Epoxy compound products

Abstract

To provide an epoxy compound product capable of forming a cured product less likely to generate outgas in a high heat environment. In an epoxy compound product according to the present disclosure, the purity of a compound represented by formula (1) is 80% or more, and the total proportion of compounds represented by formula (a), compounds represented by formula (b), and compounds represented by formula (c) is 1 mass% or less. [In the formula, X represents a single bond or a linking group. The cyclohexane ring and the benzene ring in the formula may have substituents on one or more of the carbon atoms constituting the ring.]

Description

[Technical Field]

[0001] This disclosure relates to high-purity epoxy compound products. This application claims priority to Japanese Patent Application No. 2023-192638, filed in Japan on November 10, 2023, and the contents of that application are incorporated herein by reference. [Background technology]

[0002] By reacting epoxy compounds with various curing agents and curing catalysts, cured products with high strength, excellent heat resistance, and transparency can be formed. For example, alicyclic epoxy compounds having two or more epoxy groups are used as raw materials for encapsulants, coatings, adhesives, inks, sealants, and the like.

[0003] Examples of the above-mentioned alicyclic epoxy compounds include 3,4-epoxycyclohexylmethyl(3',4'-epoxy)cyclohexanecarboxylate and 3,4-epoxy-6-methyl-cyclohexylmethyl(3',4'-epoxy-6'-methyl)cyclohexanecarboxylate (see Patent Documents 1 and 2). [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] International Publication No. 2019 / 138988 [Patent Document 2] U.S. Patent No. 2890194 [Overview of the project] [Problems that the invention aims to solve]

[0005] However, conventional alicyclic epoxy compound products contain low-boiling compounds as impurities. For example, in products containing cured alicyclic epoxy compounds, these low-boiling compounds volatilize under high-temperature conditions, causing outgassing. When outgassing occurs, for example, if the cured product is used as a encapsulant for semiconductor devices such as organic LEDs, cracks may form in the inorganic material film of the semiconductor device, resulting in insufficient sealing.

[0006] Therefore, the object of this disclosure is to provide epoxy compound products that can form cured products that are less prone to outgassing in high-temperature environments. [Means for solving the problem]

[0007] In other words, this disclosure relates to a compound represented by the following formula (1) having a purity of 80% or more, The present invention provides an epoxy compound product in which the total content of the compound represented by formula (a) below, the compound represented by formula (b) below, and the compound represented by formula (c) below is 1% by mass or less. [ka] [In the formula, X represents a single bond or a linking group. The cyclohexane ring and benzene ring in the formula may have substituents on one or more of the carbon atoms constituting the ring.]

[0008] The compound represented by formula (1) above is preferably an epoxidized compound of the compound represented by formula (2) below, using an aliphatic percarboxylic acid. [ka] [In formula (2), X represents a single bond or a linking group, and is the same as in formula (1). The cyclohexene ring in formula (2) may have substituents on one or more of the carbon atoms constituting the ring.]

[0009] The above aliphatic percarboxylic acid is preferably peracetic acid.

[0010] The present disclosure also provides a curable composition containing the above epoxy compound product, a curing agent and / or a curing catalyst.

[0011] The present disclosure also provides a curable composition containing the above epoxy compound product, other epoxy compounds and / or oxetane compounds.

[0012] The above curable composition is preferably an adhesive, a sealant, a coating agent, or a hard coat agent.

[0013] The present disclosure also provides a cured product of the above curable composition.

[0014] The present disclosure also provides an optical member including the above cured product.

[0015] The present disclosure also provides a method for producing the above epoxy compound product, which produces the above epoxy compound product through the following epoxidation step, the following first low-boiling component removal step, the following high-boiling component removal step, and the following second low-boiling component removal step. Epoxidation step: A step of reacting a compound represented by the following formula (2) with an organic peracid to obtain a reaction product

Chemical formula

Advantages of the Invention

[0016] The epoxy compound product of the present disclosure can form a cured product that is less likely to generate outgas in a high-temperature environment.

Brief Description of the Drawings

[0017] [Figure 1] The 1H-NMR spectrum of alicyclic epoxy compound product 1 prepared in Example 1 is shown. [Figure 2] The chromatogram obtained by GC-MS of alicyclic epoxy compound product 1 prepared in Example 1 is shown. [Figure 3] The peak report obtained by GC-MS for alicyclic epoxy compound product 1 prepared in Example 1 is shown. [Modes for carrying out the invention]

[0018] [Epoxy compound products] The epoxy compound product of this disclosure contains a compound represented by the following formula (1), and its purity (or content) is 80% or higher. [ka]

[0019] In formula (1), X represents a single bond or a linking group. The cyclohexane ring (cyclohexene oxide group) in formula (1) may have substituents on one or more of the carbon atoms constituting the ring.

[0020] Examples of the linking groups include divalent hydrocarbon groups, alkenylene groups in which part or all of the carbon-carbon double bonds are epoxidized, carbonyl groups, ether bonds, thiol bonds, ester bonds, carbonate groups, amide groups, -SO-, -SO2-, -CBr2-, -C(CBr3)2-, -C(CF3)2-, and groups formed by linking multiple of these groups. In particular, the linking group is preferably a group selected from the group consisting of ether bonds, thiol bonds, -SO-, -SO2-, -CH2-, -C(CH3)2-, -CBr2-, -C(CBr3)2-, and -C(CF3)2-.

[0021] Examples of the above-mentioned divalent hydrocarbon groups include linear or branched alkylene groups having 1 to 18 carbon atoms, and divalent alicyclic hydrocarbon groups. Examples of linear or branched alkylene groups having 1 to 18 carbon atoms include methylene groups, methylmethylene groups, dimethylmethylene groups, ethylene groups, propylene groups, and trimethylene groups. Examples of the above-mentioned divalent alicyclic hydrocarbon groups include divalent cycloalkylene groups (including cycloalkylidene groups) such as 1,2-cyclopentylene groups, 1,3-cyclopentylene groups, cyclopentylidene groups, 1,2-cyclohexylene groups, 1,3-cyclohexylene groups, 1,4-cyclohexylene groups, and cyclohexylidene groups.

[0022] Examples of alkenylene groups in which part or all of the carbon-carbon double bonds are epoxidized (sometimes referred to as "epoxidized alkenylene groups") include linear or branched alkenylene groups having 2 to 8 carbon atoms, such as vinylene, propenylene, 1-butenylene, 2-butenylene, butadienylene, pentenylene, hexenylene, heptenylene, and octenylene groups. In particular, the epoxidized alkenylene group is preferably an alkenylene group in which all of the carbon-carbon double bonds are epoxidized, and more preferably an alkenylene group having 2 to 4 carbon atoms in which all of the carbon-carbon double bonds are epoxidized.

[0023] Examples of substituents that the cyclohexane ring may have include a halogen atom, an oxygen atom, a hydrocarbon group which may have a halogen atom, and an alkoxy group which may have substituents. If there are multiple substituents, the substituents may be the same or different.

[0024] Typical examples of alicyclic epoxy compounds represented by formula (1) above include (3,4,3',4'-diepoxy)bicyclohexyl and compounds represented by the following formulas (i-1) to (i-10). In formulas (i-5) and (i-7) below, l and m represent integers from 1 to 30, respectively. In formula (i-5) below, R' is an alkylene group having 1 to 8 carbon atoms, and among these, linear or branched alkylene groups having 1 to 3 carbon atoms, such as methylene, ethylene, propylene, and isopropylene groups, are preferred. In formulas (i-9) and (i-10) below, n1 to n6 represent integers from 1 to 30, respectively. Other examples of alicyclic epoxy compounds represented by formula (i) above include 2,2-bis(3,4-epoxycyclohexyl)propane, 1,2-bis(3,4-epoxycyclohexane-1-yl)ethane, 1,2-epoxy-1,2-bis(3,4-epoxycyclohexane-1-yl)ethane, and bis(3,4-epoxycyclohexylmethyl)ether. [ka] [ka]

[0025] Furthermore, examples of compounds represented by formula (1) include epoxy-modified siloxanes. Examples of epoxy-modified siloxanes include linear or cyclic polyorganosiloxanes having a structural unit represented by the following formula (i'). [ka]

[0026] In the above equation (i'), R 3 R represents a substituent containing a group represented by the following formula (1a) or a substituent containing a group represented by the following formula (1b), 4 This indicates an alkyl group or alkoxy group. [ka]

[0027] In equations (1a) and (1b), R 1a , R 1b These represent identical or different linear or branched alkylene groups, such as linear or branched alkylene groups having 1 to 10 carbon atoms, including methylene group, methylmethylene group, dimethylmethylene group, ethylene group, propylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, and decamethylene group.

[0028] The epoxy equivalent (in accordance with JIS K7236) of the above epoxy-modified siloxane is, for example, 100 to 400, preferably 150 to 300.

[0029] As the epoxy-modified siloxane mentioned above, commercially available products such as the compound represented by the following formula (i'-1) (trade name "KR-470", manufactured by Shin-Etsu Chemical Co., Ltd.) can be used. [ka]

[0030] The purity of the compound represented by formula (1) above is preferably 85% or higher, more preferably 90% or higher, and even more preferably 91% or higher, from the viewpoint of further reducing the amount of outgassing generated by the cured product, and may be 92% or higher, 93% or higher, 95% or higher, or 96% or higher.

[0031] The purity of the compound represented by formula (1) in the epoxy compound product can be calculated as the percentage of peak area obtained by gel permeation chromatography (GPC). Alternatively, the purity of the compound represented by formula (1) in the epoxy compound product may be calculated by determining the percentage of peak area corresponding to the compounds represented by formulas (a) to (c) and excluding the remaining percentage. If the shoulders of the peaks overlap, the peak areas are separated by perpendicular lines to the baseline passing through the troughs of the peaks.

