WO2025100400A1 - Epoxy compound product - Google Patents

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

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

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

Known examples of the above 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).

International Publication No. 2019/138988 U.S. Pat. No. 2,890,194

However, conventional alicyclic epoxy compound products contain low-boiling compounds as impurities, and there is a problem that, for example, in products that include a cured product obtained by curing an alicyclic epoxy compound, the low-boiling compounds volatilize in a high-heat environment, generating outgassing. If outgassing occurs, for example, when the cured product is used as a sealant for semiconductor elements such as organic electroluminescence (EL), cracks may occur in the inorganic material film in the semiconductor element, resulting in insufficient sealing.

The objective of this disclosure is therefore to provide an epoxy compound product capable of forming a cured product that is less likely to generate outgassing in a high-heat environment.

［式中、Ｘは単結合または連結基を示す。式におけるシクロヘキサン環およびベンゼン環は、環を構成する炭素原子の１以上に置換基を有していてもよい。］ That is, the present 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 having a total content of 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) of 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.]

［式（２）中、Ｘは単結合または連結基を示し、式（１）におけるものと同じである。式（２）におけるシクロヘキセン環は、環を構成する炭素原子の１以上に置換基を有していてもよい。］ The compound represented by the above formula (1) is preferably an epoxidation 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.]

The aliphatic percarboxylic acid is preferably peracetic acid.

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

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

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

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

The present disclosure also provides an optical member comprising the above-mentioned cured product.

［式（２）中、Ｘは単結合または連結基を示す。式（２）におけるシクロヘキセン環は、環を構成する炭素原子の１以上に置換基を有していてもよい。］
　第一脱低沸工程：薄膜蒸留器を使用した蒸留により低沸点成分を除去する工程
　脱高沸工程：蒸留により高沸点成分を除去する工程
　第二脱低沸工程：蒸留塔を使用した蒸留により前記式（ａ）～（ｃ）で表される化合物の除去を行う工程 The present disclosure also provides a method for producing the epoxy compound product, which produces the epoxy compound product 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.
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 distiller. 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 the formulae (a) to (c) by distillation using a distillation column.

The epoxy compound products disclosed herein can form cured products that are less likely to outgas in high-heat environments.

1 shows the ¹ H-NMR spectrum of the alicyclic epoxy compound product 1 prepared in Example 1. 1 shows a chromatogram obtained by GC-MS of the alicyclic epoxy compound product 1 prepared in Example 1. 1 shows a peak report obtained by GC-MS of the alicyclic epoxy compound product 1 prepared in Example 1.

[Epoxy compound products]
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.

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.

Examples of the linking group include a divalent hydrocarbon group, an alkenylene group in which some or all of the carbon-carbon double bonds have been 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 -, groups in which a plurality of these are linked together, etc. Among these, the linker is preferably a group selected from the group consisting of an ether bond, a thiol bond, -SO-, -SO ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ -, -CBr ₂ -, -C(CBr ₃ ) ₂ -, and -C(CF ₃ ) ₂ -.

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

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 "epoxidized alkenylene group") includes, for example, straight-chain 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.

Examples of the substituents that the cyclohexane ring may have include halogen atoms, oxygen atoms, or hydrocarbon groups that may have halogen atoms, and alkoxy groups that may have substituents. When the cyclohexane ring has multiple substituents, the multiple substituents may be the same or different.

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. In formula (i-5) below, R' 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.

The compound represented by the formula (1) may be an epoxy-modified siloxane. The epoxy-modified siloxane may be, for example, a linear or cyclic polyorganosiloxane having a structural unit represented by the following formula (i'):

In the above formula (i'), ^R3 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 ^R4 represents an alkyl group or an alkoxy group.

In formula (1a) and formula (1b), R ^1a and R ^1b are the same or different and represent a linear or branched alkylene group, 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, or a decamethylene group, which is a linear or branched alkylene group having 1 to 10 carbon atoms.

The epoxy equivalent of the above epoxy-modified siloxane (based on JIS K7236) is, for example, 100 to 400, preferably 150 to 300.

As the epoxy-modified siloxane, for example, a commercially available product such as the compound represented by the following formula (i'-1) (product name "KR-470", manufactured by Shin-Etsu Chemical Co., Ltd.) can be used.

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

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). The purity of the compound represented by formula (1) in the epoxy compound product may be calculated and the remaining ratio after excluding the peak area ratios corresponding to the compounds represented by formulas (a) to (c). When the peak shoulders overlap, the peak areas are separated by a perpendicular line to the baseline that passes through the valleys of the peaks.

In addition, the epoxy compound product has a 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) of 1 mass % or less, preferably 0.8 mass % or less, more preferably 0.6 mass % or less, and even more preferably 0.3 mass % or less, relative to the total amount (100 mass %) of the epoxy compound product. The total content may be, for example, 0.005 mass % or more, 0.01 mass % or more, or 0.05 mass % or more. The epoxy compound product may contain one, two, or three types of the compounds represented by the above formulas (a) to (c), or may not contain any at all.

