Epoxy compound product

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

Epoxy compound products

[0001] This disclosure relates to high-purity epoxy compound products. This application claims priority from Japanese Patent Application No. 2023-192638, filed November 10, 2023, the contents of which are incorporated herein by reference.

[0002] By reacting epoxy compounds with various curing agents and curing catalysts, it is possible to form cured products having high strength and excellent heat resistance, transparency, etc. For example, alicyclic epoxy compounds having two or more epoxy groups are used as raw materials for sealing materials, coating agents, adhesives, inks, sealants, etc.

[0003] Known examples of the 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).

[0004] International Publication No. 2019 / 138988 U.S. Patent No. 2,890,194

[0005] However, conventional alicyclic epoxy compound products contain low-boiling compounds as impurities, and there is a problem that, for example, in products including a cured product obtained by curing the alicyclic epoxy compound, the low-boiling compounds volatilize and outgas under high-temperature conditions. If outgassing occurs, for example, when the cured product is used as an encapsulant for a semiconductor element such as an organic EL element, cracks may occur in the inorganic material film in the semiconductor element, resulting in insufficient encapsulation.

[0006] Therefore, an object of the present disclosure is to provide an epoxy compound product that can form a cured product that is less likely to outgas in a high-temperature environment.

[0007] That is, the present disclosure provides an epoxy compound product in which the purity of the compound represented by the following formula (1) is 80% or more, and the total content of the compound represented by the following formula (a), the compound represented by the following formula (b), and the compound represented by the following 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 a substituent on one or more of the carbon atoms constituting the ring.]

[0008] The compound represented by the formula (1) above is preferably an epoxidized product of a compound represented by the following formula (2) with an aliphatic percarboxylic acid. [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 a substituent on one or more of the carbon atoms constituting the ring.]

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

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

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

[0012] The 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 curable composition.

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

[0015] The present disclosure also provides a method for producing the epoxy compound product, which comprises the following epoxidation step, the following first step for removing low-boiling points, the following step for removing high-boiling points, and the following second step for removing low-boiling points: Epoxidation step: a step of reacting a compound represented by the following formula (2) with an organic peracid to obtain a reaction product: [In formula (2), X represents a single bond or a linking group. The cyclohexene ring in formula (2) may have a substituent on one or more of the carbon atoms constituting the ring.] First low-boiling point removal step: A step of removing low-boiling point components by distillation using a thin-film still. High-boiling point removal step: A step of removing high-boiling point components by distillation. Second low-boiling point removal step: A step of removing the compounds represented by formulas (a) to (c) by distillation using a distillation column.

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

[0017] Alicyclic epoxy compound product 1 prepared in Example 1 １ 1H-NMR spectrum. ...

[0018] [Epoxy Compound Product] The epoxy compound product of the present disclosure contains a compound represented by the following formula (1), and has a purity (or content) of 80% or more.

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

[0020] Examples of the linking group include a divalent hydrocarbon group, an alkenylene group in which part or all of the carbon-carbon double bonds are epoxidized, a carbonyl group, an ether bond, a thiol bond, an ester bond, a carbonate group, an amide group, -SO-, -SO ２ --, --CBr ２ -, -C(CBr ３ ) ２ -, -C(CF ３ ) ２ Examples of the linking group include an ether bond, a thiol bond, —SO—, and —SO ２ -, -CH ２ -, -C(CH ３ ) ２--, --CBr ２ -, -C(CBr ３ ) ２ -, and -C(CF ３ ) ２ - is preferably a group selected from the group consisting of

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

[0022] Examples of the alkenylene group in the alkenylene group in which some or all of the carbon-carbon double bonds have been epoxidized (sometimes referred to as an "epoxidized alkenylene group") 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. In particular, the epoxidized alkenylene group is preferably an alkenylene group in which all of the carbon-carbon double bonds have been epoxidized, and more preferably an alkenylene group having 2 to 4 carbon atoms in which all of the carbon-carbon double bonds have been epoxidized.

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

[0024] Representative examples of the alicyclic epoxy compound represented by formula (1) above include (3,4,3',4'-diepoxy)bicyclohexyl and compounds represented by formulas (i-1) to (i-10) below. In formulas (i-5) and (i-7) below, l and m each represent an integer of 1 to 30. R' in formula (i-5) below is an alkylene group having 1 to 8 carbon atoms, and among these, a linear or branched alkylene group having 1 to 3 carbon atoms, such as a methylene group, an ethylene group, a propylene group, or an isopropylene group, is preferred. In formulas (i-9) and (i-10) below, n1 to n6 each represent an integer of 1 to 30. Further, other examples of the alicyclic epoxy compound represented by the above formula (i) include 2,2-bis(3,4-epoxycyclohexyl)propane, 1,2-bis(3,4-epoxycyclohexan-1-yl)ethane, 1,2-epoxy-1,2-bis(3,4-epoxycyclohexan-1-yl)ethane, and bis(3,4-epoxycyclohexylmethyl)ether.

[0025] The compound represented by formula (1) above also includes epoxy-modified siloxanes. Examples of the epoxy-modified siloxanes include linear or cyclic polyorganosiloxanes having a structural unit represented by formula (i') below:

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

[0027] In formula (1a) and formula (1b), R １ａ , R １ｂ are the same or different and represent a linear or branched alkylene group, and examples thereof include linear or branched alkylene groups having 1 to 10 carbon atoms such as a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, and a decamethylene group.

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

[0029] As the epoxy-modified siloxane, for example, a commercially available product 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.

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

[0031] The purity of the compound represented by formula (1) in the epoxy compound product can be calculated as the peak area ratio by gel permeation chromatography (GPC). Alternatively, the purity of the compound represented by formula (1) in the epoxy compound product may be calculated by excluding the peak area ratios corresponding to the compounds represented by formulas (a) to (c). When peak shoulders overlap, the peak areas are separated by a perpendicular line to the baseline that passes through the valleys of the peaks.

[0032] Furthermore, the epoxy compound product contains a compound represented by the following formula (a), a compound represented by the following formula (b), and a compound represented by the following formula (c) in a total content of 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, relative to the total amount (100% by mass) of the epoxy compound product. The total content may be, for example, 0.005% by mass or more, 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 no compounds at all.