[0032] Furthermore, the epoxy compound product has a total content ratio of the compound represented by formula (a), the compound represented by formula (b), and the compound represented by formula (c) below, which is 1% by mass or less, preferably 0.8% by mass or less, more preferably 0.6% by mass or less, and even more preferably 0.3% by mass or less, based on the total amount (100% by mass) of the epoxy compound product. The total content ratio is, for example, 0.005% by mass or more, and may be 0.01% by mass or more, or 0.05% by mass or more. The epoxy compound product may contain one, two, or three of the compounds represented by formulas (a) to (c), or may contain none at all. [ka]

[0033] In formulas (a) to (c), X represents a single bond or a linking group, corresponding to X in formula (1), and is the same as X in formula (1). The cyclohexane ring and benzene ring in formulas (a) to (c) may have substituents on one or more of the carbon atoms constituting the ring. Examples of such substituents include those described and illustrated as substituents that the cyclohexane ring in formula (1) may have. If there are multiple substituents, these substituents may be the same or different.

[0034] The compounds represented by formulas (a) to (c) above do not have epoxy groups, and therefore do not harden when a composition containing the epoxy compound product is cured. As a result, the compounds represented by formulas (a) to (c) above remain in the cured product. When the cured product is subjected to a high-temperature environment, the compounds represented by formulas (a) to (c) above volatilize and outgas. The epoxy cured product above has a total content of 1% by mass or less of the compounds represented by formulas (a) to (c) above, so these compounds are less likely to remain in the cured product, and the amount of outgassing is reduced. In addition, it is possible to obtain effects such as small curing shrinkage, reduced curling during curing, excellent adhesion to the substrate, improved curability by active energy rays, shortened curing process, and excellent heat resistance and transparency of the cured product.

[0035] The total content of the compound represented by formula (a), the compound represented by formula (b), and the compound represented by formula (c) can be calculated as the percentage of peak areas obtained by gas chromatography and mass spectrometry (GC-MS), respectively. The compounds represented by formulas (a) to (c) are detected in gas chromatography, for example, in a relative retention time range of 0.7 to 0.72 (for example, earlier than RT17.8min in the chromatogram shown in Figure 2), when the relative retention time of the peak of the compound represented by formula (1) is set to 1.0.

[0036] The Hazen color number (APHA) of the above epoxy compound product is preferably 105 or less, more preferably 103 or less, even more preferably 100 or less, even more preferably 50 or less, even more preferably 15 or less, even more preferably 10 or less, and particularly preferably 8 or less.

[0037] (Method of manufacturing epoxy compound products) The epoxy compound product described above is obtained by epoxidizing the compound represented by the following formula (2) with an organic peracid. [ka]

[0038] In formula (2), X represents a single bond or a linking group, corresponding to X in formula (1), and is the same as X in formula (1). The cyclohexene ring in formula (2) may have substituents on one or more of the carbon atoms constituting the ring. Examples of such substituents are those described and illustrated as substituents that the cyclohexane ring in formula (1) may have. If there are multiple substituents, these substituents may be the same or different.

[0039] More specifically, the epoxy compound product described above can be manufactured through the following epoxidation step, the first deboiling step, the high-boiling step, and the second deboiling step. The order of the above steps is not particularly limited; for example, the first deboiling step and the second deboiling step may be performed in either order, but it is preferable to perform them in the order of the first deboiling step, the high-boiling step, and the second deboiling step. Epoxylation step: A step in which a compound represented by formula (2) above is reacted with an organic peracid to obtain a reaction product. First low-boiling point removal step: A step in which low-boiling point components are removed by distillation. De-boiling point process: A process to remove high-boiling point components by distillation. Second low-boiling step: A step in which compounds represented by formulas (a) to (c) are removed by distillation.

[0040] Furthermore, after the epoxidation step is completed, and before the first low-boiling step, the second low-boiling step, and the high-boiling step, the reaction product obtained may be washed with water to remove the organic peracids and their decomposition products used in the reaction (washing step).

[0041] (1) Epoxy process The epoxidation step is a step in which an organic peracid is reacted with the compound represented by formula (2) above to obtain a reaction product. In this step, a reaction product containing the compound represented by formula (1) above is obtained.

[0042] Examples of the above-mentioned organic peracids include performic acid, peracetic acid, perpropionic acid, m-chloroperbenzoic acid, trifluoroperacetic acid, and perbenzoic acid. One or more of the above-mentioned organic peracids may be used. The above-mentioned organic peracids are preferably aliphatic percarboxylic acids, and more preferably peracetic acid.

[0043] The above-mentioned aliphatic percarboxylic acid is preferably an oxygen oxide of the corresponding aldehyde. Such aliphatic percarboxylic acid is substantially water-free and can reduce the likelihood of ring-opening of the epoxy group.

[0044] The amount of organic peracid used is, for example, 0.5 to 3 moles per mole of the compound represented by formula (2) above.

[0045] The epoxidation reaction can be carried out in the presence of a solvent. Examples of such solvents include aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, isopropylbenzene, diethylbenzene, and p-cymene; alicyclic hydrocarbons such as cyclohexane and decalin; aliphatic hydrocarbons such as n-hexane, heptane, octane, nonane, and decane; alcohols such as cyclohexanol, hexanol, heptanol, octanol, nonanol, and furfuryl alcohol; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; esters such as ethyl acetate, n-amyl acetate, cyclohexyl acetate, isoamyl propionate, and methyl benzoate; polyhydric alcohols such as ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether, and diethylene glycol monoethyl ether, and their derivatives; halogen compounds such as chloroform, dimethyl chloride, carbon tetrachloride, and chlorobenzene; and ethers such as 1,2-dimethoxyethane. The above solvents may be used individually or in combination of two or more.

[0046] The amount of solvent used is, for example, about 0.2 to 10 times the mass of the compound represented by formula (2) above.

[0047] For the epoxidation reaction, stabilizers of organic peracids (e.g., ammonium hydrogen phosphate, potassium pyrophosphate, 2-ethylhexyl tripolyphosphate, etc.) or polymerization inhibitors (e.g., hydroquinone, piperidine, ethanolamine, phenothiazine, etc.) may be used as needed.

[0048] The reaction temperature for the epoxidation reaction is, for example, 0 to 70°C. The reaction atmosphere is not particularly limited as long as it does not inhibit the reaction, and may be any of the following: air, nitrogen, or argon.

[0049] (2) Washing process The above washing step is a process of removing organic peracids and their decomposition products, which are organic acids, contained in the reaction product obtained through the epoxidation step, by washing with water. In addition, a base such as sodium hydroxide may be used to neutralize the organic peracids during washing with water.

[0050] The amount of water used is, for example, about 0.1 to 3 times (v / v) the amount of reaction product. For washing, equilibrium extractors such as mixer-settler type extractors, extraction columns, or centrifugal extractors can be used.

[0051] (3) First low-boiling removal step The first low-boiling step described above is a step of distilling off components (e.g., solvent, water, etc.) with a lower boiling point than the compound represented by formula (1) that are contained in the reaction product. In this step, low-boiling point components other than the compounds represented by formulas (a) to (c) are mainly removed, but some of the compounds represented by formulas (a) to (c) may also be removed. By subjecting the product to this step, the content of low molecular weight compounds mixed into the epoxy compound product can be made extremely low.

[0052] In the first low-boiling step, it is preferable to use a thin-film evaporator for distillation. Distillation is preferably carried out under conditions of a heating temperature in the range of 50 to 200°C and a pressure in the range of 1 to 760 torr. Distillation can also be carried out in two stages by changing the pressure and temperature.

[0053] When subjecting the reaction product to the first low-boiling step, it is preferable to add a polymerization inhibitor to suppress the ring-opening polymerization reaction of the compound represented by formula (1) above. The amount of polymerization inhibitor to be added varies slightly depending on its type and distillation temperature, but it is preferably in the range of, for example, 1 to 10,000 ppm by mass (particularly 10 to 2,000 ppm by mass) relative to the reaction product.

[0054] In the first low-boiling step, components with lower boiling points than the compounds represented by formulas (a) to (c) are evaporated and removed from the reaction product, thereby obtaining a mixture of the compounds represented by formulas (a) to (c), the compound represented by formula (1), and components with higher boiling points as bottom output.

[0055] (4) High boiling process The above-mentioned high-boiling step is a step of distilling off components with higher boiling points than the compounds represented by formulas (a) to (c) and the compound represented by formula (1) that are contained in the reaction product. When the above-mentioned high-boiling step is performed after the above-mentioned low-boiling step, the above-mentioned high-boiling step is a step of evaporating and distilling off the compounds represented by formula (1) and the compounds represented by formulas (a) to (c) from the bottom liquid obtained after the above-mentioned low-boiling step, which is a mixture of the compounds represented by formulas (a) to (c), the compound represented by formula (1), and components with higher boiling points than them. By subjecting the epoxy compound product to this step, the content of high molecular weight compounds mixed in can be made extremely low.

[0056] In the deboiling step, both a distillation column and a thin-film evaporator can be used for distillation, but it is preferable to use a thin-film evaporator in order to reduce the residence time during distillation. Distillation is preferably carried out under conditions of a heating temperature of 250°C or lower (preferably 230°C or lower) from the viewpoint of suppressing the decomposition of the compound represented by formula (1) and the increase in coloration, and the ring-opening polymerization of the epoxy group of the compound represented by formula (1) and the resulting gelation. The distillation temperature is preferably 50°C or higher, more preferably 100°C or higher. Also, from the same viewpoint, distillation is preferably carried out under conditions of a pressure of 3 torr or lower (preferably 0.7 torr or lower). The above pressure is preferably 0.01 torr or higher, and may be 0.02 torr or higher, from the viewpoint of achieving a higher purity of the epoxy compound product.