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 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 above-mentioned substituent include those exemplified and explained as the substituents that the cyclohexane ring in formula (1) may have. When there are multiple substituents, the multiple substituents may be the same or different.

The compounds represented by the above formulas (a) to (c) do not have epoxy groups, and therefore do not harden when a composition containing an epoxy compound product is cured. As a result, the compounds represented by the above formulas (a) to (c) remain in the cured product. When the cured product is exposed to a high-heat environment, the compounds represented by the above formulas (a) to (c) volatilize and become outgassed. Since the total content of the compounds represented by the above formulas (a) to (c) in the above epoxy cured product is 1 mass% or less, these compounds are less likely to remain in the cured product, and the amount of outgassing is reduced. In addition, the effects of small curing shrinkage, reduced curling during curing, excellent adhesion to substrates, improved curability with active energy rays, which allows the curing process to be shortened, and excellent heat resistance and transparency of the cured product are also obtained.

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

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.

(Method of manufacturing epoxy compound products)
The above epoxy compound product can be obtained by epoxidizing a compound represented by the following formula (2) with an organic peracid.

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 substituents that the cyclohexane ring in formula (1) may have. When there are multiple substituents, the multiple substituents may be the same or different.

More specifically, the epoxy compound product can be produced through the following epoxidation step, the following first low-boiling step, the following high-boiling step, and the following second low-boiling step. The order of the steps is not particularly limited, and for example, either the first low-boiling step or the second low-boiling step may be performed first, but it is particularly preferable to perform the steps in the order of the first low-boiling step, the high-boiling step, and the second low-boiling step.
Epoxidation step: a step of reacting the 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 the compounds represented by the formulae (a) to (c) by distillation.

In addition, after the epoxidation process is completed, and before the first low-boiling point removal process, the second low-boiling point removal process, and the high-boiling point removal process, a process (cleaning process) may be provided in which the obtained reaction product is washed with water to remove the organic peroxy acid used in the reaction and its decomposition products.

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

Examples of the organic peracid include performic acid, peracetic acid, perpropionic acid, m-chloroperbenzoic acid, trifluoroperacetic acid, and perbenzoic acid. Only one type of the organic peracid may be used, or two or more types may be used. The organic peracid is preferably an aliphatic percarboxylic acid, and more preferably peracetic acid.

The above aliphatic percarboxylic acid is preferably an oxygen oxide of the corresponding aldehyde. Such an aliphatic percarboxylic acid contains substantially no moisture, and can make it difficult for the ring opening of the epoxy group to occur.

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

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 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, and derivatives thereof; 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.

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

If necessary, stabilizers for organic peracids (e.g., ammonium hydrogen phosphate, potassium pyrophosphate, 2-ethylhexyl tripolyphosphate, etc.) and polymerization inhibitors (e.g., hydroquinone, piperidine, ethanolamine, phenothiazine, etc.) may be used in the epoxidation reaction.

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, etc.

(2) Washing step The washing step is a step of removing the organic peracid and its decomposition product, which are contained in the reaction product obtained through the epoxidation step, by washing with water. In addition, the organic peracid may be neutralized by using a base such as sodium hydroxide during the water washing.

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

(3) First low-boiling component removal step The first low-boiling component 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, mainly low-boiling components other than the compounds represented by formulas (a) to (c) are removed, but 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.

In the first low boiling point removal process, 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.

When subjecting the reaction product 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) above. The amount of polymerization inhibitor added varies slightly depending on the type and distillation temperature, but it is preferable that the amount is 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.

In the first low boiling point removal step, components with a lower boiling point than the compounds represented by the above formulas (a) to (c) are evaporated and removed from the reaction product, and a mixture of the compounds represented by the above formulas (a) to (c), the compound represented by the above formula (1), and components with a higher boiling point than these is obtained as the bottoms.

(4) High-boiling point removal step The high-boiling point removal step is a step of distilling off components having a higher boiling point than the compounds represented by the formulas (a) to (c) and the compound represented by the formula (1) contained in the reaction product. 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 compounds represented by the formulas (1) and (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 having a higher boiling point than these, which is the bottoms obtained after 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.

In the high boiling point removal step, either a distillation column or 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. The distillation is preferably carried out under conditions of a heating temperature of 250°C or less (preferably 230°C or less) from the viewpoint of preventing the compound represented by the above formula (1) from decomposing and increasing the degree of coloration, and preventing the epoxy group of the compound represented by the above formula (1) from ring-opening polymerization and gelling. The distillation temperature is preferably 50°C or more, more preferably 100°C or more. From the same viewpoint, the distillation is preferably carried out under conditions of a pressure of 3 torr or less (preferably 0.7 torr or less). The pressure is preferably 0.01 torr or more, and may be 0.02 torr or more, from the viewpoint of increasing the purity of the epoxy compound product.

(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 formulae (a) to (c) contained in the reaction product. By subjecting the reaction product to this step, the content of the compounds represented by the formulae (a) to (c) mixed in the epoxy compound product can be extremely reduced.

