Epoxy compound preparation

Abstract

The present invention provides an epoxy compound product capable of forming a cured product that is less likely to generate outgassing in a high-heat environment. In the case of the epoxy compound product of the present disclosure, the purity of a compound represented by the following formula (1) is 80% or greater, and the total proportion 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) 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 optionally have a substituent at one or more of the carbon atoms constituting the ring.]

Description

Technical Field

[0001] This disclosure relates to a high-purity epoxy compound article. Furthermore, this application claims priority to Japanese Patent Application No. 2023-192638, filed on November 10, 2023, the contents of which are incorporated herein by reference. Background Technology

[0002] Epoxy compounds, through reaction with various curing agents and catalysts, can form cured products with excellent properties such as high strength, 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, and sealants.

[0003] Examples of the aforementioned alicyclic epoxy compounds include 3,4-epoxycyclohexylmethyl (3',4'-epoxy)cyclohexylcarbamate and 3,4-epoxy-6-methyl-cyclohexylmethyl (3',4'-epoxy-6'-methyl)cyclohexylcarbamate (see Patent Documents 1 and 2).

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: International Publication No. 2019 / 138988

[0007] Patent Document 2: US Patent No. 2,890,194 Summary of the Invention

[0008] The problem that the invention aims to solve

[0009] However, conventional alicyclic epoxy compound products contain low-boiling-point compounds as impurities, which presents problems such as the following: in products containing cured alicyclic epoxy compounds, these low-boiling-point compounds volatilize and cause degassing under high-temperature environments. If degassing occurs, for example, when the cured product is used as a sealing material for semiconductor devices such as organic EL, cracks may sometimes form in the inorganic material film within the semiconductor device, resulting in insufficient sealing.

[0010] Therefore, the purpose of this disclosure is to provide an epoxy compound article that can form a cured product that is not prone to degassing under high-temperature conditions.

[0011] Solution for solving the problem

[0012] That is, this disclosure provides an epoxy compound article, wherein the purity of the compound represented by formula (1) is 80% or more, and the total content of 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.

[0013] [Chemical Formula 1]

[0014]

[0015] [In the formula, X represents a single bond or a linking group. Optionally, the cyclohexane ring and the benzene ring may have substituents on more than one carbon atom constituting the ring.]

[0016] The compound represented by formula (1) above is preferably an epoxide formed from an aliphatic peroxycarboxylic acid of the compound represented by formula (2) below.

[0017] [Chemical Formula 2]

[0018]

[0019] [In formula (2), X represents a single bond or a linking group, the same as X in formula (1). The cyclohexene ring in formula (2) may optionally have substituents on more than one of the carbon atoms constituting the ring.]

[0020] The aliphatic peroxycarboxylic acid mentioned above is preferably peracetic acid.

[0021] Furthermore, this disclosure provides a curable composition comprising the aforementioned epoxy compound article, curing agent, and / or curing catalyst.

[0022] Furthermore, this disclosure provides a curable composition comprising the above-mentioned epoxy compound article, other epoxy compounds and / or oxetane compounds.

[0023] The above-mentioned curable composition is preferably an adhesive, sealant, coating agent or hard coating agent.

[0024] Furthermore, this disclosure provides a cured product, which is a cured product of the above-described curable composition.

[0025] Furthermore, this disclosure provides an optical component having the aforementioned cured material.

[0026] Furthermore, this disclosure provides a method for manufacturing an epoxy compound article, which is a method for manufacturing the epoxy compound article described above, wherein the epoxy compound article is manufactured by performing the following epoxidation process, the following first de-low boiling point removal process, the following high boiling point removal process, and the following second de-low boiling point removal process.

[0027] Epoxidation process: The process of reacting the compound shown in formula (2) with an organic peroxy acid to obtain the reaction product.

[0028] [Chemical Formula 2]

[0029]

[0030] [In formula (2), X represents a single bond or a linking group. The cyclohexene ring in formula (2) may optionally have substituents on one or more carbon atoms constituting the ring.]

[0031] The first step is to remove low-boiling-point components through distillation using a thin-film still.

[0032] High-boiling-point removal process: The process of removing high-boiling-point components through distillation.

[0033] The second low-boiling step is a step of removing the compounds shown in formulas (a) to (c) by distillation using a distillation column.

[0034] Invention Effects

[0035] The epoxy compound articles disclosed herein can form cured products that are not prone to degassing under high-temperature environments. Attached Figure Description

[0036] Figure 1 This refers to the alicyclic epoxy compound article 1 produced in Example 1. 1 H-NMR spectrum.

[0037] Figure 2 The chromatogram of the alicyclic epoxy compound product 1 prepared in Example 1 is shown by GC-MS.

[0038] Figure 3 This represents the peak report obtained by GC-MS for the alicyclic epoxy compound product 1 prepared in Example 1. Detailed Implementation

[0039] [Epoxy compound products]

[0040] The epoxy compound articles disclosed herein contain a compound represented by the following formula (1), the purity (or content) of which is 80% or more.

[0041] [Chemical Formula 3]

[0042]

[0043] In formula (1), X represents a single bond or a linking group. The cyclohexane ring (epoxycyclohexyl) in formula (1) optionally has substituents on one or more carbon atoms constituting the ring.

[0044] Examples of linking groups include: divalent hydrocarbon groups, alkenyl groups with part or all of the carbon-carbon double bond epoxidized, carbonyl groups, ether bonds, thiol bonds, ester bonds, carbonate groups, amide groups, -SO-, -SO2-, -CBr2-, -C(CBr3)2-, -C(CF3)2-, and groups formed by linking multiple of these groups. Among these linkers, groups from the group consisting of ether bonds, thiol bonds, -SO-, -SO2-, -CH2-, -C(CH3)2-, -CBr2-, -C(CBr3)2-, and -C(CF3)2- are preferred.