[0057] (5)Second low boiling step The second low-boiling step described above is a step of distilling off the compounds represented by formulas (a) to (c) contained in the reaction product. By subjecting the product to this step, the content of the compounds represented by formulas (a) to (c) that are mixed into the epoxy compound product can be made extremely low.

[0058] In the second low-boiling step, it is preferable to use a distillation column for distillation. When the second low-boiling step is performed after the high-boiling step, in the second low-boiling step, the distillate obtained through the high-boiling step is introduced into a distillation column, and the compounds represented by formulas (a) to (c) are removed by evaporation from the mixture of the compound represented by formula (1) and the compounds represented by formulas (a) to (c), and the compound represented by formula (1) is obtained as the bottom liquid.

[0059] For example, a packed column or a tray column can be used as the distillation column. The actual number of stages in the distillation column is preferably 14 or more, and is preferably 14 to 100 stages, and particularly preferably 14 to 50 stages, in order to further improve the purity of the product.

[0060] In the second low-boiling step, distillation is preferably carried out at a temperature of 250°C or lower (e.g., 50-250°C) and with a residence time at the bottom of the tank of less than 10 hours (e.g., 1 hour or more but less than 10 hours). Distillation can also be carried out in two stages by changing the pressure and temperature. By setting the heating temperature to 260°C or lower, ring-opening polymerization of the epoxy compound can be suppressed and distillation can be carried out smoothly, and by setting the heating temperature to 250°C or lower, discoloration of the resulting epoxy compound can be suppressed.

[0061] By processing the reaction product, particularly by performing the first low-boiling step, the high-boiling step, and the second low-boiling step in this order, the epoxy compound product can be obtained that contains the compound represented by formula (1) in high purity and has a significantly reduced amount of the compounds represented by formulas (a) to (c).

[0062] Epoxy compound products obtained by distillation purification using a general thin-film still (WFE) tend to contain a high amount of the compounds represented by formulas (a) to (c) above. Furthermore, if the reaction product is distilled in a distillation column without performing the low-boiling and high-boiling steps using a WFE, or after the solvent has been removed by the low-boiling step, the residence time at the bottom of the column becomes long, resulting in significant discoloration and gelation due to ring-opening polymerization. Moreover, it was impossible to separate the compounds represented by formulas (a) to (c) above from the compound represented by formula (1) above in purification using a WFE. On the other hand, if the low-boiling and high-boiling steps are performed simultaneously in a distillation column, the residence time at the bottom of the column becomes long, resulting in significant discoloration and gelation due to ring-opening polymerization. In contrast, by performing precision distillation under conditions such as 14 or more stages in the distillation column, a heating temperature of 250°C or less, and a residence time at the bottom of the column of less than 10 hours, after performing the low-boiling and high-boiling steps using a WFE, the compounds represented by formulas (a) to (c) above can be efficiently removed.

[0063] [Curable composition] The compound represented by formula (1) above is a curable compound, and a curable composition can be obtained using the epoxy compound product described above. The curable composition includes the epoxy compound product described above.

[0064] (curable compound) The above curable composition contains, as a curable compound, at least the compound represented by formula (1) contained in the epoxy compound product described above. The above curable composition may also contain other curable compounds other than the compound represented by formula (1). The other curable compounds may be one or two or more.

[0065] Examples of the above-mentioned other curable compounds include other epoxy compounds other than the compound represented by formula (1) above, compounds having one or more oxetane groups in their molecule (sometimes referred to as "oxetane compounds"), and compounds having one or more vinyl ether groups in their molecule (sometimes referred to as "vinyl ether compounds"). The above-mentioned curable composition may contain the above-mentioned other epoxy compounds and / or oxetane compounds as the other compounds.

[0066] The above-mentioned other epoxy compounds are compounds having one or more epoxy groups (oxyranyl groups) in their molecules. Among these other epoxy compounds, compounds having two or more epoxy groups (preferably 2 to 6, more preferably 2 to 4) in their molecules are preferred.

[0067] Other epoxy compounds mentioned above include alicyclic epoxy compounds, aromatic epoxy compounds, and aliphatic epoxy compounds.

[0068] The above-mentioned alicyclic epoxy compounds include, but are not particularly limited to, known or conventional compounds having one or more alicyclic rings and one or more epoxy groups in their molecule. Examples include (I) compounds in which an epoxy group is directly bonded to an alicyclic ring by a single bond; and (II) compounds having both an alicyclic ring and a glycidyl ether group in their molecule (glycidyl ether type epoxy compounds).

[0069] Examples of compounds in which an epoxy group is directly bonded to the alicyclic ring (I) above by a single bond include the compound represented by the following formula (ii). [ka]

[0070] In formula (ii), R'' is a group obtained by removing p hydroxyl groups (-OH) from the structural formula of a p-valent alcohol (a p-valent organic group), and p and n are natural numbers. Examples of p-valent alcohols [R''(OH)p] include polyhydric alcohols such as 2,2-bis(hydroxymethyl)-1-butanol (alcohols with 1 to 15 carbon atoms). p is preferably 1 to 6, and n is preferably 1 to 30. When p is 2 or greater, the n in each group within the parentheses ( ) (outer parentheses) may be the same or different. Specific examples of compounds represented by the above formula (ii) include the 1,2-epoxy-4-(2-oxyranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol [for example, trade name "EHPE3150" (manufactured by Daicel Corporation)].

[0071] Examples of compounds having an alicyclic ring and a glycidyl ether group in the molecule (II) above include glycidyl ethers of alicyclic alcohols (especially alicyclic polyhydric alcohols). More specifically, examples include hydrogenated compounds of bisphenol A type epoxy compounds such as 2,2-bis[4-(2,3-epoxypropoxy)cyclohexyl]propane and 2,2-bis[3,5-dimethyl-4-(2,3-epoxypropoxy)cyclohexyl]propane (hydrogenated bisphenol A type epoxy compounds); bis[o,o-(2,3-epoxypropoxy)cyclohexyl]methane, bis[o,p-(2,3-epoxypropoxy)cyclohexyl]methane, bis[p,p-(2,3-epoxypropoxy)cyclohexyl]methane, bis[3,5-dimethyl-4-( Examples include hydrogenated compounds of bisphenol F type epoxy compounds such as 2,3-epoxypropoxy)cyclohexyl]methane (hydrogenated bisphenol F type epoxy compounds); hydrogenated bisphenol type epoxy compounds; hydrogenated phenol novolac type epoxy compounds; hydrogenated cresol novolac type epoxy compounds; hydrogenated cresol novolac type epoxy compounds of bisphenol A; hydrogenated naphthalene type epoxy compounds; hydrogenated epoxy compounds of epoxy compounds obtained from trisphenolmethane; and hydrogenated epoxy compounds of other epoxy compounds having aromatic rings.

[0072] The above aromatic epoxy compounds are compounds having one or more aromatic rings (aromatic hydrocarbon rings or aromatic heterocycles) and one or more epoxy groups within the molecule. Among aromatic epoxy compounds, compounds in which a glycidoxy group is bonded to one or more carbon atoms constituting an aromatic ring (particularly an aromatic hydrocarbon ring) (aromatic glycidyl ether epoxy compounds) are preferred.

[0073] Examples of the aromatic epoxy compounds include epibis-type glycidyl ether epoxy resins obtained by the condensation reaction of bisphenols [e.g., bisphenol A, bisphenol F, bisphenol S, fluorenebisphenol, etc.] with epihalohydrins; high molecular weight epibis-type glycidyl ether epoxy resins obtained by further addition reactions of these epibis-type glycidyl ether epoxy resins with the above bisphenols; and phenols [e.g., phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol]. Examples include novolac alkyl-type glycidyl ether epoxy resins obtained by condensing polyhydric alcohols obtained by condensing polyhydric alcohols [e.g., formaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, salicylaldehyde, etc.] with epihalohydrins, and epoxy compounds in which two phenol skeletons are bonded to the 9th position of a fluorene ring, and glycidyl groups are bonded directly or via alkylene oxy groups to the oxygen atoms obtained by removing hydrogen atoms from the hydroxyl groups of these phenol skeletons.

[0074] Examples of the above-mentioned aliphatic epoxy compounds include glycidyl ethers of alcohols (where q is a natural number) that do not have a q-valent cyclic structure; glycidyl esters of monovalent or polyvalent carboxylic acids [e.g., acetic acid, propionic acid, butyric acid, stearic acid, adipic acid, sebacic acid, maleic acid, itaconic acid, etc.]; epoxides of oils and fats having double bonds, such as epoxides of linseed oil, epoxides of soybean oil, and epoxides of castor oil; and epoxides of polyolefins (including polyalkadienes), such as epoxides of polybutadiene. Examples of alcohols that do not have the q-valent cyclic structure include monohydric alcohols such as methanol, ethanol, 1-propyl alcohol, isopropyl alcohol, and 1-butanol; dihydric alcohols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, polyethylene glycol, and polypropylene glycol; and polyhydric alcohols of trihydric or higher valencies such as glycerin, diglycerin, erythritol, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, and sorbitol. The q-valent alcohol may also be polyether polyol, polyester polyol, polycarbonate polyol, or polyolefin polyol.

[0075] The above oxetane compounds include known and commonly used compounds having one or more oxetane rings in the molecule, and are not particularly limited, but examples include 3,3-bis(vinyloxymethyl)oxetane, 3-ethyl-3-(hydroxymethyl)oxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-[(phenoxy)methyl]oxetane, 3-ethyl-3-(hexyloxymethyl)oxetane, 3-ethyl-3-(chloromethyl)oxetane, 3,3-bis(chloromethyl)oxetane, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, bis{[1 Examples include ethyl(3-oxetanyl)methyl ether, 4,4'-bis[(3-ethyl-3-oxetanyl)methoxymethyl]bicyclohexyl, 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]cyclohexane, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, 3-ethyl-3-{[(3-ethyloxetan-3-yl)methoxy]methyl}oxetane, xylylenebisoxetane, 3-ethyl-3-{[3-(triethoxysilyl)propoxy]methyl}oxetane, oxetanylsilsesquioxane, and phenol novolac oxetane.