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 formulas (a) to (c) are distilled off by evaporation from a 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 a bottoms liquid.

As the distillation tower, for example, a packed tower or a plate tower can be used. The actual number of stages in the distillation tower is preferably 14 or more, and preferably 14 to 100 stages, and particularly preferably 14 to 50 stages, in order to further improve the purity of the product.

In the second low-boiling point removal step, the distillation is preferably carried out at a temperature of 250°C or less (e.g., 50-250°C) and with a residence time at the bottom of the distillation vessel of less than 10 hours (e.g., 1 hour or more and 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 at 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 at 250°C or less, discoloration of the obtained epoxy compound can be suppressed.

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, the epoxy compound product can be obtained that contains the compound represented by formula (1) in high purity and has extremely reduced amounts of the compounds represented by formulas (a) to (c).

Epoxy compound products obtained by distillation purification using a general thin film distillation apparatus (WFE) tend to have a high content of the compounds represented by the above formulas (a) to (c). In addition, if the low boiling point removal step and the high boiling point removal step using a WFE are not performed, or if the reaction product from which the solvent has been removed by the low boiling point removal step is distilled in a distillation column, the residence time at the bottom of the vessel is long, resulting in significant coloring and gelation due to ring-opening polymerization. In addition, it was impossible to separate the compounds represented by the above formulas (a) to (c) and the compound represented by the above formula (1) in purification using a WFE. On the other hand, if the low boiling point removal step and the high boiling point removal step are performed at the same time using a distillation column, the residence time at the bottom of the vessel is long, resulting in significant coloring 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 an actual number of stages of 14 or more, a heating temperature of 250°C or less, and a residence time at the bottom of the vessel of less than 10 hours, particularly after performing the low boiling point removal step and the high boiling point removal step using a WFE.

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

(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.

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

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

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

The above-mentioned alicyclic epoxy compounds include known or conventional compounds having one or more alicyclic rings and one or more epoxy groups in the molecule, and are not particularly limited, but examples thereof include (I) a compound in which an epoxy group is directly bonded to an alicyclic ring via a single bond; (II) a compound having an alicyclic ring and a glycidyl ether group in the molecule (glycidyl ether type epoxy compound), etc.

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

In formula (ii), R" is a group (p-valent organic group) obtained by removing p hydroxyl groups (-OH) from the structural formula of p-valent alcohol, and p and n each represent a natural number. Examples of p-valent alcohols [R"(OH)p] include polyhydric alcohols (alcohols having 1 to 15 carbon atoms, etc.) 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 in each group in ( ) (in the outer parentheses) may be the same or different. Specific examples of compounds represented by the above formula (ii) include 1,2-epoxy-4-(2-oxiranyl)cyclohexane adducts of 2,2-bis(hydroxymethyl)-1-butanol [for example, product name "EHPE3150" (manufactured by Daicel Corporation)].

Examples of the above (II) compounds having an alicyclic ring and a glycidyl ether group in the molecule include, for example, glycidyl ethers of alicyclic alcohols (particularly, alicyclic polyhydric alcohols). More specifically, for example, compounds obtained by hydrogenating 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; hydrogenated epoxy compounds of other epoxy compounds having aromatic rings.

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 the aromatic epoxy compounds, compounds in which a glycidoxy group is bonded to one or more carbon atoms constituting an aromatic ring having carbon atoms (particularly an aromatic hydrocarbon ring) (aromatic glycidyl ether epoxy compounds) are preferred.

The above-mentioned aromatic epoxy compounds include, for example, epi-bis-type glycidyl ether type 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 epi-bis-type glycidyl ether type epoxy resins obtained by further addition reaction of these epi-bis-type glycidyl ether type epoxy resins with the above-mentioned bisphenols; phenols [e.g., phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol, etc.]; Examples of such resins include novolak alkyl type glycidyl ether epoxy resins obtained by condensing polyhydric alcohols obtained by condensing polyhydric alcohols (e.g., phenol F, bisphenol S, etc.) with aldehydes (e.g., formaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, salicylaldehyde, etc.) with epihalohydrin; and epoxy compounds in which two phenol skeletons are bonded to the 9-position of the fluorene ring, and glycidyl groups are bonded to the oxygen atoms obtained by removing the hydrogen atoms from the hydroxyl groups of these phenol skeletons, either directly or via alkyleneoxy groups.

Examples of the aliphatic epoxy compounds include glycidyl ethers of alcohols not having a q-valent cyclic structure (q is a natural number); glycidyl esters of mono- or polyvalent carboxylic acids [e.g., acetic acid, propionic acid, butyric acid, stearic acid, adipic acid, sebacic acid, maleic acid, itaconic acid, etc.]; epoxidized products of oils and fats having double bonds, such as epoxidized linseed oil, epoxidized soybean oil, and epoxidized castor oil; epoxidized products of polyolefins (including polyalkadienes), such as epoxidized polybutadiene, etc. Examples of the q-valent alcohol that does not have 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 polyether polyol, polyester polyol, polycarbonate polyol, polyolefin polyol, or the like.