[0045] Examples of divalent hydrocarbon groups include straight-chain or branched alkylene groups and divalent alicyclic hydrocarbon groups with 1 to 18 carbon atoms. Examples of straight-chain or branched alkylene groups with 1 to 18 carbon atoms include methylene, methylmethylene, dimethylmethylene, ethylene, propylene, and trimethylene. Examples of divalent alicyclic hydrocarbon groups include 1,2-cyclopentylene, 1,3-cyclopentylene, cyclopentylene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene, and cyclohexylene, etc., which are divalent cycloalkylene groups (including cycloalkylene groups).

[0046] Examples of alkenyl groups (sometimes called "epoxidized alkenyl groups") in which part or all of the aforementioned carbon-carbon double bonds are epoxidized include: vinylidene, propenide, 1-butenide, 2-butenide, butadienylene group, pentenide, hexenide, heptenide, octene, and other straight-chain or branched alkenyl groups with 2 to 8 carbon atoms. In particular, alkenyl groups in which all of the carbon-carbon double bonds are epoxidized are preferred, and alkenyl groups in which all of the carbon-carbon double bonds are epoxidized with 2 to 4 carbon atoms are more preferred.

[0047] Substituents optionally present in the cyclohexane ring may include, for example, halogen atoms, hydrocarbon groups optionally having oxygen or halogen atoms, and alkoxy groups optionally having substituents. In the case of multiple substituents, these multiple substituents may optionally be the same or different.

[0048] Representative examples of alicyclic epoxy compounds shown in formula (1) above include: (3,4,3',4'-diepoxy)bicyclohexane, and compounds shown in formulas (i-1) to (i-10) below. It should be noted that in formulas (i-5) and (i-7) below, l and m represent integers from 1 to 30. In formula (i-5) below, R' is an alkylene group having 1 to 8 carbon atoms, preferably a straight-chain or branched alkylene group having 1 to 3 carbon atoms, such as methylene, ethylene, propylene, or isopropylene. In formulas (i-9) and (i-10) below, n1 to n6 represent integers from 1 to 30. In addition, as alicyclic epoxy compounds represented by formula (i) above, other examples include 2,2-bis(3,4-epoxycyclohexyl)propane, 1,2-bis(3,4-epoxycyclohexane-1-yl)ethane, 1,2-epoxy-1,2-bis(3,4-epoxycyclohexane-1-yl)ethane, bis(3,4-epoxycyclohexylmethyl) ether, etc.

[0049] [Chemical Formula 4]

[0050]

[0051] [Chemical Formula 5]

[0052]

[0053] Furthermore, epoxy-modified siloxanes can be listed as compounds represented by formula (1) above. Examples of such epoxy-modified siloxanes include chain-like or cyclic polyorganosiloxanes having structural units represented by formula (i') below.

[0054] [Chemical Formula 6]

[0055]

[0056] In the above formula (i'), R 3 R represents a substituent containing a group represented by formula (1a) below or a substituent containing a group represented by formula (1b) below. 4 It indicates alkyl or alkoxy.

[0057] [Chemical Formula 7]

[0058]

[0059] In equations (1a) and (1b), R 1a R 1bThe same or different indicates straight-chain or branched alkylene groups, such as methylene, methylmethylene, dimethylmethylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, decamethylene, etc., which are straight-chain or branched alkylene groups with 1 to 10 carbon atoms.

[0060] The epoxy equivalent (according to JIS K7236) of the above-mentioned epoxy-modified siloxane is, for example, 100 to 400, preferably 150 to 300.

[0061] As the aforementioned epoxy-modified siloxane, for example, commercially available products such as the compound shown in the following formula (i'-1) (trade name "KR-470", manufactured by Shin-Etsu Chemical Industry Co., Ltd.) can be used.

[0062] [Chemical Formula 8]

[0063]

[0064] From the viewpoint of further reducing the amount of degassing generated from the solidified product, the purity of the compound shown in formula (1) above is preferably 85% or more, more preferably 90% or more, even more preferably 91% or more, and may also be 92% or more, 93% or more, 95% or more, or 96% or more.

[0065] The purity of the compound represented by formula (1) in the above-mentioned epoxy compound product can be calculated as a proportion based on the peak area of ​​gel permeation chromatography (GPC). Furthermore, the purity of the compound represented by formula (1) in the above-mentioned epoxy compound product can be obtained by calculating the proportion of the peak area corresponding to the compounds represented by formulas (a) to (c) and then removing the remaining proportion. In the case of overlapping peak shoulders, the peak area is defined by a vertical line relative to the baseline that passes through the area between the peaks and valleys.

[0066] Furthermore, regarding the aforementioned epoxy compound articles, relative to the total amount (100% by mass) of the aforementioned epoxy compound articles, the total content of the compounds shown in formula (a), formula (b), and 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 0.3% by mass or less. The aforementioned total content is, for example, 0.005% by mass or more, or 0.01% by mass or more, or 0.05% by mass or more. The aforementioned epoxy compound articles may contain one, two, or three of the compounds shown in formulas (a) to (c), or may contain none at all.

[0067] [Chemical Formula 9]

[0068]

[0069] In formulas (a) to (c), X represents a single bond or a linking group, corresponding to X in formula (1), and is the same as X in formula (1). The cyclohexane ring and benzene ring in formulas (a) to (c) may optionally have substituents on one or more carbon atoms constituting the ring. Examples of substituents that may be optionally present on the cyclohexane ring in formula (1) are provided. In cases where multiple substituents are present, these multiple substituents may optionally be the same or different.