[0076] The vinyl ether compounds mentioned above are not particularly limited, but can be known or conventional compounds having one or more vinyl ether groups in the molecule. For example, 2-hydroxyethyl vinyl ether (ethylene glycol monovinyl ether), 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxyisopropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 2-hydroxybutyl vinyl ether, 3-hydroxyisobutyl vinyl ether, 2-hydroxyisobutyl vinyl ether, 1-methyl-3-hydroxypropyl vinyl ether, 1-methyl-2-hydroxypropyl vinyl ether, 1-hydroxymethylpropyl vinyl ether, 4-hydroxycyclohexyl vinyl ether, 1,6-hexanediol monovinyl ether, 1,6-hexanediol divinyl ether, 1,8-octanediol divinyl ether, 1,4-cyclohexanedimethanol monovinyl ether, 1,4-cyclohexanedimethanol divinyl ether, 1,3-cyclohexanedimethanol monovinyl ether, 1,3-cyclohexanedimethanol divinyl ether, 1,2-cyclohexanedimethanol monovinyl ether, 1,2-Cyclohexanedimethanol divinyl ether, p-xylene glycol monovinyl ether, p-xylene glycol divinyl ether, m-xylene glycol monovinyl ether, m-xylene glycol divinyl ether, o-xylene glycol monovinyl ether, o-xylene glycol divinyl ether, ethylene glycol divinyl ether, diethylene glycol monovinyl ether, diethylene glycol divinyl ether, triethylene glycol monovinyl ether, triethylene glycol divinyl ether, tetraethylene glycol monovinyl ether, tetraethylene glycol divinyl ether, pentaethylene glycol monovinyl ether, pentaethylene glycol divinyl ether, oligoethylene glycol monovinyl ether, oligoethylene glycol divinyl ether, polyethylene glycol monovinyl ether, polyethylene glycol divinyl ether, dipropylene glycol monovinyl ether, dipropylene glycol divinyl ether, tripropylene glycol mono Divinyl ether, tripropylene glycol divinyl ether, tetrapropylene glycol monovinyl ether, tetrapropylene glycol divinyl ether, pentapropylene glycol monovinyl ether, pentapropylene glycol divinyl ether, oligopropylene glycol monovinyl ether, oligopropylene glycol divinyl ether, polypropylene glycol monovinyl ether, polypropylene glycol divinyl ether, isosorbide divinyl ether, oxanorbornene divinyl ether, phenyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, octyl vinyl ether, cyclohexyl vinyl ether, hydroquinone divinyl ether, 1,4-butanediol divinyl ether, cyclohexanedimethanol divinyl ether, trimethylolpropane divinyl ether, trimethylolpropane trivinyl ether, bisphenol A divinyl ether, bisphenol F divinyl ether, hydroxyoxanorbornane methanol divinyl ether, 1,Examples include 4-cyclohexanediol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, and dipentaerythritol hexanyl ether.

[0077] The proportion of the compound represented by formula (1) in the total amount (100% by mass) of curable compounds contained in the above curable composition is, for example, 50% by mass or more (for example, 50 to 100% by mass), preferably 60% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more.

[0078] The above curable composition preferably contains, in addition to the curable compound, one or more selected from the group consisting of, for example, a curing agent, a curing accelerator, and a curing catalyst. The above curable composition preferably contains a curing agent and / or a curing catalyst.

[0079] The total content of the curable compound, curing agent, and / or curing accelerator in the total amount (100% by mass) of the above curable composition is, for example, 60% by mass or more, preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and particularly preferably 95% by mass or more.

[0080] The total content of the curable compound and curing catalyst in the total amount (100% by mass) of the above curable composition is, for example, 60% by mass or more, preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and particularly preferably 95% by mass or more.

[0081] The content ratio of compounds other than the curable compound, curing agent, curing accelerator, and curing catalyst, relative to the total amount (100% by mass) of the above curable composition, is, for example, 50% by mass or less, and preferably 40% by mass or less.

[0082] (Hardening agent) As the curing agent mentioned above, for example, known or conventional curing agents for epoxy resins such as acid anhydrides (acid anhydride-based curing agents), amines (amine-based curing agents), polyamide resins, imidazoles (imidazole-based curing agents), polymercaptans (polymercaptan-based curing agents), phenols (phenol-based curing agents), polycarboxylic acids, dicyandiamides, and organic acid hydrazides can be used. One or more of the curing agents may be used.

[0083] Examples of the above acid anhydrides include methyltetrahydrophthalic anhydride (4-methyltetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, etc.), methylhexahydrophthalic anhydride (4-methylhexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, etc.), dodecenyl succinic anhydride, methylendomethylenetetrahydrophthalic anhydride, phthalic anhydride, maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methylcyclohexenidica Examples include rubonic anhydrides, pyromellitic anhydride, trimellitic anhydride, benzophenonetetracarboxylic anhydride, nadic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, 4-(4-methyl-3-pentenyl)tetrahydrophthalic anhydride, succinic anhydride, adipic anhydride, sebadic anhydride, dodecanedioic anhydride, methylcyclohexenetetracarboxylic anhydride, vinyl ether maleic anhydride copolymer, and alkylstyrene-maleic anhydride copolymer. Among these, from the viewpoint of ease of handling, acid anhydrides that are liquid at 25°C [for example, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, dodecenyl succinic anhydride, methylendomethylenetetrahydrophthalic anhydride, etc.] are preferred.

[0084] Examples of the above amines include aliphatic polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenediamine, diethylaminopropylamine, and polypropylenetriamine; mensendiamine, isophoronediamine, bis(4-amino-3-methyldicyclohexyl)methane, diaminodicyclohexylmethane, bis(aminomethyl)cyclohexane, N-aminoethylpiperazine, and 3,9-bis(3-aminopropyl)-3,4,8. Examples include alicyclic polyamines such as 10-tetraoxaspiro[5,5]undecane; mononuclear polyamines such as m-phenylenediamine, p-phenylenediamine, torylene-2,4-diamine, torylene-2,6-diamine, mesitylene-2,4-diamine, 3,5-diethyltrylene-2,4-diamine, and 3,5-diethyltrylene-2,6-diamine; and aromatic polyamines such as biphenylenediamine, 4,4-diaminodiphenylmethane, 2,5-naphthylenediamine, and 2,6-naphthylenediamine.

[0085] Examples of the polyamide resins mentioned above include polyamide resins having either a primary amino group or a secondary amino group, or both, within the molecule.

[0086] Examples of the above imidazoles include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, and 1-cyanoethyl-2 Examples include undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2-methylimidazolium isocyanurate, 2-phenylimidazolium isocyanurate, 2,4-diamino-6-[2-methylimidazolyl-(1)]-ethyl-s-triazine, and 2,4-diamino-6-[2-ethyl-4-methylimidazolyl-(1)]-ethyl-s-triazine.

[0087] Examples of the above-mentioned polymercaptans include liquid polymercaptans and polysulfide resins.

[0088] Examples of the phenols mentioned above include novolac-type phenolic resins, novolac-type cresol resins, aralkyl resins such as p-xylylene-modified phenolic resins and p-xylylene-m-xylylene-modified phenolic resins, terpene-modified phenolic resins, dicyclopentadiene-modified phenolic resins, and triphenolpropane.

[0089] Examples of the polycarboxylic acids mentioned above include adipic acid, sebacic acid, terephthalic acid, trimellitic acid, and carboxyl group-containing polyesters.

[0090] As a curing agent, acid anhydrides (acid anhydride-based curing agents) are preferred from the viewpoint of heat resistance and transparency of the resulting cured product. For example, commercially available products such as "Ricacid MH-700" and "Ricacid MH-700F" (both manufactured by Shin-Nippon Rika Co., Ltd.) and "HN-5500" (manufactured by Hitachi Chemical Co., Ltd.) can be used.

[0091] The curing agent content (amount blended) is preferably 50 to 200 parts by mass, and more preferably 80 to 150 parts by mass, per 100 parts by mass of the total amount of epoxy compounds contained in the curable composition. More specifically, when using acid anhydrides as the curing agent, it is preferable to use them in a ratio of 0.5 to 1.5 equivalents per equivalent of epoxy groups in all epoxy compounds contained in the curable composition. When the curing agent content is 50 parts by mass or more, curing can proceed sufficiently, and the toughness of the resulting cured product tends to improve. On the other hand, when the curing agent content is 200 parts by mass or less, discoloration is further suppressed, and a cured product with excellent hue tends to be obtained.

[0092] (Curing accelerator) If the above curable composition contains a curing agent, it is preferable that it further contains a curing accelerator. The curing accelerator has the effect of accelerating the reaction rate when a compound having an epoxy group (oxyranyl group) reacts with the curing agent.

[0093] Examples of the curing accelerators mentioned above include 1,8-diazabicyclo[5.4.0]undecene-7(DBU) or its salts (e.g., phenol salt, octyl salt, p-toluenesulfonate, formate, tetraphenylborate salt, etc.), 1,5-diazabicyclo[4.3.0]nonene-5(DBN) or its salts (e.g., phenol salt, octyl salt, p-toluenesulfonate, formate, tetraphenylborate salt, etc.); benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, Examples include tertiary amines such as N,N-dimethylcyclohexylamine; imidazoles such as 2-ethyl-4-methylimidazole and 1-cyanoethyl-2-ethyl-4-methylimidazole; phosphate esters; phosphines such as triphenylphosphine and tris(dimethoxy)phosphine; phosphonium compounds such as tetraphenylphosphonium tetra(p-tolyl)borate; organometallic salts such as zinc octylate, tin octylate, and zinc stearate; and metal chelates such as aluminum acetylacetone complexes. One or more of the above curing accelerators may be used.