The above-mentioned oxetane compounds include known or conventional compounds having one or more oxetane rings in the molecule, and are not particularly limited thereto. 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, phenol novolac oxetane, etc.

The vinyl ether compound may be any known or conventional compound having one or more vinyl ether groups in the molecule, and is not particularly limited. Examples of the vinyl ether compound include, but are not limited to, 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, tetra Ethylene 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, 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, 1,4-cyclohexanediol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, etc.

The proportion of the compound represented by the above formula (1) in the total amount (100 mass%) of the 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.

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.

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

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.

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.

(Hardening agent)
As the curing agent, for example, known or commonly used 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, organic acid hydrazides, etc. The curing agents may be used alone or in combination of two or more kinds.

The above-mentioned acid anhydrides include, for example, methyltetrahydrophthalic anhydride (4-methyltetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, etc.), methylhexahydrophthalic anhydride (4-methylhexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, etc.), dodecenyl succinic anhydride, methyl endomethylene tetrahydrophthalic anhydride, phthalic anhydride, maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylcyclohexene diphthalate, Examples of the acid anhydride 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, and alkylstyrene-maleic anhydride copolymer. Among these, from the viewpoint of handling, acid anhydrides that are liquid at 25° C. [e.g., methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, dodecenyl succinic anhydride, methyl end methylene tetrahydrophthalic anhydride, etc.] are preferred.

The above amines include, for example, 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 , 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; aromatic polyamines such as biphenylenediamine, 4,4-diaminodiphenylmethane, 2,5-naphthylenediamine, and 2,6-naphthylenediamine.

Examples of the polyamide resin include polyamide resins that have either or both of a primary amino group and a secondary amino group in the molecule.

The above imidazoles include, for example, 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, 1-cyanoethyl- Examples include 2-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.

Examples of the polymercaptans include liquid polymercaptan and polysulfide resin.

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

Examples of the polycarboxylic acids include adipic acid, sebacic acid, terephthalic acid, trimellitic acid, and carboxyl group-containing polyesters.

As a curing agent, from the viewpoint of heat resistance and transparency of the obtained cured product, acid anhydrides (acid anhydride-based curing agents) are preferable, and for example, commercially available products such as "RIKACID MH-700" and "RIKACID MH-700F" (both manufactured by New Japan Chemical Co., Ltd.) and "HN-5500" (manufactured by Hitachi Chemical Co., Ltd.) can be used.

The content (mixture 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 the epoxy compounds contained in the curable composition. More specifically, when an acid anhydride is used as the curing agent, it is preferable to use it in a ratio of 0.5 to 1.5 equivalents per equivalent of epoxy groups in all the epoxy compounds contained in the curable composition. When the content of the curing agent is 50 parts by mass or more, curing can be sufficiently advanced, and the toughness of the obtained cured product tends to be improved. On the other hand, when the content of the curing agent is 200 parts by mass or less, coloring is further suppressed, and a cured product with excellent hue tends to be obtained.

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

The above-mentioned curing accelerators include, for example, 1,8-diazabicyclo[5.4.0]undecene-7 (DBU) or a salt thereof (e.g., phenol salt, octylate salt, p-toluenesulfonate salt, 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 salt, formate salt, tetraphenylborate salt, etc.); benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol. , tertiary amines such as N,N-dimethylcyclohexylamine; imidazoles such as 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole; phosphate esters; phosphines such as triphenylphosphine, tris(dimethoxy)phosphine; phosphonium compounds such as tetraphenylphosphonium tetra(p-tolyl)borate; organic metal salts such as zinc octylate, tin octylate, zinc stearate; metal chelates such as aluminum acetylacetone complex. The above curing accelerators may be used alone or in combination of two or more.

As the curing accelerator, for example, 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.) can be used.

The content (mixture 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. If 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, if the content of the curing accelerator is 5 parts by mass or less, coloring is further suppressed, and a cured product with excellent hue tends to be obtained.

(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 the formula (1) above, thereby curing the curable composition. Examples of the curing catalyst include cationic polymerization initiators (photocationic polymerization initiators, thermal cationic polymerization initiators, etc.) that generate cationic species by applying light irradiation or heat treatment, and initiate polymerization, Lewis acid-amine complexes, Bronsted acid salts, imidazoles, etc. The curing catalyst may be used alone or in combination of two or more.

Furthermore, examples of the photocationic polymerization initiator include sulfonium salts (particularly triarylsulfonium salts) such as triarylsulfonium hexafluorophosphate (e.g., p-phenylthiophenyldiphenylsulfonium hexafluorophosphate, etc.) 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.

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 tris(pentafluoroethyl)trifluorophosphate, Examples include 4-(4-(2-thioxanthonylthio)phenyl]sulfonium tetrakis(pentafluorophenyl)borate, diphenyl[4-(phenylthio)phenyl]sulfonium hexafluorophosphate, 4-(4-biphenylylthio)phenyl-4-biphenylylphenylsulfonium tris(pentafluoroethyl)trifluorophosphate, bis[4-(diphenylsulfonio)phenyl]sulfi phenyltris(pentafluorophenyl)borate, [4-(2-thioxanthonylthio)phenyl]phenyl-2-thioxanthonylsulfonium phenyltris(pentafluorophenyl)borate, and 4-(phenylthio)phenyldiphenylsulfonium hexafluoroantimonate.

