the ring of the ring. The structure of the epoxy group (disubstituted) or the structure of three substitutions (trisubstituted). The isomer of the disubstituted product is solid with: 2-disubstituted (〇-(o)), i-, 3-disubstituted (m), and 1,4-substituted (p- (I), and the isomer of the trisubstituted product are: hydrazine, ], trisubstituted, hydrazine, 2,4_trisubstituted, H5-substituted. The cyclohexylation compound used in the production method of the present invention is a mixture of such isomers (may be the same disubstituted, same trisubstituted or a mixture of disubstituted and trisubstituted) However, in the case of a mixture of the same disubstituted materials, from the viewpoint of high temperature resistance and low viscosity, it is preferable that the content of the m_ thing and the p_ substance is high, the substance and the substance 90% or more, preferably 95% by weight or more is suitable for use. Further, from the viewpoint of high temperature resistance of the cured acrylic resin, it is preferably a trisubstituted product, particularly preferably a 1,2,4-trisubstituted product. The epoxy acrylate of the present invention can be produced by a reaction of an epoxycyclohexane compound with an unsaturated carboxylic acid. In this reaction, the epoxy group of the epoxycyclohexane compound is ring cleavage and then bonded to an unsaturated carboxylic acid to form an ester linkage. Such ring-opening can occur from either the α-position or the β-position, but the epoxy acrylate (α adduct) of the above general formula (1) which is opened at the α-position will become a main component, and The epoxy acrylate (β adduct) of the above general formula (2) which is opened at the β-position will be an accessory component. There are two kinds of epoxy acrylates of the general formula (2). In other words, there is a case where both of A and B in the general formula (2) are a group containing an ester bond (β adduct) represented by the formula (3), and a general formula (2) A is a group containing an ester bond represented by the formula (3) (β adduct), and a part or all of Β is a group containing an ester bond (α adduct) represented by the formula (4). The former is referred to as a full beta adduct, and the latter is referred to as a semi-beta adduct, which is referred to as a beta adduct. The ratio of total beta adduct formation is very low compared to the semi-beta adduct. Further, in the case where both of ruthenium and osmium in the general formula (2) are those having an ester bond (α-addition) represented by the formula (3), the same formula as (1) will be used. In the above production method, the ratio of the α adduct to the β adduct is usually from 100/0.01 to 1 00/70, preferably from 100/0.1 to 1 00/5 0. Therefore, in the above production method, an epoxy acrylate containing both the α adduct of the present invention and the β adduct can be usually obtained. If the epoxy acrylate containing both the α adduct and the β adduct is distinguished from the epoxy acrylate formed only by the epoxy acrylate of the general formula (1), the former is called The epoxy acrylate composition is referred to as an epoxy acrylate of the general formula (1), and if it is not particularly necessary to distinguish it, the two are referred to as epoxy acrylate. When the epoxy acrylate of the general formula (1) is to be separated from the epoxy acrylate composition, it can be isolated by a known method. In addition, the content of the main component is preferably 60% or more, preferably 70% or more, and the subcomponent is preferably 4% by weight or less, preferably 30% or less. In the above production method, an epoxy acrylate represented by the general formula (1) and -11 - 201245141 (2) can be obtained. Because these epoxy acrylates are all ring-ring compound compounds, there are chair forms, boat forms, and there are cis (Cis) and trans (trans) isomers. Or the main component and the subcomponent of the optical isomer may be a mixture containing such isomers. According to the above-mentioned manufacturing method, the epoxy acrylates represented by the general formulas (1) and (2) are both epoxy acrylates, even if they contain the general formulas (1) and (2). The composition of the epoxy acrylate represented is still referred to as epoxy acrylate. The epoxy acrylate