[0070] The compounds shown in formulas (a) to (c) above do not have epoxy groups, and therefore will not cure when the composition containing the epoxy compound is cured. Therefore, the compounds shown in formulas (a) to (c) above will remain in the cured product. Furthermore, when the cured product is placed in a high-heat environment, the compounds shown in formulas (a) to (c) above volatilize and become degassed. In the case of the epoxy cured product above, the total content of the compounds shown in formulas (a) to (c) above is 1% by mass or less, thus these compounds are less likely to remain in the cured product, and the amount of degassed is reduced. In addition, it also results in low curing shrinkage, reduced curling during curing, excellent adhesion to the substrate, improved curing performance based on active energy rays, shorter curing time, and excellent heat resistance and transparency of the cured product.

[0071] The total proportions of the compounds shown in formula (a), formula (b), and formula (c) can be calculated as the proportions of peak areas based on gas chromatography and mass spectrometry (GC-MS), respectively. For example, in gas chromatography, when the relative retention time of the peak of the compound shown in formula (1) is set to 1.0, the compounds shown in formulas (a) to (c) have relative retention times in the range of 0.7 to 0.72 (e.g., in...). Figure 2 In the chromatogram shown, the range earlier than RT17.8 min was detected.

[0072] The Hassen color number (APHA) of the above-mentioned 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.

[0073] (Manufacturing method of epoxy compound products)

[0074] The above-mentioned epoxy compound products are obtained by epoxidizing the compound shown in formula (2) below with organic peroxy acid.

[0075] [Chemical Formula 2]

[0076]

[0077] In formula (2), X represents a single bond or linking group, corresponding to X in formula (1), and is the same as X in formula (1). The cyclohexene ring in formula (2) may optionally have substituents on one or more carbon atoms constituting the ring. Examples of substituents that may be optionally present on the cyclohexane ring in formula (1) are provided. In the case of multiple substituents, these multiple substituents may optionally be the same or different.

[0078] More specifically, the aforementioned epoxy compound product can be manufactured through the following epoxidation process, the following first de-low-boiling point removal process, the following high-boiling point removal process, and the following second de-low-boiling point removal process. It should be noted that the order of the above processes is not particularly limited. For example, either the first de-low-boiling point removal process or the second de-low-boiling point removal process can be performed first. Preferably, the first de-low-boiling point removal process, the high-boiling point removal process, and the second de-low-boiling point removal process are performed sequentially.

[0079] Epoxidation process: The process of reacting the compound shown in formula (2) above with an organic peroxy acid to obtain the reaction product.

[0080] The first step is the removal of low-boiling-point components through distillation.

[0081] High-boiling-point removal process: The process of removing high-boiling-point components through distillation.

[0082] Second low-boiling point removal process: The process of removing the compounds shown in formulas (a) to (c) by distillation.

[0083] In addition, after the epoxidation process and before the first de-low boiling point process, the second de-low boiling point process, and the de-high boiling point process, a process (washing process) can be provided to wash the obtained reaction product with water to remove the organic peroxy acid used in the reaction and its decomposition products.

[0084] (1) Epoxidation process

[0085] The epoxidation process is a process in which the compound shown in formula (2) above is reacted with an organic peroxyacid to obtain a reaction product. In this process, a reaction product containing the compound shown in formula (1) above can be obtained.

[0086] Examples of the aforementioned organic peroxyacids include peroxyformic acid, peracetic acid, perpropionic acid, m-chloroperoxybenzoic acid, trifluoroperacetic acid, and peroxybenzoic acid. Only one or more of these organic peroxyacids may be used. Aliphatic peroxycarboxylic acids are preferred, and peracetic acid is more preferred.

[0087] The aforementioned aliphatic peroxycarboxylic acids are preferably oxides of their corresponding aldehydes and oxygen. Such aliphatic peroxycarboxylic acids are essentially anhydrous and do not readily undergo ring-opening of epoxide groups.

[0088] The amount of organic peroxy acid used is, for example, 0.5 to 3 moles relative to 1 mole of the compound shown in formula (2) above.

[0089] Epoxidation reactions can be carried out in the presence of a solvent. Examples of such solvents include: aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene, diethylbenzene, and p-isopropyltoluene; alicyclic hydrocarbons such as cyclohexane and decahydronaphthalene; 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; polyols and their derivatives 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. One of the solvents mentioned above may be used, or two or more may be used.

[0090] The amount of solvent used is, for example, about 0.2 to 10 times the mass of the compound shown in formula (2) above.

[0091] In the epoxidation reaction, stabilizers such as organic peroxy acids (e.g., ammonium hydrogen phosphate, potassium pyrophosphate, 2-ethylhexyl tripolyphosphate, etc.) and polymerization inhibitors (e.g., hydroquinone, piperidine, ethanolamine, phenothiazine, etc.) can be used as needed.

[0092] The reaction temperature for epoxidation is, for example, 0–70°C. There are no particular restrictions on the reaction atmosphere, as long as it does not hinder the reaction; for example, it can be any atmosphere such as air, nitrogen, or argon.

[0093] (2) Cleaning process

[0094] The above-mentioned cleaning process is a process of removing organic peroxy acids and organic acids as decomposition products contained in the reaction products obtained from the epoxidation process by washing with water. In addition, the organic peroxy acids can be neutralized by using an alkali such as sodium hydroxide during water washing.

[0095] The amount of water used is, for example, about 0.1 to 3 times (v / v) the amount of reaction product. Water washing can be performed using a balanced extractor such as a mixer-sedimentator type, an extraction tower, or a centrifugal extractor.

[0096] (3) First process for removing low-boiling point

[0097] The first low-boiling point removal step described above is a process of distilling away components (such as solvents, water, etc.) in the reaction product that have a lower boiling point than the compound shown in formula (1) above. In this step, low-boiling point components other than the compounds shown in formulas (a) to (c) above are mainly removed, but a portion of the compounds shown in formulas (a) to (c) above can also be removed. By implementing this step, the content of low molecular weight compounds mixed in epoxy compound products can be reduced to an extremely low level.