The photocationic polymerization initiator may be a commercially available product. Examples of the commercially available product include those sold under the trade names "Cyracure UVI-6970", "Cyracure UVI-6974", "Cyracure UVI-6990", and "Cyracure UVI-950" (all manufactured by Union Carbide Corporation, USA), "Omnirad 250", "Omnirad 261", "Omnirad 264", and "CG-24-61" (all manufactured by IGM Resins), and "Opt "Optomer SP-150", "Optomer SP-151", "Optomer SP-170", "Optomer SP-171" (all manufactured by ADEKA Corporation), "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 Co., Ltd.), "CD-1010", "CD-1011", "CD-1012" (all manufactured by Sartomer, USA), "CPI-100P", "CPI-101A" (all manufactured by San-Apro Ltd.), etc.

The above-mentioned thermal cationic polymerization initiators include, for example, aryl diazonium salts, aryl iodonium salts, aryl sulfonium 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 G.E.); "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 "CG-24-61" (manufactured by BASF) can be preferably used.

Examples of the Lewis acid-amine complex 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.

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

The above imidazoles include, for example, 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, 1-cyanoethyl- Examples include 2-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.

The content (mixture 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 speed of the curable composition increases, and the heat resistance and transparency of the cured product tend to be improved in a balanced manner.

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; defoamers, leveling agents, silane coupling agents, surfactants, inorganic fillers, flame retardants, colorants, ion adsorbents, pigments, fluorescent materials, and mold release agents. Only one type of the additives may be used, or two or more types may be used.

The curable composition can be prepared by stirring and mixing the above-mentioned components in a heated state as necessary. For the stirring and mixing, known or conventional stirring and mixing means can be used, such as various mixers such as dissolvers and homogenizers, kneaders, roll mills, bead mills, and self-revolving stirrers. After stirring and mixing, the mixture may be degassed under vacuum.

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

In the curable composition, the total ratio of the compound represented by formula (a), the compound represented by formula (b), and the compound represented by formula (c) to the total amount (100 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 mass% or less, preferably 0.8 mass% or less, more preferably 0.6 mass% or less, and even more preferably 0.4 mass% or less. The above ratio can be calculated from the peak area ratio obtained by GC-MS.

The curable composition has fast curing properties, and the curing time (or gel time) at 80° C. when a thermal cationic polymerization initiator is used is, for example, 600 seconds or less, preferably 500 seconds or less. The curing time (or gel time) at 120° C. when an acid anhydride curing agent is used is, for example, 900 seconds or less, preferably 800 seconds or less. The curable composition has a curing time (or gel time) when a photocationic polymerization initiator is used, under ultraviolet irradiation (illuminance 3000 mJ/cm ² ), for example, 300 seconds or less, preferably 150 seconds or less.

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 is below the above range, curing will be insufficient, and conversely, if it exceeds the above range, decomposition of the resin components 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.

[Cured product]
The curable composition is cured to obtain a cured product, which has a small amount of outgassing in a high-temperature environment, is resistant to cure shrinkage, and has excellent transparency and heat resistance.

The cured product has excellent transparency, and its light transmittance (3 mm thickness) of 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. When a thermal cationic polymerization initiator is used, the 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 light transmittance of the cured product 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 attachment paste agent, or the like, the luminous intensity emitted from the optical semiconductor device tends to be higher.

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, even 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.

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.

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 calculated from the density change based on the following formula by measuring the density of the curable composition before curing and the cured product after curing.
Volumetric shrinkage rate r = {(ds-dl)/dl} x 100
dl: specific gravity of the liquid before hardening. Measured using a density and specific gravity meter "DA-640" (manufactured by Kyoto Electronics Manufacturing Co., Ltd.
ds: Specific gravity of solid after hardening, measured by solid specific gravity measurement method.

The outgassing amount of the cured product when heated for 30 minutes at 110° C. 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 as the mass reduction rate calculated based on the following formula by measuring the masses of the cured product before and after heating.
Mass reduction rate={(mass of cured product before heating−mass of cured product after heating)/mass of cured product before heating}×100

The bending strength of the cured product after it is molded 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 bending strength can be measured, for example, by the method described in the Examples below.

After the cured product is molded into a shape of 4 mm thick x 10 mm wide x 80 mm long, the flexural modulus 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.

The bending elongation of the cured product after it is molded into a shape of 4 mm thickness x 10 mm width x 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.

The above-mentioned curable composition can be used for various applications such as sealants, adhesives, coating agents, hard coat agents, electrical insulating materials (such as automotive insulating materials), laminates, inks (such as inks for inkjet printing, UV inks), sealants, resists, composite materials, transparent substrates, transparent sheets, transparent films, optical elements, optical lenses, photolithography, electronic paper, touch panels, solar cell substrates, optical waveguides, light guide plates, and holographic memories.