[0033] In formulas (a) to (c), X represents a single bond or a linking group, corresponds to X in formula (1), and is the same as X in formula (1). The cyclohexane ring and the benzene ring in formulas (a) to (c) may have a substituent on one or more of the carbon atoms constituting the ring. Examples of the substituent include those exemplified and explained as the substituent that the cyclohexane ring in formula (1) may have. When a plurality of substituents are present, the plurality of substituents may be the same or different.

[0034] Because the compounds represented by formulas (a) to (c) do not contain epoxy groups, they do not cure when a composition containing an epoxy compound product is cured. As a result, the compounds represented by formulas (a) to (c) remain in the cured product. When the cured product is exposed to a high-temperature environment, the compounds represented by formulas (a) to (c) volatilize and outgas. By ensuring that the total content of the compounds represented by formulas (a) to (c) is 1% by mass or less, these compounds are less likely to remain in the cured product, reducing the amount of outgassing. Furthermore, the epoxy cured product exhibits the following effects: small cure shrinkage, reduced curl during curing, excellent adhesion to substrates, improved curability with active energy rays, allowing for a shorter curing process, and excellent heat resistance and transparency of the cured product.

[0035] The total content ratios 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 ratio of peak areas measured by gas chromatography and mass spectrometry (GC-MS). For example, when the relative retention time of the peak of the compound represented by formula (1) is set to 1.0, the compounds represented by formulas (a) to (c) are detected in a range of relative retention times of 0.7 to 0.72 (for example, a range earlier than RT 17.8 min in the chromatogram shown in FIG. 2).

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

[0037] (Method for Producing Epoxy Compound Product) The epoxy compound product is obtained by epoxidizing a compound represented by the following formula (2) with an organic peracid.

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

[0039] More specifically, the epoxy compound product can be produced through the following epoxidation step, the following first low-boiling point removal step, the following high-boiling point removal step, and the following second low-boiling point removal step. The order of the above steps is not particularly limited; for example, either the first low-boiling point removal step or the second low-boiling point removal step may be performed first, but it is preferable to perform the steps in the order of the first low-boiling point removal step, the high-boiling point removal step, and the second low-boiling point removal step. Epoxidation step: a step of reacting a compound represented by the above formula (2) with an organic peracid to obtain a reaction product. First low-boiling point removal step: a step of removing low-boiling point components by distillation. High-boiling point removal step: a step of removing high-boiling point components by distillation. Second low-boiling point removal step: a step of removing compounds represented by formulas (a) to (c) by distillation.

[0040] Furthermore, after the completion of the epoxidation step, and before the first low-boiling point removal step, the second low-boiling point removal step, and the high-boiling point removal step, a step (washing step) may be provided in which the obtained reaction product is washed with water to remove the organic peracid used in the reaction and its decomposition products.

[0041] (1) Epoxidation Step The epoxidation step is a step of reacting the compound represented by formula (2) with an organic peracid to obtain a reaction product. In this step, a reaction product containing the compound represented by formula (1) is obtained.

[0042] Examples of the organic peracid include performic acid, peracetic acid, perpropionic acid, m-chloroperbenzoic acid, trifluoroperacetic acid, and perbenzoic acid. The organic peracid may be used singly or in combination. The organic peracid is preferably an aliphatic percarboxylic acid, and more preferably peracetic acid.

[0043] The aliphatic percarboxylic acid is preferably an oxygen oxide of the corresponding aldehyde. Such an aliphatic percarboxylic acid is substantially free of water and can make it difficult for the ring opening of the epoxy group to occur.

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

[0045] The epoxidation reaction can be carried out in the presence of a solvent. Examples of the solvent 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 and derivatives thereof such as ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether, and diethylene glycol monoethyl ether; halogen compounds such as chloroform, dimethyl chloride, carbon tetrachloride, and chlorobenzene; and ethers such as 1,2-dimethoxyethane. The above solvents may be used alone or in combination of two or more.

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

[0047] In the epoxidation reaction, a stabilizer for the organic peracid (e.g., ammonium hydrogen phosphate, potassium pyrophosphate, 2-ethylhexyl tripolyphosphate, etc.), a polymerization inhibitor (e.g., hydroquinone, piperidine, ethanolamine, phenothiazine, etc.), etc. may be used, if necessary.

[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, for example, an air atmosphere, a nitrogen atmosphere, an argon atmosphere, or the like.

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

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

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

[0052] In the first low-boiling point removal step, it is preferable to use a thin-film evaporator for distillation. The 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. The distillation can also be carried out in two stages by changing the pressure and temperature.

[0053] When the reaction product is subjected to the first low-boiling point removal step, it is preferable to add a polymerization inhibitor in order to suppress the ring-opening polymerization reaction of the compound represented by formula (1). The amount of polymerization inhibitor added varies slightly depending on the type and distillation temperature, but 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 point removal step, components having a boiling point lower than that of the compounds represented by the above formulas (a) to (c) are evaporated and removed from the reaction product, whereby a mixture of the compounds represented by the above formulas (a) to (c), the compound represented by the above formula (1), and components having a boiling point higher than those compounds is obtained as the bottoms.

[0055] (4) High-boiling point removal step The high-boiling point removal step is a step of distilling off components contained in the reaction product that have a boiling point higher than that of the compounds represented by the formulas (a) to (c) and the compound represented by the formula (1). When the high-boiling point removal step is carried out after the first low-boiling point removal step, the high-boiling point removal step is a step of evaporating and distilling off the compound represented by the formula (1) and the compounds represented by the formulas (a) to (c) from a mixture of the compounds represented by the formulas (a) to (c), the compound represented by the formula (1), and components with a boiling point higher than those compounds, which is the bottoms obtained through the first low-boiling point removal step. By carrying out this step, the content of high-molecular-weight compounds mixed into the epoxy compound product can be extremely reduced.

[0056] In the high-boiling point removal step, either a distillation column or a thin-film evaporator can be used for distillation, but it is desirable to use a thin-film evaporator in order to reduce the residence time during distillation. The distillation is preferably carried out at a heating temperature of 250°C or less (preferably 230°C or less) from the viewpoint of preventing the compound represented by formula (1) from decomposing and increasing the degree of coloration, or from preventing the epoxy group in the compound represented by formula (1) from ring-opening polymerization and gelation. The distillation temperature is preferably 50°C or higher, more preferably 100°C or higher. From the same viewpoint, the distillation is preferably carried out at a pressure of 3 torr or less (preferably 0.7 torr or less). The pressure is preferably 0.01 torr or higher, and may be 0.02 torr or higher, from the viewpoint of further increasing the purity of the epoxy compound product.