[0094] As the curing accelerator mentioned above, commercially available products such as "U-CATSA 506", "U-CAT SA102", "U-CAT 5003", "U-CAT 18X", and "U-CAT 12XD" (development product) (all manufactured by Sunapro Co., Ltd.); "TPP-K" and "TPP-MK" (both manufactured by Hokko Chemical Industry Co., Ltd.); and "PX-4ET" (manufactured by Nippon Chemical Industrial Co., Ltd.) can be used.

[0095] The content (amount blended) of the curing accelerator is preferably 0.01 to 5 parts by mass, more preferably 0.02 to 3 parts by mass, and even more preferably 0.03 to 3 parts by mass, per 100 parts by mass of the curing agent. When the content of the curing accelerator is 0.01 parts by mass or more, a more efficient curing acceleration effect tends to be obtained. On the other hand, when the content of the curing accelerator is 5 parts by mass or less, discoloration is further suppressed, and a cured product with excellent hue tends to be obtained.

[0096] (curing catalyst) The above curable composition may contain a curing catalyst instead of a curing agent. The curing catalyst has the function of curing the curable composition by initiating and / or promoting the curing reaction (polymerization reaction) of a cationic curable compound such as the compound represented by formula (1) above. Examples of curing catalysts include cationic polymerization initiators (photo-cationic polymerization initiators, thermal cationic polymerization initiators, etc.) that generate cationic species by light irradiation or heat treatment to initiate polymerization, as well as Lewis acid / amine complexes, Brønsted salts, and imidazoles. One type of curing catalyst may be used, or two or more types may be used.

[0097] Furthermore, examples of the above-mentioned photocationic polymerization initiators include sulfonium salts such as triarylsulfonium hexafluorophosphate (e.g., p-phenylthiophenyldiphenylsulfonium hexafluorophosphate) and triarylsulfonium hexafluoroantimonate (especially triarylsulfonium salts); iodonium salts such as diaryliodonium hexafluorophosphate, diaryliodonium hexafluoroantimonate, bis(dodecylphenyl)iodonium tetrakis(pentafluorophenyl)borate, and iodonium[4-(4-methylphenyl-2-methylpropyl)phenyl]hexafluorophosphate; phosphonium salts such as tetrafluorophosphonium hexafluorophosphate; and pyridinium salts such as N-hexylpyridinium tetrafluoroborate.

[0098] Specifically, the above photocationic polymerization initiators include (4-hydroxyphenyl)methylbenzylsulfonium tetrakis(pentafluorophenyl)borate, 4-(4-biphenylylthio)phenyl-4-biphenylylphenylsulfonium tetrakis(pentafluorophenyl)borate, 4-(phenylthio)phenyldiphenylsulfonium phenyltris(pentafluorophenyl)borate, [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium phenyltris(pentafluorophenyl)borate, diphenyl[4-(phenylthio)phenyl]sulfonium tris(pentafluoroethyl)trifluorophosphate, diphenyl[4-(phenylthio)phenyl]sulfonium tetrakis(pentafluorophenyl)borate, diphenyl[4-(phenylthio)phenyl]sulfonium hexafluorophosphate, and 4-(4-biphenylylthio)phenyl-4-biphenylylphenylsulfonium Examples include tris(pentafluoroethyl)trifluorophosphate, bis[4-(diphenylsulfonio)phenyl]sulfenyltris(pentafluorophenyl)borate, [4-(2-thiooxantonylthio)phenyl]phenyl-2-thiooxantonylsulfonium phenyltris(pentafluorophenyl)borate, and 4-(phenylthio)phenyldiphenylsulfonium hexafluoroantimonate.

[0099] The above photocationic polymerization initiator may be a commercially available product. Examples of commercially available products include the following: "Cyracure UVI-6970", "Cyracure UVI-6974", "Cyracure UVI-6990", "Cyracure UVI-950" (all manufactured by Union Carbide, USA), "Omnirad250", "Omnirad261", "Omnirad264", "CG-24-61" (all manufactured by IGM Resins), "Optomer SP-150", "Optomer SP-151", "Optomer SP-170", "Optomer SP-171" (all manufactured by ADEKA Corporation), and "DAICAT "II" (manufactured by Daicel Corporation), "UVAC1590", "UVAC1591" (both manufactured by Daicel Ornex Corporation), "CI-2064", "CI-2639", "CI-2624", "CI-2481", "CI-2734", "CI-2855", "CI-2823", "CI-2758", "CIT-1682" (all manufactured by Nippon Soda Co., Ltd.), "PI-2074" (manufactured by Rhodia, tetrakis(pentafluorophenyl) borate) Examples include toricumyliodonium salt, "FFC509" (manufactured by 3M), "BBI-102", "BBI-101", "BBI-103", "MPI-103", "TPS-103", "MDS-103", "DTS-103", "NAT-103", "NDS-103" (all manufactured by Midori Chemical Co., Ltd.), "CD-1010", "CD-1011", "CD-1012" (all manufactured by Sartomer, USA), "CPI-100P", "CPI-101A" (both manufactured by Sunapro Co., Ltd.).

[0100] Examples of the above-mentioned thermal cationic polymerization initiators include aryldiazonium salts, aryliodonium salts, arylsulfonium salts, and allene-ion complexes. Commercially available products such as "PP-33," "CP-66," and "CP-77" (all manufactured by ADEKA Corporation); "FC-509" (manufactured by 3M); "UVE1014" (manufactured by GE); "Sun-Aid SI-60L," "Sun-Aid SI-80L," "Sun-Aid SI-100L," "Sun-Aid SI-110L," and "Sun-Aid SI-150L" (all manufactured by Sanshin Chemical Industry Co., Ltd.); and "CG-24-61" (manufactured by BASF) can be preferably used.

[0101] Examples of the Lewis acid-amine complexes mentioned above include BF3·n-hexylamine, BF3·monoethylamine, BF3·benzylamine, BF3·diethylamine, BF3·piperidine, BF3·triethylamine, BF3·aniline, BF4·n-hexylamine, BF4·monoethylamine, BF4·benzylamine, BF4·diethylamine, BF4·piperidine, BF4·triethylamine, BF4·aniline, PF5·ethylamine, PF5·isopropylamine, PF5·butylamine, PF5·laurylamine, PF5·benzylamine, and AsF5·laurylamine.

[0102] Examples of the Brønsted salts mentioned above include aliphatic sulfonium salts, aromatic sulfonium salts, iodonium salts, and phosphonium salts.

[0103] Examples of the above imidazoles include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, and 1-cyanoethyl-2 Examples include undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2-methylimidazolium isocyanurate, 2-phenylimidazolium isocyanurate, 2,4-diamino-6-[2-methylimidazolyl-(1)]-ethyl-s-triazine, and 2,4-diamino-6-[2-ethyl-4-methylimidazolyl-(1)]-ethyl-s-triazine.

[0104] The content (amount blended) of the curing catalyst is preferably 0.01 to 5 parts by mass, more preferably 0.02 to 4 parts by mass, and even more preferably 0.03 to 3 parts by mass, per 100 parts by mass of the cationic curable compound contained in the curable composition. When the content of the curing catalyst is within the above range, the curing speed of the curable composition tends to increase, and the heat resistance and transparency of the cured product tend to improve in a well-balanced manner.

[0105] The above-mentioned curable composition may contain additives in addition to the components described above, as needed. Examples of such additives include polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, and glycerin; defoamers, leveling agents, silane coupling agents, surfactants, inorganic fillers, flame retardants, colorants, ion adsorbents, pigments, phosphors, and mold release agents. One or more of these additives may be used.

[0106] The above-mentioned curable composition can be prepared by stirring and mixing the above-mentioned components while heating them as needed. For the stirring and mixing, known or conventional stirring and mixing means such as various mixers such as dissolvers and homogenizers, kneaders, roll mills, bead mills, and self-rotating stirring devices can be used. After stirring and mixing, degassing may be performed under vacuum.

[0107] The proportion of the compound represented by formula (1) in the above curable composition to the total amount (100% by mass) of the compound represented by formula (1), the compound represented by formula (a), the compound represented by formula (b), and the compound represented by formula (c) is 80% by mass or more, preferably 85% by mass or more, more preferably 90% by mass or more, even more preferably 91% by mass or more, and may be 92% by mass or more, 93% by mass or more, 95% by mass or more, or 96% by mass or more. The above proportion can be calculated from the proportion of peak areas obtained by GC-MS.

[0108] In the curable composition described above, the total proportion of the compound represented by formula (a), the compound represented by formula (a), the compound represented by formula (b), and the compound represented by formula (c) in relation to the total amount (100% by mass) of the compound represented by formula (1), the compound represented by formula (a), the compound represented by formula (b), and the compound represented by formula (c) is 1% by mass or less, preferably 0.8% by mass or less, more preferably 0.6% by mass or less, and even more preferably 0.4% by mass or less. The above proportion can be calculated from the proportion of peak areas obtained by GC-MS.

[0109] The above curable composition has rapid curing properties, and the curing time (or gel time) at 80°C when using a thermal cationic polymerization initiator is, for example, 600 seconds or less, preferably 500 seconds or less. Furthermore, the curing time (or gel time) at 120°C when using an acid anhydride curing agent for the above curable composition is, for example, 900 seconds or less, preferably 800 seconds or less. Furthermore, when using a photocationic polymerization initiator for the above curable composition, the curing time (or gel time) at ultraviolet irradiation (illuminance 3000 mJ / cm²) is... 2The curing time (or gel time) in this process is, for example, 300 seconds or less, preferably 150 seconds or less.