[Sealant]
The encapsulant includes the curable composition. The encapsulant can be preferably used for encapsulating an optical semiconductor (optical semiconductor element) in an optical semiconductor device. By using the encapsulant, an optical semiconductor element can be encapsulated with a cured product (=encapsulant) that is excellent in transparency and heat resistance and is unlikely to undergo curing shrinkage. In addition, since outgassing is unlikely to occur in a high-heat environment, cracks are unlikely to occur, and the reliability of members such as semiconductor elements encapsulated by the encapsulant is maintained.

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 of only the curable composition.

[glue]
The adhesive contains the curable composition. The adhesive can be used in various applications that require excellent transparency, heat resistance, and resistance to cure shrinkage, such as applications for adhering and fixing a member or the like to an adherend, specifically, a die attachment paste for adhering and fixing an optical semiconductor element to a metal electrode in an optical semiconductor device; a lens adhesive for fixing a lens of a camera or the like to an adherend or bonding lenses together; an optical film adhesive for fixing an optical film (e.g., a polarizer, a polarizer protective film, a retardation film, etc.) to an adherend or bonding optical films together or an optical film to another film. In addition, since outgassing is unlikely to occur in a high-heat environment, cracks are unlikely to occur, and the reliability of the bonded member is maintained.

The above adhesive can be particularly preferably used as a die attachment paste (or die bond agent). By using the above adhesive as a die attachment 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. In addition, 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.

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 of only the curable composition.

[Coating agent]
The coating agent includes the curable composition. The coating agent can be used in various applications that require excellent handling, transparency, and heat resistance. In addition, the coating agent is unlikely to undergo curing shrinkage and curling when applied and cured.

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 of only the curable composition.

[Hard Coating Agent]
The hard-coating agent includes the curable composition. The hard-coating agent can be used in various applications that require excellent handling, 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 unlikely to undergo curing shrinkage and curling.

The content ratio 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 of only the curable composition.

[Optical components]
The optical member can be obtained using the cured product. The optical member includes a cured product of the curable composition. Examples of the optical member include an optical semiconductor device in which an optical semiconductor element is sealed by the cured product, an optical semiconductor device in which an optical semiconductor element is bonded to an electrode by the cured product, and an optical semiconductor device in which an optical semiconductor element is bonded to an electrode by the cured product and the optical semiconductor element is sealed by the cured product. The optical member has a configuration in which the optical member is sealed and bonded by the cured product, and therefore has excellent heat resistance and high light extraction efficiency. In addition, outgassing is unlikely to occur in a high-heat environment, so that cracks are unlikely to occur and the reliability of the optical semiconductor element and the optical member is maintained.

Each aspect disclosed in this specification may be combined with any other feature disclosed in this specification. Each configuration in each embodiment and their combinations are merely examples, and additions, omissions, substitutions, and other modifications of configurations are possible as appropriate within the scope of the spirit of this disclosure. Furthermore, each invention related to this disclosure is not limited to the embodiments or the examples below, but is limited only by the scope of the claims.

Below, 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.

Example 1
(Epoxidation process)
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 a solution of peracetic acid in ethyl acetate (peracetic acid concentration: 29.2%, water content: 0.31%) was added dropwise over about 5 hours so that the temperature in the reaction system was 35° C. After completion of the dropwise addition of peracetic acid, the mixture was aged at 35° C. for 3 hours to terminate the reaction.

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

(First low boiling process, high boiling process)
The reaction crude liquid having undergone the above-mentioned washing step was subjected to a 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 subjected to a 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.

(Second low boiling 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 type distillation column having an actual number of 20 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 bottom residence time of less than 10 hours were recovered to obtain an alicyclic epoxy compound product 1 (295 g) of Example 1.

Example 2
An alicyclic epoxy compound product 2 of Example 2 was obtained in the same manner as in Example 1, except that in the second low boiling point removal step, the components distilled at a column top temperature of 160 to 165°C were recovered.

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

Example 4
A 20 L SUS316 jacketed reactor equipped with a stirrer was charged with 5000 g of 3,4-cyclohexenylmethyl (3,4-cyclohexene) carboxylate, and then heated to an internal temperature of 25° C. 13790 g of a 30% solution of peracetic acid in ethyl acetate was added dropwise over 6 hours, and then aging was carried out for 3 hours. The internal temperature was maintained at 30° C. during the dropwise addition and aging. In this way, 18790 g of a reaction crude liquid containing 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexane carboxylate was obtained. Then, the reaction crude liquid was subjected to a washing step and a first low boiling point removal step in the same manner as in Example 1, and the bottoms obtained through the first low boiling point removal step were charged into a high boiling point removal distillation tower having a tower diameter of 40 mm and consisting of a perforated plate tower with an actual number of 10 stages, and the high boiling point removal step was carried out in the same manner as in Example 1, except that the bottoms obtained through the first low boiling point removal step were charged into the fifth stage from the bottom of the high boiling point removal distillation tower, and then the second low boiling point removal step was carried out in the same manner as in Example 1, to obtain an alicyclic epoxy compound product 4 of Example 4.