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

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

[0059] The distillation column may be, for example, a packed column, a plate column, etc. The actual number of plates in the distillation column is preferably 14 or more, and is preferably 14 to 100 plates, particularly preferably 14 to 50 plates, in order to further improve the purity of the product.

[0060] In the second low-boiling point removal step, the distillation is preferably carried out at a temperature of 250°C or less (e.g., 50 to 250°C) and a residence time at the bottom of the distillation vessel of less than 10 hours (e.g., 1 hour or more but less than 10 hours). The distillation can also be carried out in two stages by changing the pressure and temperature. By setting the heating temperature to 260°C or less, 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 less, coloration of the obtained epoxy compound can be suppressed.

[0061] By treating the reaction product, particularly by carrying out the first low-boiling point removal step, the high-boiling point removal step, and the second low-boiling point removal step in this order, it is possible to obtain the epoxy compound product containing the compound represented by formula (1) at a high purity and with extremely reduced amounts of the compounds represented by formulas (a) to (c).

[0062] Epoxy compound products obtained by distillation purification using a typical thin-film still (WFE) tend to contain a high content of the compounds represented by the above formulas (a) to (c). Furthermore, if the reaction product is distilled in a distillation column without performing the low-boiling point removal step and the high-boiling point removal step using a WFE, or if the reaction product from which the solvent has been removed by the low-boiling point removal step is distilled, the residence time at the bottom of the distillation column is long, resulting in significant discoloration and gelation due to ring-opening polymerization. Furthermore, purification using a WFE has not been able to separate the compounds represented by the above formulas (a) to (c) from the compound represented by the above formula (1). On the other hand, if the low-boiling point removal step and the high-boiling point removal step are performed simultaneously using a distillation column, the residence time at the bottom of the distillation column is long, resulting in significant discoloration and gelation due to ring-opening polymerization. In contrast, the compounds represented by the above formulas (a) to (c) can be efficiently removed by performing precision distillation under conditions of a distillation column with 14 or more actual plates, a heating temperature of 250°C or less, and a residence time at the bottom of the distillation column of less than 10 hours, particularly after performing the low-boiling point removal step and the high-boiling point removal step using a WFE.

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

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

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

[0066] The other epoxy compounds are compounds having one or more epoxy groups (oxiranyl groups) in the molecule. Among them, the other epoxy compounds are preferably compounds having two or more (preferably 2 to 6, more preferably 2 to 4) epoxy groups in the molecule.

[0067] The other epoxy compounds include alicyclic epoxy compounds, aromatic epoxy compounds, and aliphatic epoxy compounds.

[0068] The alicyclic epoxy compound includes known or commonly used compounds having one or more alicyclic rings and one or more epoxy groups in the molecule, and is not particularly limited. Examples include (I) a compound in which an epoxy group is directly bonded to an alicyclic ring via a single bond; and (II) a compound having an alicyclic ring and a glycidyl ether group in the molecule (glycidyl ether type epoxy compound).

[0069] The above-mentioned (I) compound in which an epoxy group is directly bonded to an alicyclic ring via a single bond includes, for example, a compound represented by the following formula (ii).

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

[0071] Examples of the compound (II) having an alicyclic ring and a glycidyl ether group in the molecule include glycidyl ethers of alicyclic alcohols (particularly 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 of such epoxy compounds include hydrogenated compounds of bisphenol F epoxy compounds such as [2,3-epoxypropoxy]cyclohexyl]methane (hydrogenated bisphenol F epoxy compounds); hydrogenated bisphenol epoxy compounds; hydrogenated phenol novolac epoxy compounds; hydrogenated cresol novolac epoxy compounds; hydrogenated cresol novolac epoxy compounds of bisphenol A; hydrogenated naphthalene epoxy compounds; hydrogenated epoxy compounds of epoxy compounds obtained from trisphenolmethane; and hydrogenated epoxy compounds of other epoxy compounds having an aromatic ring.

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

[0073] Examples of the aromatic epoxy compounds include epibis-type glycidyl ether epoxy resins obtained by a condensation reaction between bisphenols [e.g., bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, etc.] and epihalohydrin; high molecular weight epibis-type glycidyl ether epoxy resins obtained by further addition reaction of these epibis-type glycidyl ether epoxy resins with the above-mentioned bisphenols; phenols [e.g., phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol B, etc.]; novolak alkyl type glycidyl ether epoxy resins obtained by condensing polyhydric alcohols obtained by condensing polyhydric alcohols [e.g., phenol (e.g., phenol F, bisphenol S)] with aldehydes [e.g., formaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, salicylaldehyde] with epihalohydrin; and epoxy compounds in which two phenol skeletons are bonded to the 9-position of a fluorene ring and a glycidyl group is bonded, directly or via an alkyleneoxy group, to the oxygen atom obtained by removing the hydrogen atom from the hydroxy group of each of the phenol skeletons.

[0074] Examples of the aliphatic epoxy compound include glycidyl ethers of q-valent alcohols (q is a natural number) that do not have a cyclic structure; glycidyl esters of monovalent or polyvalent carboxylic acids [for example, acetic acid, propionic acid, butyric acid, stearic acid, adipic acid, sebacic acid, maleic acid, itaconic acid, etc.]; epoxidized products of fats and oils having double bonds, such as epoxidized linseed oil, epoxidized soybean oil, and epoxidized castor oil; and epoxidized products of polyolefins (including polyalkadiene), such as epoxidized polybutadiene. Examples of the q-valent alcohol not having a 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 trihydric or higher polyhydric alcohols such as glycerin, diglycerin, erythritol, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, and sorbitol. The q-valent alcohol may be a polyether polyol, a polyester polyol, a polycarbonate polyol, or a polyolefin polyol.

[0075] The oxetane compound includes known or commonly used compounds having one or more oxetane rings in the molecule, and is not particularly limited to, for example, 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 -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, xylylene bisoxetane, 3-ethyl-3-{[3-(triethoxysilyl)propoxy]methyl}oxetane, oxetanyl silsesquioxane, and phenol novolac oxetane.

[0076] The vinyl ether compound may be any known or commonly used compound having one or more vinyl ether groups in the molecule, and is not particularly limited. Examples of the vinyl ether compound include 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,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 monovinyl ether monovinyl 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, hydroxyoxanorbornanemethanol divinyl ether, 1,Examples include 4-cyclohexanediol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, and dipentaerythritol hexavinyl ether.