[0098] In the first low-boiling point removal process, distillation is preferably performed using a thin-film evaporator. Distillation is preferably carried out under conditions ranging from a heating temperature of 50 to 200°C and a pressure of 1 to 760 torr. Distillation can also be carried out in two stages by varying the pressure and temperature.

[0099] When performing the first de-boiling step on the reaction product, it is preferable to add a polymerization inhibitor from the perspective of suppressing the ring-opening polymerization reaction of the compound shown in formula (1) above. The amount of polymerization inhibitor added varies slightly depending on its 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.

[0100] In the first de-boiling step, components with lower boiling points than the compounds shown in formulas (a) to (c) above are removed from the reaction product by evaporation, and a mixture of the compounds shown in formulas (a) to (c) above, the compounds shown in formula (1) above, and components with higher boiling points than them is obtained as a residual liquid.

[0101] (4) High-boiling point removal process

[0102] The aforementioned high-boiling point removal process is a process of distilling away components in the reaction product whose boiling points are higher than those of the compounds shown in formulas (a) to (c) and the compound shown in formula (1). When the aforementioned high-boiling point removal process is performed after the aforementioned first low-boiling point removal process, the high-boiling point removal process involves distilling off the compounds shown in formula (1) and the compounds shown in formulas (a) to (c) from the residual liquid obtained after the aforementioned first low-boiling point removal process, i.e., a mixture of the compounds shown in formulas (a) to (c), the compound shown in formula (1), and components with boiling points higher than them. By implementing this process, the content of high molecular weight compounds mixed in with epoxy compound products can be reduced to an extremely low level.

[0103] In the de-boiling process, distillation can be carried out using either a distillation column or a thin-film evaporator, but a thin-film evaporator is preferred for the purpose of suppressing residence time during distillation. From the viewpoint of suppressing the decomposition of the compound shown in formula (1) and the resulting increase in color intensity, or the ring-opening polymerization of the epoxy groups of the compound shown in formula (1) and the resulting gelation, distillation is preferably carried out at a heating temperature of 250°C or lower (preferably 230°C or lower). The distillation temperature is preferably 50°C or higher, more preferably 100°C or higher. Furthermore, from the same viewpoint, distillation is preferably carried out at a pressure of 3 torr or lower (preferably 0.7 torr or lower). From the viewpoint of further improving the purity of the epoxy compound product, the pressure is preferably 0.01 torr or higher, and may also be 0.02 torr or higher.

[0104] (5) Second process for removing low-boiling point

[0105] The second low-boiling point removal process described above is a process of distilling away the compounds represented by formulas (a) to (c) contained in the reaction products. By implementing this process, the content of the compounds represented by formulas (a) to (c) mixed in the epoxy compound products can be reduced to an extremely low level.

[0106] In the second low-boiling point removal process, a distillation column is preferably used for distillation. When the second low-boiling point removal process is performed after the above-mentioned high-boiling point removal process, the distillate obtained from the above-mentioned high-boiling point removal process is introduced into a distillation column, and the compounds shown in formulas (a) to (c) are removed by distillation from the mixture of the compounds shown in formula (1) and the compounds shown in formulas (a) to (c) by evaporation, and the compound shown in formula (1) is obtained as a residual liquid.

[0107] As a distillation column, for example, a packed column or a plate column can be used. The actual number of plates in the distillation column is preferably 14 or more, and considering the further improvement of the purity of the product, it is preferably 14 to 100, and particularly preferably 14 to 50.

[0108] In the second de-boiling step, distillation is preferably carried out at a temperature below 250°C (e.g., 50–250°C) and a residence time at the bottom of the vessel of less than 10 hours (e.g., more than 1 hour and less than 10 hours). Distillation can also be carried out in two stages by varying the pressure and temperature. By setting the heating temperature below 260°C, the ring-opening polymerization of the epoxy compound can be suppressed, allowing distillation to proceed smoothly. Furthermore, by setting the heating temperature below 250°C, the coloring of the obtained epoxy compound can be suppressed.

[0109] By processing the reaction product, especially by sequentially performing the first de-boiling step, the de-high boiling step, and the second de-boiling step, the above-mentioned epoxy compound product containing the compound shown in formula (1) with high purity and with a significant reduction in the compounds shown in formulas (a) to (c) can be obtained.

[0110] Epoxy compound products obtained by distillation purification using a conventional thin-film still (WFE) tend to contain a high content of the compounds shown in formulas (a) to (c) above. Furthermore, if the low-boiling and high-boiling point removal processes using a WFE are not performed, or if the reaction product obtained after solvent removal through the low-boiling point removal process is distilled in a distillation column, the residence time at the bottom of the vessel becomes longer, resulting in significant coloring and gelation caused by ring-opening polymerization. Moreover, in purification using a WFE, it is impossible to separate the compounds shown in formulas (a) to (c) above from the compound shown in formula (1) above. On the other hand, if the low-boiling point removal and high-boiling point removal processes are performed together using a distillation column, the residence time at the bottom of the vessel becomes longer, resulting in significant coloring and gelation caused by ring-opening polymerization. In contrast, in particular, after performing the low-boiling and high-boiling removal processes using WFE, precision distillation is carried out under the conditions of having an actual number of trays of 14 or more in the distillation column, a heating temperature of 250°C or less, and a residence time at the bottom of the vessel of less than 10 hours, thereby efficiently removing the compounds shown in formulas (a) to (c) above.

[0111] [Curing composition]

[0112] The compound represented by formula (1) above is a curable compound, and the curable composition can be obtained by using the above-described epoxy compound article. The above-described curable composition comprises the above-described epoxy compound article.

[0113] (Curing compounds)

[0114] The curable composition described above contains at least one compound of formula (1) contained in the epoxy compound article described above as a curable compound. The curable composition described above may also contain other curable compounds besides the compound of formula (1) described above. The other curable compounds may be only one or more.