Comparative Example 1
An 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.

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

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

(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 filter with a pore size of 0.50 μm (product name "DISMIC13JP050AN", manufactured by Toyo Roshi Kaisha, Ltd.). The obtained THF solution of the alicyclic epoxy compound product was analyzed by GPC, and the proportion of the peak area corresponding to the compounds represented by the above formulas (a) to (c) was calculated, and the excluded proportion was taken 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 are as follows.
Apparatus: HLC-8220GPC (manufactured by Tosoh Corporation)
Detector: Differential refractometer (RI detector)
Precolumn: TSKGUARD COLUMN SUPER HZ-L 4.6mm x 20mm
Column: Sample side TSK-GEL SUPER HZM-N 4.6mm x 150mm x 4 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 phase flow rate: 0.35 ml/min Sample injection volume: 10 μl
Data collection time: 10 to 26 minutes after sample injection

(3) GC-MS
The alicyclic epoxy compound product of each example was analyzed by gas chromatography under the following measurement conditions. The components contained in the alicyclic epoxy compound product were identified based on the molecular weight. The molecular weight of the detected peak was analyzed by mass spectrometry. The total content of the compounds represented by 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 device: Product name "Agilent 7890GC5977B MSD", manufactured by Agilent Technologies, Inc. Column packing material: (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

(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 x cell width 20 x height 55). A value of 105 or less is considered good, and a value of 15 or less is considered excellent.

Example 5
0.6 parts by mass of a thermal cationic catalyst "SAN-AID SI-100L" (product name, manufactured by Sanshin Chemical Industry Co., Ltd.) was mixed with 100 parts by mass of the alicyclic epoxy compound product of each example, and the mixture was stirred using a planetary stirring device (product name "Awatori Rentaro AR-250", manufactured by Thinky Corporation), and further degassed to obtain each curable composition.

Example 6
The alicyclic epoxy compound product of each example was mixed with an acid anhydride curing agent (trade name "RIKACID MH-700" manufactured by New Japan Chemical Co., Ltd.) and a curing accelerator (trade name "PX-4MP" manufactured by Nippon Chemical Industry Co., Ltd.) such that the ratio of the epoxy equivalent of the compound represented by the 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.

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

Examples 8 to 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 (product name "JER828", manufactured by Mitsubishi Chemical Corporation) were used as another epoxy compound to prepare the curable composition of Example 8. The hue (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.

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 an oxetane compound instead of 10 parts by mass of the bisphenol A type epoxy compound (product name "JER828", manufactured by Mitsubishi Chemical Corporation) of Example 8. The hue (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.

(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 (product name "Rheometer MCR302", manufactured by Anton Paar Japan Co., Ltd.). Specifically, the curable compositions (thermal cationic catalyst) of Examples 5, 9, and 13 were heated to 80°C, the curable compositions (acid anhydride curing agent) of Examples 6, 10, and 14 were heated to 120°C, and the curable compositions (UV cationic catalyst) of Examples 7, 11, and 15 were irradiated with ultraviolet light. The curing profile was measured by the rheometer method (dynamic viscoelasticity evaluation), the temperature curve of the loss modulus at a constant frequency was measured, and the point where the two elastic modulus curves measuring G' (storage modulus) and G'' (loss modulus) intersected was defined as the gel point. The time from when the set temperature (80°C or 120°C) was reached or when ultraviolet irradiation (illuminance 3000 mJ/ ^cm2 ) began to reach the gel point was used as the starting point and 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.

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, for the epoxy compound product obtained in Example 4, it was further heated at 150° C. for 30 minutes to perform post-cure, and a cured product was produced.

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

(7) Light transmittance For each of the cured products (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 (product 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 as good, and 75% or more was judged as excellent. For the cured products of the curable compositions of Examples 6, 10, and 14, a transmittance of 85% or more was judged as good, and 90% or more was judged as excellent.

(8) Glass transition temperature (Tg)
The glass transition temperature of each of the cured products 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 glass transition temperature of 200° C. or higher was judged as good, and a glass transition 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 glass transition temperature of 230° C. or higher was judged as good, and a glass transition 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: Tensile Measurement temperature: 25°C to 320°C Heating rate: 5°C/min

(9) Curl 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 each cured product was obtained by irradiating ultraviolet rays with a high pressure mercury lamp for ultraviolet curing under conditions of an integrated light amount of 1200 mJ/ ^cm2 . When the cured product was placed on the upper side and the outer side was lifted, the height of the square was measured and the average value was calculated. If the curl height was more than 5 mm, it was judged to be poor (x), if it was 5 mm or less, it was judged to be good (◯), and if it was 1 mm or less, it was judged to be excellent (◎).