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

[0078] The curable composition preferably contains, in addition to the curable compound, one or more selected from the group consisting of a curing agent, a curing accelerator, and a curing catalyst. The 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 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 the curing catalyst in the total amount (100% by mass) of the 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 of compounds other than the curable compound, curing agent, curing accelerator, and curing catalyst relative to the total amount (100 mass%) of the curable composition is, for example, 50 mass% or less, and preferably 40 mass% or less.

[0082] (Curing Agent) Examples of the curing agent that can be used include known or commonly used curing agents for epoxy resins, such as acid anhydrides (acid anhydride curing agents), amines (amine curing agents), polyamide resins, imidazoles (imidazole curing agents), polymercaptans (polymercaptan curing agents), phenols (phenol curing agents), polycarboxylic acids, dicyandiamides, and organic acid hydrazides. Only one type of the curing agent may be used, or two or more types may be used.

[0083] Examples of the acid anhydrides include methyltetrahydrophthalic anhydride (4-methyltetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, etc.), methylhexahydrophthalic anhydride (4-methylhexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, etc.), dodecenyl succinic anhydride, methyl endomethylenetetrahydrophthalic anhydride, phthalic anhydride, maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylcyclohexene dicarboxylic acid, Examples of suitable acid anhydrides include carboxylic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenone tetracarboxylic anhydride, nadic anhydride, methyl nadic anhydride, hydrogenated methyl nadic anhydride, 4-(4-methyl-3-pentenyl)tetrahydrophthalic anhydride, succinic anhydride, adipic anhydride, sebacic anhydride, dodecanedioic anhydride, methylcyclohexene tetracarboxylic anhydride, vinyl ether maleic anhydride copolymer, alkylstyrene-maleic anhydride copolymer, etc. Among these, from the viewpoint of handleability, acid anhydrides that are liquid at 25°C [e.g., methyl tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, dodecenyl succinic anhydride, methyl-endomethylene tetrahydrophthalic anhydride, etc.] are preferred.

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

[0085] Examples of the polyamide resin include polyamide resins having either or both of a primary amino group and a secondary amino group in the molecule.

[0086] Examples of the 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-methylimidazole. 1-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2-methylimidazolium isocyanurate, 2-phenylimidazolium isocyanurate, 2,4-diamino-6-[2-methylimidazolyl-(1)]-ethyl-s-triazine, 2,4-diamino-6-[2-ethyl-4-methylimidazolyl-(1)]-ethyl-s-triazine, and the like.

[0087] Examples of the polymercaptans include liquid polymercaptan and polysulfide resin.

[0088] Examples of the phenols include aralkyl resins such as novolac-type phenolic resins, novolac-type cresol resins, 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 include adipic acid, sebacic acid, terephthalic acid, trimellitic acid, and carboxy group-containing polyesters.

[0090] As the curing agent, acid anhydrides (acid anhydride-based curing agents) are preferred from the viewpoint of the heat resistance and transparency of the resulting cured product, and for example, commercially available products such as those under the trade names "RIKACID MH-700" and "RIKACID MH-700F" (both manufactured by New Japan Chemical Co., Ltd.) and those under the trade name "HN-5500" (manufactured by Hitachi Chemical Co., Ltd.) can be used.

[0091] The content (amount) of the curing agent is preferably 50 to 200 parts by mass, 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 an acid anhydride is used as the curing agent, it is preferably used in a proportion of 0.5 to 1.5 equivalents per equivalent of epoxy groups in all epoxy compounds contained in the curable composition. When the content of the curing agent is 50 parts by mass or more, curing can proceed sufficiently, and the toughness of the resulting cured product tends to be improved. On the other hand, when the content of the curing agent is 200 parts by mass or less, coloration is further suppressed, and a cured product with excellent hue tends to be obtained.

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

[0093] Examples of the curing accelerator include 1,8-diazabicyclo[5.4.0]undecene-7 (DBU) or a salt thereof (e.g., phenol salt, octylate salt, p-toluenesulfonate, formate salt, tetraphenylborate salt, etc.), 1,5-diazabicyclo[4.3.0]nonene-5 (DBN) or a salt thereof (e.g., phenol salt, octylate salt, p-toluenesulfonate, formate salt, tetraphenylborate salt, etc.); benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, Examples of the curing accelerator 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; organic metal salts such as zinc octoate, tin octoate and zinc stearate; and metal chelates such as aluminum acetylacetone complex. One or more of the above curing accelerators may be used.

[0094] Examples of the curing accelerator include commercially available products such as those under the trade names "U-CATSA 506," "U-CAT SA102," "U-CAT 5003," "U-CAT 18X," and "U-CAT 12XD" (developed products) (all manufactured by San-Apro Co., Ltd.); those under the trade names "TPP-K" and "TPP-MK" (all manufactured by Hokko Chemical Industry Co., Ltd.); and those under the trade name "PX-4ET" (manufactured by Nippon Chemical Industry Co., Ltd.).

[0095] The content (blending amount) 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 part 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, coloration is further suppressed, and a cured product with excellent hue tends to be obtained.

[0096] (Curing Catalyst) The curable composition may contain a curing catalyst instead of a curing agent. The curing catalyst has the function of initiating and / or accelerating the curing reaction (polymerization reaction) of a cationic curable compound such as the compound represented by formula (1), thereby curing the curable composition. Examples of curing catalysts include cationic polymerization initiators (photocationic polymerization initiators, thermal cationic polymerization initiators, etc.) that generate cationic species and initiate polymerization by applying light irradiation, heat treatment, etc., Lewis acid-amine complexes, Bronsted acid salts, imidazoles, etc. The curing catalysts may be used alone or in combination of two or more.

[0097] Examples of the photocationic polymerization initiator include sulfonium salts (particularly triarylsulfonium salts) such as triarylsulfonium hexafluorophosphate (for example, p-phenylthiophenyldiphenylsulfonium hexafluorophosphate) and triarylsulfonium hexafluoroantimonate; 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] Specific examples of the photocationic polymerization initiator 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 thereof include tris(pentafluoroethyl)trifluorophosphate, bis[4-(diphenylsulfonio)phenyl]sulfiphenyltris(pentafluorophenyl)borate, [4-(2-thioxanthonylthio)phenyl]phenyl-2-thioxanthonylsulfonium phenyltris(pentafluorophenyl)borate, and 4-(phenylthio)phenyldiphenylsulfonium hexafluoroantimonate.