of the present invention is reacted at 50 to 200 ° C in the presence of a catalyst, an unsaturated carboxylic acid, as needed, in the presence of a catalyst, a polymerization inhibitor (p〇lymerization inhibitor). It can be made up to 50 hours. The raw material feeding ratio of the epoxycyclohexane compound and the unsaturated carboxylic acid is 10 0/5 to 5/100', preferably 100, based on the molar ratio of the epoxycyclohexane compound to the unsaturated carboxylic acid. The reaction ratio of /10 to ίο/loo is preferably a catalyst which can be used at this time, and an alkali metal hydroxide such as sodium hydroxide 'potassium hydroxide, triethylamine or benzyl dimethyl hydride A tertiary amine such as a tertiary amine, a quaternary ammonium salt such as tetramethylammonium chloride, a phosphine such as an imidazole compound 'triphenylphosphine, or a scaly salt such as tetra-n-butylphosphonium tetraphenyl borate. These catalysts may be used alone or in combination of two or more. In terms of the amount of catalyst used, although it varies depending on the catalyst to be used, it is preferably 1 to 100 moles, more preferably 0.1 to 80 moles per mole of the epoxycyclohexane compound. . In the case of the polymerization inhibitor which can be used in the reaction, a polymerization inhibitor which is well known as a polymerization inhibitor of the ethylene-12-201245141-based compound may, for example, be phenothiazine or methoxymorphine. An amine such as anthracene, a hindered amine, a benzoquinone, a methoxybenzoquinone, a phenol, a butyl phenol, a butyl hydroxytoluene or a phenol such as cresol, and preferably a phenol. class. These polymerization inhibitors may be used alone or in combination of two or more. The amount of the polymerization inhibitor used is preferably from 0.001 to 10 moles, more preferably from 0.01 to 1 mole, per 100 moles of the epoxycyclohexane compound, although it varies depending on the catalyst to be used. When the reaction is carried out, an organic solvent can also be used if necessary. The organic solvent may, for example, be an aromatic hydrocarbon solvent such as toluene or xylene, or a ketone solvent such as MIBK (methyl isobutyl ketone) or MEK (methyl ethyl ketone). The amount of the solvent to be used is usually 50 to 5000 parts by weight, preferably 1 to 2000 parts by weight, based on 100 parts by weight of the total of the epoxycyclohexane compound and the unsaturated carboxylic acid. When the reaction is carried out, air or oxygen may be introduced if necessary. From the viewpoint of control of the reaction, it is preferred to introduce air. From the epoxy acrylate obtained by the reaction, an epoxy acrylate which can be obtained by the general formula) is used as a main component, and an epoxy acrylate-like isomer of the general formula (2) is used as a mixture of sub-components, or n number a different mixture. When these mixtures are used as a resin raw material, they can be used as an epoxy acrylate. When it is used as a raw material for an organic drug or the like, it can be purified or separated by recrystallization or the like. As the epoxycyclohexane compound, those obtained by subjecting a vinylcyclohexyl compound to epoxidation by a peroxide can be used. The compound obtained from -13-201245141 has a lower chlorine content because it does not use epichlorohydrin. As the peroxide, peracid, hydrogen peroxide, or an oxide obtained by the method can be used. The acrylic cured product of the present invention contains the above-mentioned general formula (1 epoxy acrylate or the above-mentioned epoxy acrylate product as a main component, and a polymerization initiator. As a polymerization initiator, it can be used as a vinyl compound. The polymerization initiator known as an initiator can be hardened by irradiation with an energy ray such as ultraviolet rays or electron beams or a radical polymerization initiator. When a curing by ultraviolet irradiation is applied, a photopolymerization initiator is added. The photopolymerization initiator is not particularly limited, and may be a photopolymerization initiator which is a type of radical which is excited by ultraviolet light and generates a radical. Specifically, an appropriate introduction can be exemplified. Benzene: benzoin (benzoin), benzoin methyl ether, phenethyl