[0115] Examples of other curable compounds include: epoxy compounds other than those shown in formula (1) above; compounds having one or more oxetane groups (sometimes referred to as "oxetane compounds"); and compounds having one or more vinyl ether groups (sometimes referred to as "vinyl ether compounds"). The curable composition may also contain the aforementioned other epoxy compounds and / or oxetane compounds as other compounds.

[0116] The aforementioned other epoxy compounds are compounds having one or more epoxy groups (ethylene oxide) within their molecules. Among these, compounds having two or more epoxy groups (preferably 2 to 6, more preferably 2 to 4) within their molecules are preferred.

[0117] Other epoxy compounds mentioned above include alicyclic epoxy compounds, aromatic epoxy compounds, and aliphatic epoxy compounds.

[0118] As for the aforementioned alicyclic epoxy compounds, there are known or conventional compounds that have one or more alicyclic rings and one or more epoxy groups in the molecule, without particular limitation. For example, the following can be listed: (I) compounds in which epoxy groups are directly bonded to the alicyclic ring by single bonds; (II) compounds in which an alicyclic ring and a glycidyl ether group are present in the molecule (glycidyl ether type epoxy compounds), etc.

[0119] As compounds in (I) above that have an epoxy group directly bonded to the alicyclic ring by a single bond, examples include compounds represented by the following formula (ii).

[0120] [Chemical Formula 10]

[0121]

[0122] In formula (ii), R” is a group (p-valent organic group) obtained by removing p hydroxyl groups (-OH) from the structural formula of a p-hydronic alcohol, where p and n represent natural numbers. As a p-hydronic alcohol [R””OH] p Examples of compounds represented by formula (ii) include polyols such as 2,2-bis(hydroxymethyl)-1-butanol (alcohols with 1 to 15 carbon atoms). p is preferably 1 to 6, and n is preferably 1 to 30. When p is 2 or more, the n in each group within the parentheses can be the same or different. Specifically, examples of compounds represented by formula (ii) include 1,2-epoxy-4-(2-epoxyethylene)cyclohexane adducts of 2,2-bis(hydroxymethyl)-1-butanol [e.g., trade name "EHPE3150" (manufactured by DAICEL Co., Ltd.)].

[0123] Examples of compounds containing an alicyclic ring and a glycidyl ether group within the molecules described in (II) above include, for example, glycidyl ethers of alicyclic alcohols (especially alicyclic polyols). More specifically, examples include, for instance, compounds formed by hydrogenating bisphenol A type epoxides (hydrogenated bisphenol A type epoxides), such as 2,2-bis[4-(2,3-epoxypropoxy)cyclohexyl]propane and 2,2-bis[3,5-dimethyl-4-(2,3-epoxypropoxy)cyclohexyl]propane; 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[o ... Compounds formed by hydrogenating bisphenol F type epoxides such as [3,5-dimethyl-4-(2,3-epoxypropoxy)cyclohexyl]methane (hydrogenated bisphenol F type epoxides); hydrogenated biphenol type epoxides; hydrogenated phenol linear phenolic type epoxides; hydrogenated cresol linear phenolic type epoxides; hydrogenated cresol linear phenolic type epoxides of bisphenol A; hydrogenated naphthalene type epoxides; hydrogenated epoxides of epoxides obtained from triphenolmethane; and hydrogenated epoxides of other epoxides having aromatic rings, etc.

[0124] The aforementioned aromatic epoxy compounds are compounds having one or more aromatic rings (aromatic hydrocarbon rings or aromatic heterocycles) and one or more epoxy groups within the molecule. Preferably, these are compounds (aromatic glycidyl ether-based epoxy compounds) formed by bonding one or more carbon atoms of an aromatic ring (especially an aromatic hydrocarbon ring) having carbon atoms with epoxypropoxy groups.

[0125] Examples of the aforementioned aromatic epoxy compounds include: epi-bis type glycidyl ether epoxy resins obtained by the condensation reaction of bisphenols (e.g., bisphenol A, bisphenol F, bisphenol S, bisphenol fluorene, etc.) with epi-halo alcohols; high molecular weight epi-bis type glycidyl ether epoxy resins obtained by further adding these epi-bis type glycidyl ether epoxy resins to the aforementioned bisphenols; and phenols (e.g., phenol, cresol, xylenol, resorcinol, phthalic acid, etc.) Polyols are obtained by condensing phenols, bisphenol A, bisphenol F, bisphenol S, etc. with aldehydes [e.g., formaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, salicylaldehyde, etc.], and then further condensing these polyols with epihaloalcohols to obtain phenolic varnishes / alkyl glycidyl ether type epoxy resins; epoxy compounds are formed by bonding two phenolic skeletons at the 9-position of the fluorene ring, and by bonding the oxygen atoms after removing hydrogen atoms from the hydroxyl groups of these phenolic skeletons directly or through alkylene oxygen groups to glycidyl groups, etc.

[0126] Examples of the aforementioned aliphatic epoxides include: glycidyl ethers of q-hydroxides (q being a natural number) that do not have a cyclic structure; glycidyl esters of mono- or polycarboxylic acids [e.g., acetic acid, propionic acid, butyric acid, stearic acid, adipic acid, sebacic acid, maleic acid, itaconic acid, etc.]; epoxides of oils containing double bonds, such as epoxidized linseed oil, epoxidized soybean oil, and epoxidized castor oil; and epoxides of polyolefins (including polyalkyl dienes), such as epoxidized polybutadiene. It should be noted that the aforementioned non-cyclic q-ols can include, for example: monohydric alcohols such as methanol, ethanol, 1-propanol, isopropanol, 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 polyols with three or more nucleotides such as glycerol, diglycerol, erythritol, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, and sorbitol. Furthermore, q-ols can also be polyether polyols, polyester polyols, polycarbonate polyols, and polyolefin polyols.