[0099] The photocationic polymerization initiator may be a commercially available product. Examples of the commercially available product include trade names "Cyracure UVI-6970," "Cyracure UVI-6974," "Cyracure UVI-6990," and "Cyracure UVI-950" (all manufactured by Union Carbide Corporation, USA), "Omnirad250," "Omnirad261," "Omnirad264," and "CG-24-61" (all manufactured by IGM Resins), "Optomer SP-150," "Optomer SP-151," "Optomer SP-170," and "Optomer SP-171" (all manufactured by ADEKA Corporation), and "DAICAT II" (manufactured by Daicel Corporation), "UVAC1590", "UVAC1591" (all manufactured by Daicel-Allnex 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 tolylcumyl iodonium 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 Industry Co., Ltd.), "CD-1010", "CD-1011", "CD-1012" (all manufactured by Sartomer Corporation, USA), "CPI-100P", "CPI-101A" (all manufactured by San-Apro Ltd.), and the like.

[0100] Examples of the thermal cationic polymerization initiator include aryl diazonium salts, aryliodonium salts, arylsulfonium salts, and allene-ion complexes. Commercially available products that can be preferably used include those under the trade names "PP-33," "CP-66," and "CP-77" (all manufactured by ADEKA Corporation); those under the trade name "FC-509" (manufactured by 3M); those under the trade name "UVE1014" (manufactured by G.E. Corporation); those under the trade names "SAN-AID SI-60L," "SAN-AID SI-80L," "SAN-AID SI-100L," "SAN-AID SI-110L," and "SAN-AID SI-150L" (all manufactured by Sanshin Chemical Industry Co., Ltd.); and those under the trade name "CG-24-61" (manufactured by BASF).

[0101] Examples of the Lewis acid-amine complex include BF ３ n-Hexylamine, BF ３ Monoethylamine, BF ３ Benzylamine, BF ３ Diethylamine, BF ３ Piperidine, BF ３ Triethylamine, BF ３ Aniline, BF ４ n-Hexylamine, BF ４ Monoethylamine, BF ４ Benzylamine, BF ４ Diethylamine, BF ４ Piperidine, BF ４ Triethylamine, BF ４ Aniline, PF ５ Ethylamine, PF ５ Isopropylamine, PF ５ ・Butylamine, PF ５ Laurylamine, PF ５ Benzylamine, AsF ５ Examples include laurylamine.

[0102] Examples of the Bronsted acid salts include aliphatic sulfonium salts, aromatic sulfonium salts, iodonium salts, and phosphonium salts.

[0103] Examples of the 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-methylimidazole. 1-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2-methylimidazolium isocyanurate, 2-phenylimidazolium isocyanurate, 2,4-diamino-6-[2-methylimidazolyl-(1)]-ethyl-s-triazine, 2,4-diamino-6-[2-ethyl-4-methylimidazolyl-(1)]-ethyl-s-triazine, and the like.

[0104] The content (blending amount) 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, relative to 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 rate of the curable composition increases, and the heat resistance and transparency of the cured product tend to be improved in a balanced manner.

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

[0106] The curable composition can be prepared by stirring and mixing the above-mentioned components, optionally in a heated state. For the stirring and mixing, known or commonly used stirring and mixing means can be used, such as various mixers such as dissolvers and homogenizers, kneaders, roll mills, bead mills, and planetary stirring devices. After stirring and mixing, the mixture may be degassed under vacuum.

[0107] In the curable composition, the proportion of the compound represented by formula (1) relative 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 proportion can be calculated from the proportion of peak areas obtained by GC-MS.

[0108] In the curable composition, 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. This amount can be calculated from the peak area ratio obtained by GC-MS.

[0109] The curable composition has fast curing properties, and when a thermal cationic polymerization initiator is used, the curing time (or gel time) at 80°C is, for example, 600 seconds or less, preferably 500 seconds or less. When an acid anhydride curing agent is used, the curing time (or gel time) at 120°C is, for example, 900 seconds or less, preferably 800 seconds or less. When a photocationic polymerization initiator is used, the curable composition is cured by ultraviolet irradiation (illuminance 3000 mJ / cm). ２ The curing time (or gel time) in the above step (2) 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, more preferably 45 to 540 minutes. If the heating temperature or heating time is below the above range, curing will be insufficient, and conversely, if it exceeds the above range, decomposition of the resin component may occur, so neither is preferable. The curing conditions depend on various conditions, 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] The curable composition is cured to obtain a cured product, which exhibits low outgassing in a high-temperature environment, is resistant to cure shrinkage, and has excellent transparency and heat resistance.

[0112] The cured product has excellent transparency, and its light transmittance (3 mm thickness) for light with a wavelength of 400 nm is preferably 40% or more, more preferably 60% or more, even more preferably 70% or more, and may be 75% or more, 80% or more, 85% or more, and particularly preferably 90% or more. The light transmittance of the cured product when a thermal cationic polymerization initiator is used is preferably 70% or more, more preferably 75% or more. The light transmittance of the cured product when an acid anhydride curing agent is used is preferably 85% or more, more preferably 90% or more. Since the curable composition forms a cured product with excellent transparency, when used as a sealant for an optical semiconductor element in an optical semiconductor device, a die attach paste agent, or the like, the luminous intensity emitted from the optical semiconductor device tends to be higher.

[0113] The 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, still more preferably 240°C or higher, and particularly preferably 250°C or higher. When a thermal cationic polymerization initiator is used, the 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 glass transition temperature of the cured product is preferably 230°C or higher, more preferably 250°C or higher.

[0114] The 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. The 10% weight loss temperature (Td10) of the cured product is preferably 355° C. or higher, and more preferably 360° C. or higher.

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

[0116] The outgassing amount of the 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 outgassing amount is determined by measuring the mass of the cured product before and after heating and calculating the mass reduction rate according to the following formula: Mass reduction rate = {(mass of cured product before heating - mass of cured product after heating) / mass of cured product before heating} x 100

[0117] The flexural strength of the cured product after molding into a shape of 4 mm thick x 10 mm wide x 80 mm long 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 flexural strength can be measured, for example, by the method described in the Examples below.

[0118] The flexural modulus of the cured product after molding into a shape of 4 mm thick x 10 mm wide x 80 mm long 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 flexural elongation of the cured product after molding into a shape of 4 mm thick x 10 mm wide x 80 mm long 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 flexural elongation can be measured, for example, by the method described in the Examples below.