ether, benzoin isopropyl ether, α-methylbenzoin and other benzoin, isobutyl benzoquinone, diphenyl phenol , diphenylphenols such as p-methyldiphenylphenol, p-chlorophenol, p-diethylaminodiphenylphenol, acetam 9,10-fluorenone, l-chloroindanone, 2-chloro Anthrone The sulfonate-containing compound such as a ketone, a diphenylate or a tetramethylthiamine-methyl sulfonyl disulfide may be used alone or in combination of two or more kinds thereof to adjust the polymerization property. The total amount of the compound is recommended to be 0.1:% by weight. Normally the activation of the ester group polymerization. For the purpose of triggering, the agent (yield acetoin α-hydroxyphenylbenzene, disulfide, etc., g 1 0 -14- 201245141), in order to promote the photopolymerization reaction using a photopolymerization initiator, may also be added Photosensitizer. The photo sensitizer is not particularly limited, and specific examples thereof include tertiary amines such as triethylamine and triethanolamine, and alkylphosphines such as triphenylphosphine. For the amount of the thioether such as thiodiglycol, a polymerizable compound (the above epoxy acrylate or epoxy acrylate composition, and other polymerizable monomers added as needed) may be recommended. The total amount of the meaning is 0.1 to 5% by weight. For the ultraviolet light source, a chemical lamp, a low pressure mercury lamp, a high pressure mercury lamp, a gas lamp (xe η ο η 1 amp ), a metal tooth compound can be used. Metal halide lamp, etc. When curing by electron beam is used, it is not necessary to use a photopolymerization initiator or a photosensitizer, and a general-purpose electron beam generating device is used to irradiate normally, 1 to 20 megabytes. Rade (megarad) The electron beam of the dose of the dose may be used. The radical polymerization initiator used in the radical polymerization of the acrylic curable composition of the present invention is not particularly limited, specifically In other words, a peroxide such as benzamidine peroxide, diisopropyl peroxycarbonate, a peroxide such as laurel, or an azo compound such as azobisisobutyronitrile may be exemplified, and these polymerization initiators may be The polymerization initiator may be used alone or in combination with a heat-curing agent or a photo-curing agent depending on the application. The polymerization inhibitor is different, but the total amount of the polymerizable compound is preferably -15 to 201245141 0.001 to 5 parts by weight, more preferably 〇.01 to 1 part by weight, but 'because the mixing ratio is due to The type of the hardener to be used varies greatly, and it is necessary to appropriately determine the optimum conditions. In the acrylic curable composition of the present invention, when necessary, the epoxy acrylate of the general formula (1) or In addition to the above-mentioned epoxy acrylate composition as the main component, ruthenium may be added with other polymer monomers formed by heat or light. However, the polymerizable component contains the epoxy of the above general formula (1) in total. The acrylate or the epoxy acrylate composition having the above-mentioned main component is preferably 50 wt% or more. The other polymerizable monomer may be a polymerizable monomer which is formed by heat or light. The various acrylate-based compounds exemplified below are used alone or in combination of two or more kinds thereof, and are used as a curable component. Monofunctional (meth) acrylates are exemplified by methyl (meth) acrylate. Ester, ethyl (meth) acrylate, n-propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, n-hexyl (meth) acrylate, 2 -ethylhexyl (meth) acrylate, mercapto (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, 2 - Hydroxyethyl (methyl) propyl Acid ester, 2-hydroxypropyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 3 · chloro-2- Hydroxypropyl (meth) acrylate, 2,3-dibromopropyl (meth) acrylate, and the like. The monofunctional (meth) acrylate is exemplified by ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, and triethyl-16-201245141 monool di(methyl). Acrylate, tetraethylene glycol di(meth)acrylate. Polyethylene glycol di(meth)acrylate 'propylene glycol di(meth)acrylic acid vinegar, monopropanol di(meth)acrylate, tripropylene glycol di(methyl)propyl sulphuric