[0127] As for the aforementioned oxetane compounds, examples include well-known or conventional compounds having one or more oxetane rings within their molecules, without particular limitation. Examples include: 3,3-bis(ethoxymethyl)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-oxetane-butylmethoxy)methyl]benzene, bis{ [1-Ethyl(3-oxetane)]methyl ether, 4,4'-bis[(3-ethyl-3-oxetane)methoxymethyl]bicyclohexane, 1,4-bis[(3-ethyl-3-oxetane)methoxymethyl]cyclohexane, 1,4-bis{[(3-ethyl-3-oxetane)methoxy]methyl}benzene, 3-ethyl-3-{[(3-ethyloxetane-3-yl)methoxy]methyl}oxetane, phenylenedimethylenedioxetane, 3-ethyl-3-{[3-(triethoxysilyl)propoxy]methyl}oxetane, oxetane-butylsilsesquioxane, phenolic varnish oxetane, etc.

[0128] As the aforementioned vinyl ether compounds, known or conventional compounds having one or more vinyl ether groups within the molecule can be used, without particular limitation. Examples 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-cyclohexanediethanol monovinyl ether, 1,4-cyclohexanediethanol divinyl ether, 1,3-cyclohexanediethanol monovinyl ether, 1,3-cyclohexanediethanol divinyl ether, 1,2-cyclohexanediethanol monovinyl ether, 1,2-cyclohexanediethanol 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 Ethers, 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, oligomeric polyethylene glycol monovinyl ether, oligomeric polyethylene 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, oligomeric propylene glycol monovinyl ether, oligomeric propylene glycol divinyl ether, polypropylene glycol monovinyl ether Ethers, 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, cyclohexanediethanol divinyl ether, trimethylolpropane divinyl ether, trimethylolpropane trivinyl ether, bisphenol A divinyl ether, bisphenol F divinyl ether, hydroxyoxanorbornene methanol divinyl ether, 1,4-cyclohexanediol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, etc.

[0129] The proportion of the compound represented by the above formula (1) to the total amount (100% by mass) of the curing compound contained in the above curing composition is, for example, 50% by mass or more (e.g., 50 to 100% by mass), preferably 60% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more.

[0130] The curable composition described above preferably contains, in addition to a curable compound, one or more components selected from the group consisting of a curing agent, a curing accelerator, and a curing catalyst. The curable composition described above preferably includes a curing agent and / or a curing catalyst.

[0131] The total content of the curing compound, curing agent and / or curing accelerator in the total amount (100% by mass) of the above-mentioned curing composition is, for example, 60% by mass or more, preferably 70% by mass or more, more preferably 80% by mass or more, further preferably 90% by mass or more, and particularly preferably 95% by mass or more.

[0132] The total content of the curing compound and the curing catalyst in the total amount (100% by mass) of the above-mentioned curing composition is, for example, 60% by mass or more, preferably 70% by mass or more, more preferably 80% by mass or more, further preferably 90% by mass or more, and particularly preferably 95% by mass or more.

[0133] The proportion of compounds other than the curing compound, curing agent, curing accelerator and curing catalyst, relative to the total amount (100% by mass) of the above curing composition, is, for example, 50% by mass or less, preferably 40% by mass or less.

[0134] (Curing agent)

[0135] As the aforementioned curing agents, for example, the following are known or commonly used curing agents for epoxy resins: acid anhydrides (acid anhydride curing agents), amines (amine curing agents), polyamide resins, imidazoles (imidazolium curing agents), polythiols (polythiols curing agents), phenols (phenol curing agents), polycarboxylic acids, dicyandiamide, organic acid hydrazides, etc. Only one of the above-mentioned curing agents may be used, or two or more may be used.

[0136] Examples of the aforementioned acid anhydrides include: methyltetrahydrophthalic anhydride (4-methyltetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, etc.), methylhexahydrophthalic anhydride (4-methylhexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, etc.), dodecenylsuccinic anhydride, methylneodymethylenetetrahydrophthalic anhydride, phthalic anhydride, maleic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride. Dicarboxylic anhydride, methylcyclohexene dicarboxylic 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, dodecanoic anhydride, methylcyclohexene tetracarboxylic anhydride, vinyl ether-maleic anhydride copolymer, alkylstyrene-maleic anhydride copolymer, etc. From an operability point of view, anhydrides that are liquid at 25°C are preferred [e.g., methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, dodecenyl succinic anhydride, methylnenomyltetrahydrophthalic anhydride, etc.].

[0137] Examples of the aforementioned amines include: ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenediamine, diethylaminopropylamine, polypropylenetriamine, and other aliphatic polyamines; menthene diamine... Alicyclic polyamines such as diamine, isophorone diamine, bis(4-amino-3-methyldicyclohexyl)methane, diaminodicyclohexylmethane, bis(aminomethyl)cyclohexane, N-aminoethylpiperazine, 3,9-bis(3-aminopropyl)-3,4,8,10-tetraoxaspiro[5,5]undecane; mononuclear polyamines such as m-phenylenediamine, p-phenylenediamine, toluene-2,4-diamine, toluene-2,6-diamine, mesitylene-2,4-diamine, 3,5-diethyltoluene-2,4-diamine, 3,5-diethyltoluene-2,6-diamine; and aromatic polyamines such as biphenylenediamine, 4,4-diaminodiphenylmethane, 2,5-naphthylenediamine, and 2,6-naphthylenediamine.

[0138] Examples of polyamide resins include those containing either or both of primary and secondary amino groups within the molecule.