[0120] The curable composition can be used for various applications such as a sealant, an adhesive, a coating agent, a hard coating agent, an electrical insulating material (such as an in-vehicle insulating material), a laminate, an ink (such as an ink for inkjet printing or a UV ink), a sealant, a resist, a composite material, a transparent substrate, a transparent sheet, a transparent film, an optical element, an optical lens, stereolithography, electronic paper, a touch panel, a solar cell substrate, an optical waveguide, a light guide plate, and a holographic memory.

[0121] [Sealant] The sealant includes the curable composition. The sealant can be preferably used for sealing an optical semiconductor (optical semiconductor element) in an optical semiconductor device. By using the sealant, the optical semiconductor element can be sealed with a cured product (sealant) that is excellent in transparency and heat resistance and is resistant to cure shrinkage. Furthermore, since outgassing is unlikely to occur in a high-heat environment, cracks are unlikely to occur, and the reliability of components such as semiconductor elements sealed with the sealant is maintained.

[0122] The content of the curable composition relative to the total amount (100% by mass) of the 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 sealant may consist solely of the curable composition.

[0123] [Adhesive] The adhesive contains the curable composition. The adhesive can be used in a variety of applications requiring excellent transparency, heat resistance, and resistance to cure shrinkage, such as applications for adhering and fixing components to adherends, specifically die-attach pastes for adhering and fixing optical semiconductor elements to metal electrodes in optical semiconductor devices; lens adhesives for fixing lenses to adherends or bonding lenses to each other; and optical film adhesives for fixing optical films (e.g., polarizers, polarizer protective films, retardation films, etc.) to adherends or bonding optical films to each other or to other films. In addition, since outgassing is unlikely to occur in high-heat environments, cracks are unlikely to occur, and the reliability of the bonded components is maintained.

[0124] The adhesive can be particularly preferably used as a die-attach paste (or die-bonding agent). By using the adhesive as a die-attach paste, an optical semiconductor device can be obtained in which an optical semiconductor element is attached to an electrode by a cured product with excellent transparency and heat resistance. Furthermore, since outgassing is unlikely to occur in a high-heat environment, cracks are unlikely to occur, and the reliability of the bonded members is maintained.

[0125] The content of the curable composition relative 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 coating agent includes the curable composition. The coating agent can be used for various applications that require excellent handleability, transparency, and heat resistance. Furthermore, when the coating agent is applied and cured, it is less likely to undergo cure shrinkage and curl.

[0127] The content of the curable composition relative to the total amount (100% by mass) of the coating 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 coating agent may consist solely of the curable composition.

[0128] [Hard Coating Agent] The hard coating agent includes the curable composition. The hard coating agent can be used for various applications that require excellent handleability, transparency, surface hardness, and heat resistance. In addition, when the hard coating agent is applied and cured to form a hard coating layer, it is less likely to undergo cure shrinkage and curl.

[0129] The content of the curable composition relative to the total amount (100% by mass) of the hard coating 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 coating agent may consist solely of the curable composition.

[0130] [Optical Component] An optical component can be obtained using the cured product. The optical component comprises a cured product of the curable composition. Examples of the optical component include an optical semiconductor device in which an optical semiconductor element is encapsulated with the cured product, an optical semiconductor device in which an optical semiconductor element is bonded to an electrode with the cured product, and an optical semiconductor device in which an optical semiconductor element is bonded to an electrode with the cured product and the optical semiconductor element is encapsulated with the cured product. Because the optical component is encapsulated and bonded with the cured product, it has excellent heat resistance and high light extraction efficiency. Furthermore, since outgassing is unlikely to occur in a high-heat environment, cracks are unlikely to occur, and the reliability of the optical semiconductor element and the optical component is maintained.

[0131] Each aspect disclosed in this specification can be combined with any other feature disclosed in this specification. Each configuration and combination thereof in each embodiment is an example, and addition, omission, substitution, and other modifications of configurations are possible as appropriate within the scope of the present disclosure. Furthermore, each invention according to this disclosure is not limited by the embodiments or the following examples, but is limited only by the scope of the claims.

[0132] Hereinafter, one embodiment of the present disclosure will be described in more detail based on examples, but the present disclosure is not limited to these examples.

[0133] Example 1 (Epoxidation Step) 1000 g of 2,2-bis(3′,4′-cyclohexenyl)propane and 3000 g of ethyl acetate were charged into a 10-liter jacketed flask, and while blowing nitrogen into the gas phase, 3072 g of an ethyl acetate solution of peracetic acid (peracetic acid concentration: 29.2%, water content: 0.31%) was added dropwise over about 5 hours so as to raise the temperature in the reaction system to 35° C. After completion of the dropwise addition of peracetic acid, the mixture was aged at 35° C. for 3 hours to complete the reaction.

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

[0135] (First low-boiling point removal step, high-boiling point removal step) The reaction crude liquid that had undergone the above-mentioned washing step was subjected to the first low-boiling point removal step in a WFE-type thin-film evaporator at a heating temperature of 150°C and a pressure of 70 Torr, and then to the high-boiling point removal step under conditions of a heating temperature of 150°C and a pressure of 0.3 Torr, thereby obtaining 609.0 g of an epoxy compound.

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

[0137] Example 2 An 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 to 165°C in the second low-boiling point removal step were recovered.

[0138] Example 3: A 20-liter SUS316 jacketed reactor equipped with a stirrer was charged with 5,000 g of 6-methyl-3-cyclohexenylmethyl (6'-methyl-3',4'-cyclohexenyl) carboxylate, and the temperature was raised to an internal temperature of 25°C. 13,790 g of a 30% ethyl acetate solution of peracetic acid was added dropwise over 6 hours, followed by aging for 3 hours. The internal temperature was maintained at 30°C during the dropwise addition and aging. Thus, 18,790 g of a crude reaction liquid containing 3,4-epoxy-6-methyl-cyclohexylmethyl (3',4'-epoxy-6'-methyl) was obtained. The crude reaction liquid was then subjected to the washing step, first low-boiling point removal step, high-boiling point removal step, and second low-boiling point removal step in the same manner as in Example 1, yielding alicyclic epoxy compound product 3 of Example 3.