acid vinegar, polypropylene glycol di(a) Acrylate, propylene glycol di(methyl)propionic acid acrylate, glycerol di(meth) acrylate, 1,3-butanediol-(meth) acrylate, 1,4-butanediol bis (A) Acrylate, 1,5-pentanediol di(meth)acrylate, hydrazine, 6-hexanediol di(meth) acrylate vinegar, neopentyl glycol di(meth) acrylate, double (oxymethyl) tricyclo[5.2.2.02,5]decane di(meth)acrylate 'cyclohexanediol di(meth)acrylate, bis[(methyl)acryloxymethyl]cyclohexane Diacrylate of acetal of alkane, trimethylpropane and pivalaldehyde, neopentyl glycol hydroxypivalate diacrylate, bisphenol A di(meth) acrylate, bisphenol A alkylene oxide The di(meth)acrylate of the adduct, and the like. The tri- or tetra-functional (meth) acrylate can be exemplified by trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, diisopentaerythritol five (a) Acrylate, diisopentaerythritol hexa(meth) acrylate, and the like. Examples of the acrylic polymerizable oligomer include epoxy (meth) acrylate, polyurethane (meth) acrylate, polyester (meth) acrylate, and polybutadiene oligomerization. (meth) acrylate, polyamido type (meth) acrylate oligomer, melamine (meth) acrylate, (meth) acrylate of cyclopentadiene oligomer, low polyoxymethylene (meth) acrylate of the polymer, and the like. Further, in addition to the above acrylate-based monomer, ruthenium may be suitably used in other poly-17-201245141 conjugated monomers such as styrene, vinyl acetate, vinyl chloride, ethylene 'acrylonitrile' vinyl ether, acrolein. Examples of the vinyl group include an olefin such as ethylene or butadiene. These heat or light-generating monomers may be used alone or in combination of two or more. The heat or light polymerizable monomer is preferably used separately depending on the application. In the acrylic curable composition of the present invention, if necessary, other components such as a chelating agent, a fiber, a coupling agent, P, a releasing agent, and a foaming agent are added. In this case, the chelating agent is: polyethylene powder, polypropylene powder, quartz, cerium oxide, carbonic acid, magnesium carbonate, stone, bentonite, egg titanium oxide, carbon black, graphite, oxidation Iron, aluminum powder, iron powder, slippery mother, kaolin clay, etc., and the fiber may, for example, be a cellulose fiber fiber, a carbon fiber, an aramid fiber, or the like, and may be exemplified by decane. A coupling agent, a titanium coupling agent, and the like. The flame retardant may, for example, be brominated bisphenol A, antimony trioxide or a phosphorus compound, and examples thereof include stearate, polyfluorene oxide, and wax. For foaming, fluorocarbon (flon, chlorofluorocarbon), dichloroethane, dinitropentamethylenetetramine, p-toluenesulfonate, or fluorofluoroethane, butane, Pentane or the like is a thermoplastic resin particle or the like which is filled in a shell of a vinyl chloride-chlorinated polymer or a styrene-(meth)acrylate polymer. The acrylic curable composition of the present invention can be easily made into an acrylic cured product in accordance with the conventional method. For example, the acrylate or epoxy acrylate composition of the present invention and the polymerization initiator are formed by polymerization of a chlorinated compound, and a flammable agent, for example, strontium silicate, sillimanite, cloud, or glass. For the coupling agent. For the release agent, the co-expansion of butane, lanthanum and diethylene is known as the epoxy heat -18-201245141 or the polymerizable monomer caused by light and other additives, if necessary, an extruder is used. a kneader, a roll, or the like is mixed to obtain an acrylic resin composition, and the acrylic resin composition is melted, molded, or molded by a transfer molding machine or the like. A hardened material can be obtained by reheating at 80 to 200 °C. Further, the acrylic curable composition of the present invention may be dissolved in a solvent and impregnated with a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber or paper, and then heated. The prepreg obtained by drying is subjected to thermopress moulding to obtain a cured product. For example, the epoxy acrylate or epoxy acrylate composition of the present invention, a polymerization initiator, and other additives are heated and stirred until uniform, and are impregnated