[0110] The heating temperature (curing temperature) during curing is preferably 45 to 200°C, more preferably 100 to 190°C, and even more preferably 100 to 180°C. The heating time (or curing time) is preferably 30 to 600 minutes, and more preferably 45 to 540 minutes. If the heating temperature or heating time falls below the above range, curing will be insufficient, and conversely, if it exceeds the above range, decomposition of the resin components may occur, so both are undesirable. The curing conditions depend on various factors, but can be appropriately adjusted, for example, by shortening the heating time when the heating temperature is high, or lengthening the heating time when the heating temperature is low.

[0111] [Cured product] A cured product is obtained by curing the above-mentioned curable composition. The cured product exhibits low outgassing in high-temperature environments, is less prone to curing shrinkage, and has excellent transparency and heat resistance.

[0112] The above cured product exhibits excellent transparency, and its light transmittance at a wavelength of 400 nm (at a thickness of 3 mm) is preferably 40% or more, more preferably 60% or more, even more preferably 70% or more, and may also be 75% or more, 80% or more, or 85% or more, with a particularly preferred transmittance of 90% or more. When a thermal cationic polymerization initiator is used, the above light transmittance of the cured product is preferably 70% or more, more preferably 75% or more. When an acid anhydride curing agent is used, the above light transmittance of the cured product is preferably 85% or more, more preferably 90% or more. Because the above curable composition forms a cured product with excellent transparency, when used as a encapsulant or die attach paste for optical semiconductor elements in optical semiconductor devices, the luminosity emitted from the optical semiconductor device tends to be higher.

[0113] The above cured product has excellent heat resistance, and its glass transition temperature (Tg-DMA) is preferably 200°C or higher, more preferably 220°C or higher, even more preferably 230°C or higher, even more preferably 240°C or higher, and particularly preferably 250°C or higher. When a thermal cationic polymerization initiator is used, the above glass transition temperature of the cured product is preferably 200°C or higher, more preferably 300°C or higher. When an acid anhydride curing agent is used, the above glass transition temperature of the cured product is preferably 230°C or higher, more preferably 250°C or higher.

[0114] The above cured product has excellent heat resistance, and its 5% weight loss temperature (Td5) is preferably 325°C or higher, more preferably 330°C or higher, and even more preferably 335°C or higher. Furthermore, the 10% weight loss temperature (Td10) of the above cured product is preferably 355°C or higher, and more preferably 360°C or higher.

[0115] The curing shrinkage rate of the above cured product is preferably 3.0% or less, more preferably 1.5% or less, and even more preferably 1.1% or less. The above curing shrinkage rate is determined by measuring the density of the curable composition before curing and the cured product after curing, and calculating the density change based on the following formula. Volume contraction rate r = {(ds-dl) / dl} × 100 dl: Specific gravity of the liquid before curing. Measured using a density hydrometer "DA-640" (manufactured by Kyoto Electronics Manufacturing Co., Ltd.). ds: Specific gravity of the solid after curing. Measured using the solid specific gravity measurement method.

[0116] The amount of outgassing of the above cured product when heated at 110°C for 30 minutes is preferably 0.1% or less, more preferably 0.09% or less, and even more preferably 0.08% or less. The amount of outgassing is determined by measuring the mass of the cured product before heating and after heating, and calculating the mass loss rate based on the following formula. Mass reduction rate = {(Mass of cured material before heating - Mass of cured material after heating) / Mass of cured material before heating} × 100

[0117] The bending strength of the cured material after molding it into a shape of 4 mm thickness × 10 mm width × 80 mm length is preferably 45 MPa or more, more preferably 50 MPa or more, and even more preferably 55 MPa or more. The upper limit is not particularly limited, but may be 300 MPa or less. The bending strength can be measured, for example, by the method described in the examples below.

[0118] The flexural modulus of the cured material after being molded into a shape of 4 mm thickness × 10 mm width × 80 mm length is preferably 2500 MPa or more, more preferably 3000 MPa or more, and even more preferably 3300 MPa or more. The upper limit is not particularly limited, but may be 5000 MPa or less. The flexural modulus can be measured, for example, by the method described in the examples below.

[0119] The bending elongation of the cured material after molding it into a shape of 4 mm thickness × 10 mm width × 80 mm length is preferably 1.0% GL or more, more preferably 1.2% GL or more, and even more preferably 1.4% GL or more. The upper limit is not particularly limited, but may be 5.0% GL or less. The bending elongation can be measured, for example, by the method described in the examples below.

[0120] The above-mentioned curable composition can be used in a variety of applications, such as encapsulants, adhesives, coatings, hard coats, electrical insulating materials (automotive insulating materials, etc.), laminates, inks (inkjet printing inks, UV inks, etc.), sealants, resists, composite materials, transparent substrates, transparent sheets, transparent films, optical elements, optical lenses, stereolithography, electronic paper, touch panels, solar cell substrates, optical waveguides, light guide plates, holographic memory, and more.

[0121] [Sealant] The above-mentioned encapsulant comprises the above-mentioned curable composition. The above-mentioned encapsulant can be preferably used for encapsulating optical semiconductors (optical semiconductor elements) in optical semiconductor devices. When the above-mentioned encapsulant is used, optical semiconductor elements can be encapsulated with a cured product (=encapsulant) that has excellent transparency and heat resistance and is less prone to curing shrinkage. Furthermore, because outgassing is less likely to occur in high-temperature environments, cracks are less likely to occur, and the reliability of semiconductor elements and other components encapsulated with the encapsulant is maintained.

[0122] The content ratio of the curable composition to the total amount (100% by mass) of the above-mentioned sealant is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more. The above-mentioned sealant may consist solely of the above-mentioned curable composition.

[0123] [glue] The above adhesive includes the above curable composition. The above adhesive can be used in various applications where excellent transparency, heat resistance, and low curing shrinkage are required, such as for bonding and fixing components to a substrate, specifically as a die attach paste for bonding and fixing optical semiconductor elements to metal electrodes in optoelectronic devices; a lens adhesive for fixing lenses in cameras and the like to a substrate or bonding lenses together; and an optical film adhesive for fixing optical films (e.g., polarizers, polarizer protective films, phase difference films, etc.) to a substrate or bonding optical films together or optical films with other films. Furthermore, because outgassing is less likely to occur in high-temperature environments, cracks are less likely to occur, and the reliability of the bonded components is maintained.

[0124] The above adhesive can be used particularly favorably as a die attach paste (or die bond agent). By using the above adhesive as a die attach paste, an optoelectronic device can be obtained in which an optoelectronic semiconductor element is bonded to an electrode with a cured product that has excellent transparency and heat resistance. Furthermore, because outgassing is less likely to occur in high-temperature environments, cracks are less likely to occur, and the reliability of the bonded components is maintained.

[0125] The content ratio of the curable composition to the total amount (100% by mass) of the adhesive is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more. The adhesive may consist solely of the curable composition.

[0126] [Coating agent] The above coating agent includes the above curable composition. The above coating agent can be used in various applications where excellent handling, transparency, and heat resistance are required. Furthermore, curing shrinkage is less likely to occur when the coating agent is applied and cured, and curling is less likely to occur.

[0127] The content ratio of the curable composition to the total amount of the coating agent (100% by mass) is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more. The coating agent may consist solely of the curable composition.

[0128] [Hard Coating Agent] The hard coat agent described above includes the curable composition described above. The hard coat agent can be used in various applications where excellent handling, transparency, surface hardness, and heat resistance are required. Furthermore, curing shrinkage is less likely to occur when the hard coat agent is applied and cured to form a hard coat layer, and curling is less likely to occur.

[0129] The content ratio of the curable composition to the total amount (100% by mass) of the hard coat agent is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more. The hard coat agent may consist solely of the curable composition.

[0130] [Optical components] An optical component can be obtained using the above cured product. The optical component comprises a cured product of the above curable composition. Examples of the optical component include an optoelectronic device in which an optoelectronic semiconductor element is sealed with the above cured product, an optoelectronic device in which an optoelectronic semiconductor element is bonded to an electrode by the above cured product, and an optoelectronic device in which an optoelectronic semiconductor element is bonded to an electrode by the above cured product and the optoelectronic semiconductor element is sealed with the above cured product. Because the optical component has a structure that is sealed and bonded with the above cured product, it has excellent heat resistance and high light extraction efficiency. In addition, outgassing is less likely to occur in high-temperature environments, so cracks are less likely to occur and the reliability of the optoelectronic semiconductor element and optical component is maintained.

[0131] Each embodiment disclosed herein can be combined with any other features disclosed herein. Each configuration and combination thereof in each embodiment is an example, and additions, omissions, substitutions, and other modifications are permitted as appropriate, without departing from the spirit of this disclosure. Furthermore, each invention relating to this disclosure is not limited by the embodiments or the following examples, but is limited solely by the claims. [Examples]

[0132] An embodiment of this disclosure will be described in more detail below based on examples, but this disclosure is not limited to these examples.

[0133] Example 1 (Epoxy treatment process) 1000g of 2,2-bis(3',4'-cyclohexenyl)propane and 3000g of ethyl acetate were placed in a 10-liter jacketed flask. While blowing nitrogen into the gas phase, 3072g of ethyl acetate peracetic acid solution (peracetic acid concentration: 29.2%, water content: 0.31%) was added dropwise over approximately 5 hours to bring the temperature in the reaction system to 35°C. After the addition of peracetic acid was complete, the mixture was aged at 35°C for 3 hours to terminate the reaction.

[0134] (Washing process) The crude reaction solution obtained above was neutralized and washed with water and sodium hydroxide solution at 15°C.