[0139] Example 4: A 20 L SUS316 jacketed reactor equipped with a stirrer was charged with 5,000 g of 3,4-cyclohexenylmethyl (3,4-cyclohexene) carboxylate, and the temperature was then raised to an internal temperature of 25°C. 13,790 g of a 30% ethyl acetate solution of peracetic acid was added dropwise over 6 hours, and the mixture was then aged for 3 hours. The internal temperature was maintained at 30°C during the dropwise addition and aging. In this way, 18,790 g of a crude reaction liquid containing 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexane carboxylate was obtained. The reaction crude liquid was then subjected to a washing step and a first low-boiling point removal step in the same manner as in Example 1, and the high-boiling point removal step was carried out in the same manner as in Example 1 except that the bottoms liquid obtained through the first low-boiling point removal step was charged into the fifth plate from the bottom of a high-boiling point removal distillation column consisting of a 10-plate perforated tray column with a column diameter of 40 mm, and thereafter the second low-boiling point removal step was carried out in the same manner as in Example 1, thereby obtaining an alicyclic epoxy compound product 4 of Example 4.

[0140] Comparative Example 1 Alicyclic epoxy compound product 5 of Comparative Example 1 was obtained in the same manner as in Example 1, except that the second low-boiling point removal step was not carried out.

[0141] <Evaluation> The alicyclic epoxy compound products of the Examples and Comparative Examples were evaluated as follows, and the results are shown in the table.

[0142] (1) １ H-NMR of the alicyclic epoxy compound product 1 of Example 1 was measured using an apparatus named "JNM-ECZ400S" (manufactured by JEOL Ltd.), solvent: deuterated chloroform, and measurement conditions: 20°C. １ The H-NMR spectrum of the alicyclic epoxy compound product 1 obtained in Example 1 was measured. １ The H-NMR spectrum is shown in FIG.

[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 (trade name "DISMIC13JP050AN", manufactured by Toyo Roshi Kaisha, Ltd.). The resulting THF solution of the alicyclic epoxy compound product was analyzed by GPC, and the percentage of the peak area corresponding to the compounds represented by the above formulas (a) to (c) was calculated. The percentage excluded was used as the purity [area %] of the alicyclic epoxy compound product. When the shoulders of adjacent peaks overlapped, the peak area was calculated by dividing the peak area by a perpendicular line from the valley of the peak to the baseline. The GPC apparatus and various conditions used were as follows: Apparatus: HLC-8220GPC (Tosoh Corporation) Detector: Differential refractometer (RI detector) Precolumn: TSKGUARD COLUMN SUPER HZ-L 4.6 mm x 20 mm Column: Sample side: TSK-GEL SUPER HZM-N 4.6 mm x 150 mm x 4 columns Reference side: TSK-GEL SUPER HZM-N 6.0 mm x 150 mm x 1 column + TSK-GEL SUPER H-RC 6.0 mm x 150 mm Thermostatic bath temperature: 40°C Mobile phase: THF Mobile phase flow rate: 0.35 ml / min Sample injection volume: 10 μl Data collection time: 10 to 26 minutes after sample injection

[0144] (3) GC-MS The alicyclic epoxy compound products of each example were analyzed by gas chromatography under the following measurement conditions. The components contained in the alicyclic epoxy compound products were identified based on their molecular weights. The molecular weights of the detected peaks were analyzed by mass spectrometry. The total content of compounds (a) to (c) was measured using a gas chromatograph under the following conditions and calculated in area %. The chromatogram obtained by GC-MS of the 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 equipment: Product name "Agilent 7890GC5977B MSD", manufactured by Agilent Technologies, Inc. Column packing: (5% phenyl)methylsiloxane Column size: Length 15 m × inner diameter 0.53 mmφ × film thickness 1.5 μm Column temperature: 100°C → (heating at 10°C / min) → 250°C (15 min) Detector: FID

[0145] (4) Hue (APHA) The hue was evaluated by determining the Hazen color number APHA using a spectroscopic colorimeter and turbidity analyzer (trade 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 0.6 parts by mass of a thermal cationic catalyst "SAN-AID SI-100L" (trade name, manufactured by Sanshin Chemical Industry Co., Ltd.) was blended with 100 parts by mass of the alicyclic epoxy compound product of each example, and the mixture was stirred using a planetary stirring device (trade name "Awatori Rentaro AR-250", manufactured by Thinky Corporation), followed by degassing to obtain each curable composition.

[0147] Example 6 The alicyclic epoxy compound product of each example, an acid anhydride curing agent with the trade name "RIKACID MH-700" (manufactured by New Japan Chemical Co., Ltd.) and a curing accelerator with the trade name "PX-4MP" (manufactured by Nippon Chemical Industry Co., Ltd.) were blended so that the ratio of the epoxy equivalent of the compound represented by formula (1) in the alicyclic epoxy compound product to the acid anhydride equivalent was 100:90, and the mixture was stirred using a planetary stirring device (trade name "Awatori Rentaro AR-250", manufactured by Thinky Corporation) and further degassed to obtain each curable composition.

[0148] Example 7 1 part by mass of a UV cationic catalyst "CPI-101A" (trade name, manufactured by San-Apro Co., Ltd.) was blended with 100 parts by mass of the alicyclic epoxy compound product of each example, and the mixture was stirred using a planetary stirring device (trade name "Awatori Rentaro AR-250", manufactured by Thinky Corporation), followed by degassing to obtain each curable composition.

[0149] Examples 8 to 11 The curable composition of Example 8 was prepared by using 90 parts by mass of the alicyclic epoxy compound product of Example 1 and 10 parts by mass of a bisphenol A epoxy compound (trade name "JER828", manufactured by Mitsubishi Chemical Corporation) as another epoxy compound instead of 100 parts by mass of the alicyclic epoxy compound product of Example 1. The color (APHA) was measured by 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 to 15 The curable composition of Example 12 was prepared by using 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) used in Example 8. The color (APHA) was measured by 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, after heating to 80°C for the curable compositions (thermal cationic catalyst) of Examples 5, 9, and 13, after heating to 120°C for the curable compositions (acid anhydride curing agent) of Examples 6, 10, and 14, and after UV irradiation for the curable compositions (UV cationic catalyst) of Examples 7, 11, and 15, the curing profile was measured by the rheometer method (dynamic viscoelasticity evaluation), and the temperature curve of the loss modulus at a constant frequency was measured. The point where the two elastic modulus curves measuring G' (storage modulus) and G'' (loss modulus) intersect was defined as the gel point. Then, the gel point was determined when the set temperature (80°C or 120°C) was reached or when UV irradiation (illuminance 3000 mJ / cm) was performed. ２ The time when the reaction started was taken as the starting point, and the time until the gel point was reached was evaluated as the reactive gel time. In Examples 5, 9, and 13, a time of 600 seconds or less was judged as good, and a time of 500 seconds or less was judged as excellent. In Examples 6, 10, and 14, a time of 900 seconds or less was judged as good, and a time of 800 seconds or less was judged as excellent. In Examples 7, 11, and 15, a time of 300 seconds or less was judged as good, and a time of 150 seconds or less was judged as excellent.