(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 a size of 76 mm long x 26 mm wide x 0.5 mm thick, and each cured product was obtained by UV irradiation using a UV irradiation device (trade name "LED-UV irradiator PSCC-60048", manufactured by CCS Corporation) with an LED lamp under irradiation conditions of a wavelength of 365 nm and an exposure dose of 2500 mJ/ ^cm2 . The above cured products were heated at 110°C for 30 minutes, and the mass reduction rate relative to the initial mass was determined under the following conditions, and was taken as the amount of outgassing. An amount of outgassing of 0.1% or less is considered good, and an amount of outgassing of 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

(11) Flexural Strength, Flexural Modulus, and Flexural Elongation Of the cured product obtained in Example 16, the cured products of each of the curable compositions obtained in Examples 9, 10, 13, and 14 were molded into a shape of 4 mm in thickness × 10 mm in width × 80 mm in length, 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.

As shown in Table 1, the alicyclic epoxy compound products of the examples had a lower amount of outgassing compared to products in which the total proportion of compounds represented by formulas (a) to (c) exceeded 1% by mass. They were also evaluated as having good hue, excellent transparency, a short reactive gel time, and fast curing properties. The cured products were also evaluated as having high light transmittance and excellent transparency, and a high Tg and excellent heat resistance. Furthermore, the alicyclic epoxy compound products of the examples were evaluated as having less cure shrinkage compared to other alicyclic epoxy compound products.

［式中、Ｘは単結合または連結基を示す。式におけるシクロヘキサン環およびベンゼン環は、環を構成する炭素原子の１以上に置換基を有していてもよい。］
［付記２］前記式（１）で表される化合物は下記式（２）で表される化合物の脂肪族過カルボン酸によるエポキシ化物である、付記１に記載のエポキシ化合物製品。

［式（２）中、Ｘは単結合または連結基を示し、式（１）におけるものと同じである。式（２）におけるシクロヘキセン環は、環を構成する炭素原子の１以上に置換基を有していてもよい。］
［付記３］前記脂肪族過カルボン酸は過酢酸である付記２に記載のエポキシ化合物製品。
［付記４］付記１～３のいずれか１つに記載のエポキシ化合物製品と、硬化剤および／または硬化触媒とを含む、硬化性組成物。
［付記５］付記１～３のいずれか１つに記載のエポキシ化合物製品と、その他のエポキシ化合物および／またはオキセタン化合物とを含む、硬化性組成物。
［付記６］接着剤、封止剤、コーティング剤、またはハードコート剤である付記４または５に記載の硬化性組成物。
［付記７］付記４～６のいずれか１つに記載の硬化性組成物の硬化物。
［付記８］付記７に記載の硬化物を備える光学部材。
［付記９］下記エポキシ化工程、下記第一脱低沸工程、下記脱高沸工程、および下記第二脱低沸工程を経て前記エポキシ化合物製品を製造する、付記１～３のいずれか１つに記載のエポキシ化合物製品の製造方法。
　エポキシ化工程：下記式（２）で表される化合物と有機過酸とを反応させて反応生成物を得る工程

［式（２）中、Ｘは単結合または連結基を示す。式（２）におけるシクロヘキセン環は、環を構成する炭素原子の１以上に置換基を有していてもよい。］
　第一脱低沸工程：薄膜蒸留器を使用した蒸留により低沸点成分を除去する工程
　脱高沸工程：蒸留により高沸点成分を除去する工程
　第二脱低沸工程：蒸留塔を使用した蒸留により前記式（ａ）～（ｃ）で表される化合物の除去を行う工程
  Variations of the invention according to the present disclosure are described below.
[Appendix 1] The purity of the compound represented by the following formula (1) is 80% or more,
An epoxy compound product, comprising 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 amount of 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] The epoxy compound product according to appendix 1, wherein the compound represented by formula (1) is an epoxidation product of a compound represented by formula (2) below 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 other epoxy compounds and/or oxetane compounds.
[Appendix 6] The curable composition according to appendix 4 or 5, which is an adhesive, a sealant, a coating agent, or a 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 component 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, comprising the steps of: an epoxidation step; a first low-boiling point removal step; a high-boiling point removal step; and a second low-boiling point 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:

[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 distiller. 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 the formulae (a) to (c) by distillation using a distillation column.

Claims (9)

The purity of the compound represented by the following formula (1) is 80% or more,
An epoxy compound product, comprising 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 amount of 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.] The epoxy compound product according to claim 1, wherein the compound represented by formula (1) is an epoxidation 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.] The epoxy compound product according to claim 2, wherein the aliphatic percarboxylic acid is peracetic acid. A curable composition comprising the epoxy compound product of claim 1 and a curing agent and/or a curing catalyst. A curable composition comprising the epoxy compound product of claim 1 and other epoxy compounds and/or oxetane compounds. The curable composition according to claim 4 or 5, which is an adhesive, a sealant, a coating agent, or a hard coat agent. A cured product of the curable composition according to claim 4 or 5. An optical member comprising the cured product according to claim 7. The method for producing an epoxy compound product according to any one of claims 1 to 3, wherein the epoxy compound product is 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.
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 distiller. 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 the formulae (a) to (c) by distillation using a distillation column.

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