[0139] Examples of the imidazoles mentioned above 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, 1-cyanoethyl-2-undecylimidazole ontyltriazine, 1-cyanoethyl-2-phenylimidazole ontyltriazine, 2-methylimidazole ontyltriazine isocyanurate, 2-phenylimidazole ontyltriazine, 2,4-diamino-6-[2-methylimidazole-(1)]-ethyl-triazine, 2,4-diamino-6-[2-ethyl-4-methylimidazole-(1)]-ethyl-triazine, etc.

[0140] Examples of polythiols include liquid polythiols and polysulfide resins.

[0141] Examples of the aforementioned phenols include: phenolic resins in the form of varnish, phenolic resins in the form of cresol in the form of varnish, terephthalic acid modified phenolic resins, terephthalic acid / isophthalic acid modified phenolic resins and other aralkyl resins, terpene modified phenolic resins, dicyclopentadiene modified phenolic resins, triphenol propane, etc.

[0142] Examples of polycarboxylic acids mentioned above include: adipic acid, sebacic acid, terephthalic acid, trimellitic acid, and carboxyl-containing polyesters.

[0143] As a curing agent, from the viewpoint of the heat resistance and transparency of the obtained cured product, acid anhydride-based curing agents are preferred. For example, commercially available products such as "RIKACID MH-700", "RIKACID MH-700F" (manufactured by Shin Nippon Rikka Co., Ltd.) and "HN-5500" (manufactured by Hitachi Chemical Co., Ltd.) can be used.

[0144] The content (amount) of the curing agent relative to 100 parts by mass of the total amount of epoxy compound contained in the curable composition is preferably 50 to 200 parts by mass, more preferably 80 to 150 parts by mass. More specifically, when using an anhydride as the curing agent, it is preferable to use it at a ratio of 0.5 to 1.5 equivalents for every 1 equivalent of epoxy groups in all the epoxy compounds contained in the above-mentioned curable composition. If the content of the curing agent is 50 parts by mass or more, curing can be carried out sufficiently, and there is a tendency to improve the strength and toughness of the resulting cured product. On the other hand, if the content of the curing agent is 200 parts by mass or less, there is a tendency to further suppress coloration and obtain a cured product with excellent hue.

[0145] (Curing accelerator)

[0146] When the above-described curable composition contains a curing agent, it is preferable to also contain a curing accelerator. The curing accelerator has the effect of accelerating the reaction rate when a compound having an epoxy group (ethylene oxide) reacts with the curing agent.

[0147] Examples of curing accelerators mentioned above include: 1,8-diazabicyclo[5.4.0]undecene-7 (DBU) or its salts (e.g., phenolates, octanoates, p-toluenesulfonates, formates, tetraphenylborates, etc.); 1,5-diazabicyclo[4.3.0]nonene-5 (DBN) or its salts (e.g., phenolates, octanoates, p-toluenesulfonates, formates, tetraphenylborates, etc.); tertiary amines such as benzyl dimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 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-toluyl)borate; organometallic salts such as zinc octanoate, tin octanoate, and zinc stearate; and metal chelates such as aluminum acetylacetone complexes. The above-mentioned curing accelerators can be used in one or more ways.

[0148] As the aforementioned curing accelerator, commercially available products such as "U-CAT SA 506", "U-CAT SA 102", "U-CAT 5003", "U-CAT 18X", "U-CAT 12XD" (developed products) (manufactured by San-Apro Co., Ltd.); "TPP-K" and "TPP-MK" (manufactured by Hokuko Chemical Industry Co., Ltd.); and "PX-4ET" (manufactured by Nippon Chemical Industry Co., Ltd.) can be used.

[0149] The content (amount) of the curing accelerator relative to 100 parts by weight of the curing agent is preferably 0.01 to 5 parts by weight, more preferably 0.02 to 3 parts by weight, and even more preferably 0.03 to 3 parts by weight. If the content of the curing accelerator is 0.01 parts by weight or more, there is a tendency to obtain a more efficient curing promotion effect. On the other hand, if the content of the curing accelerator is 5 parts by weight or less, there is a tendency to further suppress coloration and obtain a cured product with excellent hue.

[0150] (Catalyst solidification)

[0151] The curable composition described above may also include a curing catalyst instead of a curing agent. The curing catalyst has the function of curing the curable composition by initiating and / or promoting the curing reaction (polymerization reaction) of cationic curable compounds such as those represented by formula (1) above. Examples of curing catalysts include: cationic polymerization initiators (photocationic polymerization initiators, thermal cationic polymerization initiators, etc.) that generate cationic species by applying light irradiation, heat treatment, etc., Lewis acid-amine complexes, Brønsted acid salts, imidazoles, etc. Only one of the above curing catalysts may be used, or two or more may be used.

[0152] In addition, examples of photocationic polymerization initiators include: triarylsulfonium hexafluorophosphate (e.g., p-phenylthiophenyl diphenylsulfonium hexafluorophosphate), triarylsulfonium hexafluoroantimonate, and other sulfonium salts (especially triarylsulfonium salts); diaryliodomonium hexafluorophosphate, diaryliodomonium hexafluoroantimonate, bis(dodecylphenyl)iodomonium tetra(pentafluorophenyl)borate, iodomonium [4-(4-methylphenyl-2-methylpropyl)phenyl] hexafluorophosphate, and other iodomonium salts; tetrafluorophosphonium hexafluorophosphate and other phosphonium salts; N-hexylpyridinium tetrafluoroborate and other pyridinium salts.