[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 of the cured products of Examples 16 to 21. Note that the epoxy compound product obtained in Example 4 was further post-cured by heating at 150°C for 30 minutes to produce a cured product.

[0153] (6) Cure Shrinkage The density of the cured product obtained in Example 16 was measured before and after curing using a density measurement method (JIS K5600 2-4), and the cure shrinkage (volume shrinkage) was calculated from the change in density based on the following formula. A value of 1.5% or less is considered to be good. Volume shrinkage r = {(ds - dl) / dl} x 100, where dl is the specific gravity of the liquid before curing. Measured using a density / specific gravity meter "DA-640" (manufactured by Kyoto Electronics Manufacturing Co., Ltd.). ds is the specific gravity of the solid after curing. Measured using a solid specific gravity measurement method.

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

[0155] (8) Glass Transition Temperature (Tg) The glass transition temperature of each cured product obtained in Example 16 was determined under the following conditions. For the cured products of the curable compositions of Examples 5, 9, and 13, a temperature of 200°C or higher was judged as good, and a temperature of 300°C or higher was judged as excellent. For the cured products of the curable compositions of Examples 6, 10, and 14, a temperature of 230°C or higher was judged as good, and a temperature of 250°C or higher was judged as excellent. Sample: length 4 mm x width 5 mm x thickness 0.5 mm Measuring device: viscoelasticity measuring device (DMA), product name "DMS6100", manufactured by Hitachi High-Tech Science Corporation Measurement mode: tension Measurement temperature: from 25°C to 320°C Heating rate: 5°C / min

[0156] (9) Curling Each of the curable compositions obtained in Examples 7, 11, and 15 was uniformly applied to a PET film (thickness: 100 μm) to a thickness of 40 μm, and the cured composition was cured with a UV-curing high-pressure mercury lamp at an integrated light dose of 1200 mJ / cm ２ Each cured product was obtained by irradiating ultraviolet light under the conditions shown above. When the cured product was placed on the top and the outer side 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 (◯), and 1 mm or less as excellent (◎).

[0157] (10) Amount of Outgassing Each of the curable compositions obtained in Examples 7, 11, and 15 was poured into a mold so as to have dimensions of 76 mm length × 26 mm width × 0.5 mm thickness, and was irradiated with UV light at a wavelength of 365 nm and an exposure dose of 2500 mJ / cm using a UV irradiation device (trade name "LED-UV Irradiator PSCC-60048", manufactured by CCS Inc.). ２Each cured product was obtained by irradiating UV light from an LED lamp under the irradiation conditions. The cured product was heated at 110°C for 30 minutes, and the mass loss rate relative to the initial mass was determined under the conditions below, and this was taken as the amount of outgassing. An outgassing amount of 0.1% or less is considered good, and 0.08% or less is considered excellent. Evaluation sample: 5 to 10 μg Measuring device: Product name "STA / 7200", manufactured by Hitachi High-Tech Science Corporation

[0158] (11) Flexural Strength, Flexural Modulus, and Flexural Elongation Of the cured products obtained in Example 16, the cured products of the curable compositions obtained in Examples 9, 10, 13, and 14 were molded into a shape of 4 mm thick x 10 mm wide x 80 mm long, and a three-point bending test was performed using a Tensilon universal testing machine (manufactured by Orientec Co., Ltd.) under conditions of an edge span of 67 mm and a bending speed of 2 mm / min to measure the flexural strength (MPa), flexural modulus (MPa), and flexural elongation (% GL) of the cured products.

[0159]

[0160] As shown in Table 1, the alicyclic epoxy compound products of the Examples had lower outgassing levels than products containing more than 1% by mass of the compounds represented by formulas (a) to (c). They were also evaluated as having good color, excellent transparency, and fast curing with a short reactive gel time. The cured products were also evaluated as having high light transmittance, excellent transparency, and high Tg, excellent heat resistance. Furthermore, the alicyclic epoxy compound products of the Examples were evaluated as having lower cure shrinkage than other alicyclic epoxy compound products.

[0161]

[0162] Variations of the present invention are described below: [Appendix 1] An epoxy compound product, in which the purity of the compound represented by the following formula (1) is 80% or more, and the total proportion of the compound represented by the following formula (a), the compound represented by the following formula (b), and the compound represented by the following 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 a substituent on one or more of the carbon atoms constituting the ring.] [Appendix 2] An epoxy compound product according to Appendix 1, wherein the compound represented by formula (1) is an epoxidized product of a compound represented by the following formula (2) with an aliphatic percarboxylic acid: [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 a substituent on one or more of the carbon atoms constituting the ring.] [Appendix 3] The epoxy compound product according to appendix 2, wherein the aliphatic percarboxylic acid is peracetic acid. [Appendix 4] A curable composition comprising the epoxy compound product according to any one of appendices 1 to 3, and a curing agent and / or a curing catalyst. [Appendix 5] A curable composition comprising the epoxy compound product according to any one of appendices 1 to 3, and another epoxy compound and / or an oxetane compound. [Appendix 6] The curable composition according to appendix 4 or 5, which is an adhesive, sealant, coating agent, or hard coat agent. [Appendix 7] A cured product of the curable composition according to any one of appendices 4 to 6. [Appendix 8] An optical member comprising the cured product according to appendix 7. [Appendix 9] A method for producing an epoxy compound product according to any one of Appendices 1 to 3, which comprises the steps of: an epoxidation step, a first step for removing low-boiling points, a step for removing high-boiling points, and a second step for removing low-boiling points. Epoxidation step: A step of reacting a compound represented by the following formula (2) with an organic peracid to obtain a reaction product: [In formula (2), X represents a single bond or a linking group. The cyclohexene ring in formula (2) may have a substituent on one or more of the carbon atoms constituting the ring.] First low-boiling point removal step: A step of removing low-boiling point components by distillation using a thin-film still. High-boiling point removal step: A step of removing high-boiling point components by distillation. Second low-boiling point removal step: A step of removing the compounds represented by formulas (a) to (c) 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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