with a glass cloth and heated to be semi-dried to volatilize the solvent. After the number of sheets is overlapped and heated and compression molded at 80 to 200 ° C, a glass cloth laminate can be produced. In this case, specific examples of the solvent for dilution which can be used are preferably toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, etc., and are used. The amount of the acrylic curable composition and the solvent for dilution is from 10 to 70% by weight, preferably from 15 to 65 % by weight. Since the cured product thus obtained has high temperature resistance, toughness, chemical resistance, and hardness, the cured acrylic resin of the present invention can be used in a wide range of fields such as optical resins. Specifically, it is also suitably used as a protective film for a solder resist resin, a resin for electroless plating resist, a hard film -19-201245141 material, a UV curable coating material, a glass substitute material, and a liquid crystal filter. In particular, it is excellent as an optical material such as a lens, a ruthenium, a color filter, or a protective film. [Embodiment] [Embodiment] Next, in order to make the features of the present invention clearer, the details will be specifically described. Here, the "parts" and "%" in the text are all weight basis. [Example 1] In a 300 ml glass three-necked flask equipped with a cooling tube, a thermometer, and an air blowing tube, '1,2,4-triepoxyethylcyclohexane 10.5 50 mmol (mole) was placed, Acrylic acid 18.01g (250mmol), benzyl triethyl hydrazine. 23g (lmmol), dibutyl thioglycolate (0.25mmol), toluene 100ml, heated in air at 80 °C, stirring. It was allowed to react for 24 hours. After the reaction, it was cooled to room temperature and washed three times with distilled water l〇〇ml. The toluene layer was separated and the methyl group was distilled off, and purified by a silica gel column using ethyl acetate + hexane (4:6) as a deeve. 13.00 g (yield) of triepoxy acrylate cyclohexane of an ambiguous and viscous liquid was obtained. The triepoxy acrylate cyclohexane was confirmed by GC (gas chromatography analysis in the general formula (1), a is 〇, X is Η, and η is an epoxy acrylate as a main component. This tri-glycidose chrome film is the glass ig represented by this example (5 g of ruthenium chloride, and the benzene after the loter color is 6 1 % method) 3 acid ester-20- 201245141 1H-NMR of cyclohexane The spectrum is shown in Fig. 1. [Comparative Example 1] In a 500-neck three-necked flask equipped with a cooling tube, a thermometer, and an air blowing tube, styrene chloride 50.0 μg (416 mm〇l) was placed. 29.98 g (416 mmol) of acrylic acid, 16 mmol of triphenylphosphine, 0.346 g (2.08 mmol) of 4-tert-butylbenzenediol, and 100 ml of toluene were heated and stirred at 60 ° C in air. Reaction for 24 hours. After the reaction, it was cooled to room temperature, and washed three times with 10 ml of distilled water. After separating the toluene layer and distilling off toluene, it was purified by a ruthenium tube column using ethyl acetate + chloroform (2:8) as a developing solution. An epoxy acrylate benzene of 54.37 g (yield 68%) of a colorless transparent liquid was obtained. [Example 2] 100 parts by weight of the triepoxy acrylate cyclohexane obtained in Example 1 and Ilgarya 1 8 4 as a polymerization initiator [Helical special medicine <; Trade name] 5 parts by weight was kneaded to prepare a composition. This is applied to a glass plate or an aluminum dish, and is coated with a release PET (polyethylene terephthalate) film and a high-pressure mercury lamp can be used in an energy ray amount of 600 mJ (mJ)/cm 2 . Ultraviolet rays are irradiated to harden them to obtain a film-like cured product. Next, the obtained cured product was used as a sample, and the pencil hardness test (P e n s i 1 t e s t ), the glass transition temperature, and the thermal expansion coefficient (αΐ) were analyzed by the following methods. The results are shown in Table 1. -21 - 201245141 (Pencil hardness) The coating film is cured to a thickness of 10 to 20 μm on a glass plate, and is measured under a load of lkg according to JIS Κ 5 600, and is applied to the hardness of the hardest pencil which is not scratched. Representation" (glass transition temperature: Tg, coefficient of thermal