[0135] (First low boiling process, high boiling process) The crude reaction solution, after undergoing the above washing process, was subjected to a first low-boiling step in a WFE type thin-film evaporator at a heating temperature of 150°C and a pressure of 70 Torr, followed by a high-boiling step under the conditions of a heating temperature of 150°C and a pressure of 0.3 Torr, yielding 609.0 g of epoxy compound.

[0136] (Second low boiling point removal process) 609.0 g of the obtained epoxy compound was placed in a 1 L four-necked flask and subjected to precision distillation in an Oldershaw distillation column with 20 stages. The bottom of the column was heated to 220°C, and the distilled components were collected at a reflux ratio of 2, a top pressure of 0.3 kPa, a top temperature of 155-165°C, and a residence time of less than 10 hours at the bottom of the column, to obtain Alicyclic epoxy compound product 1 (295 g) of Example 1.

[0137] Example 2 Alicyclic epoxy compound product 2 of Example 2 was obtained in the same manner as in Example 1, except that the components distilled at a column top temperature of 160-165°C in the second low-boiling step were recovered.

[0138] Example 3 5000 g of 6-methyl-3-cyclohexenylmethyl (6'-methyl-3',4'-cyclohexenyl)carboxylate was placed in a 20 L jacketed SUS316 reactor equipped with a stirrer, and the temperature was raised to 25°C. 13790 g of a 30% ethyl acetate peracetic acid solution was added dropwise over 6 hours, followed by 3 hours of aging. The internal temperature was maintained at 30°C during the addition and aging. In this way, 18790 g of crude reaction solution containing 3,4-epoxy-6-methyl-cyclohexylmethyl (3',4'-epoxy-6'-methyl) was obtained. Then, the crude reaction solution was subjected to a washing step, a first low-boiling step, a high-boiling step, and a second low-boiling step in the same manner as in Example 1 to obtain the alicyclic epoxy compound product 3 of Example 3.

[0139] Example 4 5000g of 3,4-cyclohexenylmethyl(3,4-cyclohexene)carboxylate was placed in a 20L jacketed SUS316 reactor equipped with a stirrer, and the temperature was raised to 25°C. 13790g of a 30% ethyl acetate peracetic acid solution was added dropwise over 6 hours, followed by 3 hours of aging. The internal temperature was maintained at 30°C during the addition and aging. In this way, 18790g of crude reaction solution containing 3,4-epoxycyclohexylmethyl(3,4-epoxy)cyclohexanecarboxylate was obtained. The crude reaction solution was then washed and subjected to a first low-boiling step in the same manner as in Example 1. The bottom liquid obtained after the first low-boiling step was charged into the 5th stage from the bottom of a 40mm diameter high-boiling distillation column consisting of 10 perforated plates, and a second low-boiling step was performed in the same manner as in Example 1 to obtain the alicyclic epoxy compound product 4 of Example 4.

[0140] Comparative Example 1 Comparative Example 1, an alicyclic epoxy compound product 5, was obtained in the same manner as in Example 1, except that the second low-boiling step was omitted.

[0141] <Rating> The following evaluations were performed on the alicyclic epoxy compound products of the examples and comparative examples. The results are shown in the table.

[0142] (1) 1 H-NMR For the alicyclic epoxy compound product 1 of Example 1, the following measurements were taken using the instrument "JNM-ECZ400S" (manufactured by JEOL Ltd.), with deuterated chloroform as the solvent and at a measurement temperature of 20°C. 1 The 1H-NMR spectrum was measured. The alicyclic epoxy compound product 1 obtained in Example 1 1 The 1H-NMR spectrum is shown in Figure 1.

[0143] (2) GPC As a pretreatment, 0.04 g of the alicyclic epoxy compound product was dissolved in 2 g of tetrahydrofuran (THF) and filtered through a 0.50 μm pore size filter (product name "DISMIC13JP050AN", manufactured by Toyo Roshi Co., Ltd.). The resulting THF solution of the alicyclic epoxy compound product was analyzed by GPC, and the percentage of peak area corresponding to the compound represented by the above formulas (a) to (c) was calculated and excluded. The purity [area %] of the alicyclic epoxy compound product was then defined. In cases where the shoulders of adjacent peaks overlapped, the peak area was divided by drawing a perpendicular line from the trough of the peak to the baseline, and the peak area was calculated. The GPC instrument and various conditions used are as follows. Equipment: HLC-8220GPC (manufactured by Tosoh Corporation) Detector: Differential refractometer (RI detector) Pre-column: TSKGUARDCOLUMN SUPER HZ-L 4.6mm x 20mm Column: Sample side TSK-GEL SUPER HZM-N 4.6mm x 150mm x 4 tubes Reference side: TSK-GEL SUPER HZM-N 6.0mm x 150mm x 1 + TSK-GEL SUPER H-RC 6.0mm x 150mm Constant temperature bath temperature: 40℃ Mobile layer: THF Mobile bed flow rate: 0.35ml / min Sample injection volume: 10 μl Data acquisition time: 10 to 26 minutes after sample injection.

[0144] (3) GC-MS For each example of alicyclic epoxy compound product, analysis was performed by gas chromatography under the measurement conditions described below. The components contained in the alicyclic epoxy compound product were then identified based on their molecular weight. The molecular weights of the detected peaks were analyzed using mass spectrometry. The total content percentage of compounds represented by compounds (a) to (c) was measured using gas chromatography under the conditions described below and calculated as area percentage. The chromatogram obtained by GC-MS for alicyclic epoxy compound product 1 obtained in Example 1 is shown in Figure 2, and the peak report is shown in Figure 3. <Measurement conditions> Measurement device: Product name "Agilent7890GC5977B MSD", manufactured by Agilent Technologies, Inc. Column packing material: (5% phenyl)methylsiloxane Column size: Length 15m x Inner diameter 0.53mmφ x Film thickness 1.5μm Column temperature: 100°C → (increase temperature at 10°C / min) → 250°C (15 minutes) Detector: FID

[0145] (4) Hue (APHA) Hue was evaluated by determining the Hazen color number APHA using a simultaneous spectral color and turbidity analyzer (product name "TZ6000", manufactured by Nippon Denshoku Industries Co., Ltd.) and a glass cell (optical path length 33 × cell width 20 × height 55). A value of 105 or less is considered good, and a value of 15 or less is considered excellent.

[0146] Example 5 For each example, 100 parts by mass of the alicyclic epoxy compound product was mixed with 0.6 parts by mass of the product name "San-Aid SI-100L" (manufactured by Sanshin Chemical Industry Co., Ltd.) as a thermal cation catalyst. The mixture was then stirred using a self-rotating stirring device (product name "Awatori Rentaro AR-250", manufactured by Shinky Co., Ltd.), and further degassed to obtain each curable composition.

[0147] Example 6 Each example of the alicyclic epoxy compound product was mixed with "Ricacid MH-700" (manufactured by Shin-Nippon Rika Co., Ltd.) as an acid anhydride curing agent and "PX-4MP" (manufactured by Nippon Chemical Industrial Co., Ltd.) as a curing accelerator, such that the ratio of epoxy equivalent to acid anhydride equivalent of the compound represented by formula (1) in the alicyclic epoxy compound product was 100:90. The mixture was then stirred using a self-rotating stirring device (product name "Awatori Rentaro AR-250", manufactured by Thinky Co., Ltd.), and further degassed to obtain each curable composition.

[0148] Example 7 To 100 parts by mass of each example of alicyclic epoxy compound product, 1 part by mass of the UV cation catalyst "CPI-101A" (manufactured by Sunapro Co., Ltd.) was added, and the mixture was stirred using a self-rotating stirring device (product name "Awatori Rentaro AR-250", manufactured by Thinky Co., Ltd.), and then degassed to obtain each curable composition.

[0149] Examples 8-11 Instead of 100 parts by mass of the alicyclic epoxy compound product of Example 1, 90 parts by mass of the alicyclic epoxy compound product of Example 1 and 10 parts by mass of a bisphenol A type epoxy compound (trade name "JER828", manufactured by Mitsubishi Chemical Corporation) were used to prepare the curable composition of Example 8. The hue (APHA) was measured using the method described above. Furthermore, the curable compositions of Examples 9 to 11 were obtained in the same manner as in Examples 5 to 7, except that the curable composition of Example 8 was used.

[0150] Examples 12-15 In Example 12, the curable composition was prepared by replacing 10 parts by mass of 3-ethyl-3{[(3-ethyloxetan-3-yl)methoxy]methyl}oxetane with 10 parts by mass of 3-ethyl-3{[(3-ethyloxetan-3-yl)methoxy]methyl}oxetane as the oxetane compound, instead of 10 parts by mass of the bisphenol A type epoxy compound (trade name "JER828", manufactured by Mitsubishi Chemical Corporation) in Example 8. The color (APHA) was also measured using the method described above. Furthermore, the curable compositions of Examples 13 to 15 were obtained in the same manner as in Examples 5 to 7, except that the curable composition of Example 12 was used.

[0151] (5) Curability The curability of the curable compositions obtained in Examples 5 to 7, 9 to 11, and 13 to 15 was measured using a gel time measuring device (trade name "Rheometer MCR302", manufactured by Anton Paar Japan Co., Ltd.). Specifically, for the curable compositions of Examples 5, 9, and 13 (thermal cationic catalysts), after heating to 80°C, for the curable compositions of Examples 6, 10, and 14 (anhydride curing agents), after heating to 120°C, and for the curable compositions of Examples 7, 11, and 15 (UV cationic catalysts), after ultraviolet irradiation, the curing profile was measured by the rheometer method (dynamic viscoelasticity evaluation), the temperature curve of the loss elastic modulus at a constant frequency was measured, and the point where two elastic modulus curves measuring G' (storage elastic modulus) and G'' (loss elastic modulus) intersect was defined and determined as the gelation point. Then, when the set temperature (80°C or 120°C) was reached, or at the start of ultraviolet irradiation (irradiance 3000 mJ / cm 2 ), the start time was taken as the starting point, and the time until the gelation point was reached was evaluated as the reactive gel time. In Examples 5, 9, and 13, it is judged to be good if it is 600 seconds or less, and excellent if it is 500 seconds or less. In Examples 6, 10, and 14, it is judged to be good if it is 900 seconds or less, and excellent if it is 800 seconds or less. In Examples 7, 11, and 15, it is judged to be good if it is 300 seconds or less, and excellent if it is 150 seconds or less.

[0152] Example 16 Each of the curable compositions obtained in Examples 5, 6, 9, 10, 13, and 14 was filled into a mold and heated in a resin curing oven at 120°C for 5 hours to obtain each cured product of Examples 16 to 21. For the epoxy compound product obtained in Example 4, it was further heated at 150°C for 30 minutes for post-curing to prepare a cured product.

[0153] (6) Curing shrinkage For the cured product obtained in Example 16, the density before and after curing was measured by the density measurement method (JIS K5600 2-4), and based on the following formula, the curing shrinkage rate (volume shrinkage rate) was determined from the density change. It is judged to be good if it is 1.5% or less. Volume shrinkage rate r = {(ds - dl) / dl} × 100 dl: Specific gravity of the liquid before curing. Measured using a density hydrometer "DA-640" (manufactured by Kyoto Electronics Industry Co., Ltd.). ds: Specific gravity of the solid after curing. Measured using the solid specific gravity measurement method.

[0154] (7)Light transmittance For each cured product (3 mm thick) obtained in Example 16, the light transmittance (in the thickness direction) of light with a wavelength of 400 nm was measured using a spectrophotometer (product name "UV-2450", 10 mm square quartz cell, 10 mm thick, manufactured by Shimadzu Corporation). For the cured products of the curable compositions in Examples 5, 9, and 13, a transmittance of 70% or more is considered good, and 75% or more is considered excellent. For the cured products of the curable compositions in Examples 6, 10, and 14, a transmittance of 85% or more is considered good, and 90% or more is considered excellent.

[0155] (8) Glass transition temperature (Tg) For each cured product obtained in Example 16, the glass transition temperature was determined under the following conditions. For the cured products of the curable compositions in Examples 5, 9, and 13, a temperature of 200°C or higher is considered good, and a temperature of 300°C or higher is considered excellent. For the cured products of the curable compositions in Examples 6, 10, and 14, a temperature of 230°C or higher is considered good, and a temperature of 250°C or higher is considered excellent. Sample: Length 4mm x Width 5mm x Thickness 0.5mm Measurement device: Viscoelasticity measuring device (DMA), product name "DMS6100", manufactured by Hitachi High-Tech Science Co., Ltd. Measurement mode: Tensile Measurement temperature: 25°C to 320°C Heating rate: 5°C / min

[0156] (9) Curl Each curable composition obtained in Examples 7, 11, and 15 was uniformly applied to a PET film (100 μm thick) to a thickness of 40 μm, and cured using a high-pressure mercury lamp for UV curing with an integrated light intensity of 1200 mJ / cm². 2 Each cured product was obtained by irradiating with ultraviolet light under the specified conditions. With the cured product facing upwards, if the outer edge was lifted, the height of the square was measured and the average value was calculated. A curl height of more than 5 mm was judged as poor (×), 5 mm or less as good (〇), and 1 mm or less as excellent (◎).

[0157] (10) Outgassing Each curable composition obtained in Examples 7, 11, and 15 was poured into a mold to a size of 76 mm in length, 26 mm in width, and 0.5 mm in thickness, and exposed using a UV irradiation device (product name "LED-UV irradiator PSCC-60048", manufactured by CCS Corporation) at a wavelength of 365 nm and an exposure dose of 2500 mJ / cm². 2 Each cured product was obtained by UV irradiation using an LED lamp under the specified irradiation conditions. The above cured products were heated at 110°C for 30 minutes, and the mass loss rate relative to the initial mass was determined under the following conditions and defined as the outgassing amount. An outgassing amount of 0.1% or less is considered good, and 0.08% or less is considered excellent. Evaluation sample: 5-10 μg Measuring device: Product name "STA / 7200", manufactured by Hitachi High-Tech Science Co., Ltd.

[0158] (11) Bending strength, bending modulus, bending elongation Of the cured products obtained in Example 16, the cured products of each curable composition obtained in Examples 9, 10, 13, and 14 were molded into a shape of 4 mm thickness × 10 mm width × 80 mm length. Using a Tensilon universal testing machine (manufactured by Orientec Co., Ltd.), a three-point bending test was performed under the conditions of edge span: 67 mm and bending speed: 2 mm / min to measure the bending strength (MPa), bending modulus (MPa), and bending elongation (%GL) of the cured products.

[0159] [Table 1]

[0160] As shown in Table 1, the alicyclic epoxy compound products of the examples exhibited less outgassing compared to products where the total proportion of compounds represented by formulas (a) to (c) exceeded 1% by mass. Furthermore, they were evaluated as having good hue, excellent transparency, a short reactive gel time, and rapid curing properties. The cured products were also evaluated as having high light transmittance, excellent transparency, a high Tg, and excellent heat resistance. In addition, the alicyclic epoxy compound products of the examples were evaluated as having less curing shrinkage compared to other alicyclic epoxy compound products.

[0161] [Table 2]

[0162] The following describes variations of the invention relating to this disclosure. [Note 1] The purity of the compound represented by the following formula (1) is 80% or higher. An epoxy compound product in which the total proportion of the compound represented by formula (a) below, the compound represented by formula (b) below, and the compound represented by formula (c) below is 1% by mass or less. [ka] [In the formula, X represents a single bond or a linking group. The cyclohexane ring and benzene ring in the formula may have substituents on one or more of the carbon atoms constituting the ring.] [Note 2] The epoxy compound product described in Note 1, wherein the compound represented by formula (1) is an epoxidized compound of the compound represented by formula (2) below, obtained by an aliphatic percarboxylic acid. [ka] [In formula (2), X represents a single bond or a linking group, and is the same as in formula (1). The cyclohexene ring in formula (2) may have substituents on one or more of the carbon atoms constituting the ring.] [Note 3] The epoxy compound product described in Note 2, wherein the aliphatic percarboxylic acid is peracetic acid. [Note 4] A curable composition comprising an epoxy compound product described in any one of Notes 1 to 3, and a curing agent and / or curing catalyst. [Note 5] A curable composition comprising an epoxy compound product described in any one of Notes 1 to 3, and other epoxy compounds and / or oxetane compounds. [Note 6] A curable composition according to Note 4 or 5, which is an adhesive, sealant, coating agent, or hard coat agent. [Note 7] A cured product of any one of the curable compositions described in Notes 4 to 6. [Note 8] An optical component comprising the cured material described in Note 7. [Note 9] A method for producing the epoxy compound product according to any one of Notes 1 to 3, comprising the following epoxidation step, the following first de-low boiling step, the following high boiling step, and the following second de-low boiling step. Epoxylation process: A process of reacting a compound represented by the following formula (2) with an organic peracid to obtain a reaction product. [ka] [In formula (2), X represents a single bond or a linking group. The cyclohexene ring in formula (2) may have substituents on one or more of the carbon atoms constituting the ring.] First low-boiling point removal step: A step to remove low-boiling point components by distillation using a thin-film distiller. De-boiling process: A process of removing high-boiling point components by distillation. Second low-boiling step: A step in which the compounds represented by formulas (a) to (c) above are removed by distillation using a distillation column.

Claims

1. The purity of the compound represented by the following formula (1) is 80% or higher, An epoxy compound product in which the total proportion of the compound represented by formula (a) below, the compound represented by formula (b) below, and the compound represented by formula (c) below is 0.005 to 1% by mass. 【Chemistry 1】 [In the formula, X represents a single bond or a linking group. The cyclohexane ring and benzene ring in the formula may have substituents on one or more of the carbon atoms constituting the ring.]

2. The epoxy compound product according to claim 1, wherein the compound represented by formula (1) is an epoxidized compound of the compound represented by formula (2) below, wherein the compound is an epoxidized compound of an aliphatic percarboxylic acid. 【Chemistry 2】 [In formula (2), X represents a single bond or a linking group, and is the same as in formula (1). The cyclohexene ring in formula (2) may have substituents on one or more of the carbon atoms constituting the ring.]

3. The epoxy compound product according to claim 2, wherein the aliphatic percarboxylic acid is peracetic acid.

4. A curable composition comprising the epoxy compound product described in claim 1 and a curing agent and / or curing catalyst.

5. A curable composition comprising the epoxy compound product described in claim 1 and other epoxy compounds and / or oxetane compounds.

6. The curable composition according to claim 4 or 5, which is an adhesive, sealant, coating agent, or hard coat agent.

7. A cured product of the curable composition according to claim 4 or 5.

8. An optical member comprising the cured product described in claim 7.

9. A method for producing an epoxy compound product according to any one of claims 1 to 3, comprising producing the epoxy compound product through the following epoxidation step, the following first de-low boiling step, the following high boiling step, and the following second de-low boiling step. Epoxylation process: A process of reacting a compound represented by the following formula (2) with an organic peracid to obtain a reaction product. 【Chemistry 2】 [In formula (2), X represents a single bond or a linking group. The cyclohexene ring in formula (2) may have substituents on one or more of the carbon atoms constituting the ring.] First low-boiling step: A process to remove low-boiling components by distillation using a thin-film distiller. De-boiling point process: A process of removing high-boiling point components by distillation. Second low-boiling step: A step in which the compounds represented by formulas (a) to (c) above are removed by distillation using a distillation column.

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