expansion; α i ) The sample was adjusted to a length of 20 mm, a width of 5 mm, and a thickness of 0.1 mm. Using SII Nanotechnology Co., Ltd.: thermomechanical analyzer ( TMA/SS) was obtained under a nitrogen atmosphere at a temperature increase rate of 7 ° C /min. (YI (yellow index) 値) A film having a thickness of 50 μm was used as a sample and evaluated in accordance with JIS K7373. (Total light transmittance: Tt) A film having a thickness of 50 μm was used as a sample and evaluated in accordance with JIS K7361-1. [Comparative Example 2] A film-like cured product was obtained under the same conditions as in Example 2 except that the epoxy acrylate benzene obtained in Comparative Example 1 was used. Next, analysis of the pencil -22-201245141 hardness, glass transition temperature, and thermal expansion coefficient (α 1 ) of the obtained cured product was carried out under the same conditions as in Example 2. The results are shown in Table 1. [Table 1] Pencil hardness Tg (t:) a 1 (ppm) YI 値 Tt (%) Example 2 2 Η 163t: 55 0. 91 94 Comparative Example 2 2 Η 158t: 58 2. 53 92 [Industry Use possibility] The epoxy acrylate of the present invention is superior in resistance to high temperature, low thermal expansion, high refractive index, transparency, weather resistance, and can be obtained as a solder resist. An epoxy acrylate, an acrylic composition, and a cured product which are useful as an optical resin such as a resin for a coating agent, a resin for electroless plating resist, a hard coating material, a UV-curing coating material, a glass substitute material, or a liquid crystal coloring film. BRIEF DESCRIPTION OF THE DRAWINGS [Fig. 1] shows an ih_nmr (hydrogen atom nuclear magnetic resonance) spectrum of tricyclohexyl methacrylate cyclohexane. -twenty three-

Claims (1)

201245141 VII. Patent application scope: 1. An epoxy acrylate represented by the following general formula (1), [Chemical 1] (In this case, X represents no hydrogen atom or methyl group, Z represents a group of C1 to C6, and may be all the same or different, η represents an integer of 2 to 3, and a represents an integer of 0 to 4). 2. The epoxy acrylate according to the first aspect of the invention, which comprises an epoxy acrylate represented by the general formula (1), and an epoxy glycerin represented by the following formula (2) as a subcomponent. [Chemical 2] -24- (3) 201245141 (here, Z represents an alkyl group of Cl to C6, which may be all the same or different, A is a group containing an ester bond represented by the formula (3), and B is a compound represented by the formula (3) or (4). The base of the ester bond, X represents a hydrogen atom or a methyl group 'a represents an integer of 〇 to 4, and b represents an integer of 1 to 2). An acrylic-based curable composition comprising the epoxy acrylate and the polymerization initiator described in claim 1 of the patent application. An acrylic curable composition comprising the epoxy acrylate and the polymerization initiator described in claim 2 of the patent application. An acrylic resin cured product obtained by molding and curing an acrylic curable composition described in the third or fourth aspect of the patent application. A method for producing an epoxy acrylate according to the first aspect of the invention, characterized in that the epoxy ring compound represented by the following general formula is reacted with a propylene or methacrylic acid, 3 -25- 201245141 (here, Z represents an alkyl group of Cl to C6, which may be all the same or different 'a' means 〇 to 4, „ represents 2 to 3). 7 · — Patent application scope The method for producing an epoxy acrylate vine according to the item 2, characterized in that the epoxy ring compound represented by the following general formula (5) is reacted with acrylic acid or methacrylic acid; (Here, Ζ represents an alkyl group of C1 to C6, which may be all the same or different, a represents a number of 〇 to 4, and η represents a number of 2 to 3). 8. The acrylic curable composition according to Item 3 or 4 of the patent application, wherein the acrylic curable composition is a stomach for an optical material. 9_ An acrylic resin cured product which is characterized in that the cured acrylic resin described in the fifth aspect of the patent application is an optical material. -26-