[0153] Specifically, examples of photocationic polymerization initiators include: (4-hydroxyphenyl)methylbenzylsulfonium tetra(pentafluorophenyl)borate, 4-(4-biphenylthio)phenyl-4-biphenylphenylsulfonium tetra(pentafluorophenyl)borate, 4-(phenylthio)phenyl diphenylsulfonium phenyl tri(pentafluorophenyl)borate, [4-(4-biphenylthio)phenyl]-4-biphenylphenylsulfonium phenyl tri(pentafluorophenyl)borate, and diphenyl[4-(phenylthio)phenyl]sulfonium tri(pentafluoroethyl)trifluorophosphate. Diphenyl[4-(phenylthio)phenyl]sulfonium tetra(pentafluorophenyl)borate, diphenyl[4-(phenylthio)phenyl]sulfonium hexafluorophosphate, 4-(4-biphenylthio)phenyl-4-biphenylphenylsulfonium tri(pentafluoroethyl)trifluorophosphate, sulfide bis[4-(diphenylsulfonium)phenyl]phenyl tri(pentafluorophenyl)borate, [4-(2-thioxanthoneylthio)phenyl]phenyl-2-thioxanthoneylsulfonium tri(pentafluorophenyl)borate, 4-(phenylthio)phenyl diphenylsulfonium hexafluoroantimonate, etc.

[0154] The aforementioned photocationic polymerization initiators can be commercially available products. Examples of such commercially available products include: "CYRACURE UVI-6970", "CYRACURE UVI-6974", "CYRACURE UVI-6990", and "CYRACURE UVI-950" (manufactured by Union Carbide, Inc., USA); "Omnirad250", "Omnirad261", "Omnirad264", and "CG-24-61" (manufactured by IGM Resins, Inc.); "Optomer SP-150", "Optomer SP-151", "Optomer SP-170", and "Optomer SP-171" (manufactured by ADEKA, Inc.); and "DAICAT". II (manufactured by DAICEL Co., Ltd.); "UVAC1590", "UVAC1591" (manufactured by DAICEL-Allnex Co., Ltd.); "CI-2064", "CI-2639", "CI-2624", "CI-2481", "CI-2734", "CI-2855", "CI-2823", "CI-2758", "CIT-1682" (manufactured by Nippon Soda Co., Ltd.); "PI-2074" (manufactured by Rhodia Co., Ltd., tetra(pentafluorophenyl)borate toluene-cumyl iodomonium salt); "FF C509 (manufactured by 3M); "BBI-102", "BBI-101", "BBI-103", "MPI-103", "TPS-103", "MDS-103", "DTS-103", "NAT-103", "NDS-103" (manufactured by Midori Chemical Co., Ltd.); "CD-1010", "CD-1011", "CD-1012" (manufactured by Sartomer, Inc., USA); "CPI-100P", "CPI-101A" (manufactured by San-Apro Co., Ltd.), etc.

[0155] Examples of suitable initiators for the aforementioned thermal cationic polymerization include: aryl diazonium salts, aryl iodonium salts, aryl sulfonium salts, and propylene-ion complexes. Preferred initiators include commercially available products under the trade names "PP-33", "CP-66", and "CP-77" (manufactured by ADEKA Corporation); "FC-509" (manufactured by 3M Corporation); "UVE1014" (manufactured by GE Corporation); "SAN-AID SI-60L", "SAN-AID SI-80L", "SAN-AID SI-100L", "SAN-AID SI-110L", and "SAN-AID SI-150L" (manufactured by Sanshin Chemical Industry Co., Ltd.); and "CG-24-61" (manufactured by BASF Corporation).

[0156] Examples of Lewis acid-amine complexes include: BF3-hexylamine, BF3-monoethylamine, BF3-benzylamine, BF3-diethylamine, BF3-piperidine, BF3-triethylamine, BF3-aniline, BF4-hexylamine, BF4-monoethylamine, BF4-benzylamine, BF4-diethylamine, BF4-piperidine, BF4-triethylamine, BF4-aniline, PF5-ethylamine, PF5-isopropylamine, PF5-butylamine, PF5-laurhodium, PF5-benzylamine, and AsF5-laurhodium.

[0157] Examples of Brønsted salts include aliphatic sulfonium salts, aromatic sulfonium salts, iodonium salts, and phosphonium salts.

[0158] Examples of the imidazoles mentioned above 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, 1-cyanoethyl-2-undecylimidazole ontyltriazine, 1-cyanoethyl-2-phenylimidazole ontyltriazine, 2-methylimidazole ontyltriazine isocyanurate, 2-phenylimidazole ontyltriazine, 2,4-diamino-6-[2-methylimidazole-(1)]-ethyl-triazine, 2,4-diamino-6-[2-ethyl-4-methylimidazole-(1)]-ethyl-triazine, etc.

[0159] The content (amount) of the curing catalyst is preferably 0.01 to 5 parts by mass relative to 100 parts by mass of the cationic curing compound contained in the curable composition, more preferably 0.02 to 4 parts by mass, and even more preferably 0.03 to 3 parts by mass. If the content of the curing catalyst is within the above range, there is a tendency to improve the curing speed of the curable composition and to achieve a good balance between the heat resistance and transparency of the cured product.

[0160] In addition to the components described above, the curable composition may also contain additives as needed. Examples of such additives include: polyols such as ethylene glycol, diethylene glycol, propylene glycol, and glycerin; defoamers, leveling agents, silane coupling agents, surfactants, inorganic fillers, flame retardants, colorants, ionomers, pigments, fluorescent agents, and release agents. Only one or more of these additives may be used.

[0161] The above-described curable composition can be prepared by stirring / mixing the components under a heated state as needed. The stirring / mixing can be performed using, for example, various known or conventional stirring / mixing units such as dissolvers, homogenizers, kneaders, roller mills, bead mills, and self-rotating / revolutionary stirring devices. Furthermore, defoaming can be performed under vacuum after stirring / mixing.

[0162] In the above-described curable composition, relative to the total amount (100% by mass) of the compound shown in formula (1), the compound shown in formula (a), the compound shown in formula (b), and the compound shown in formula (c), the proportion of the compound shown in formula (1) 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 also be 92% by mass or more, 93% by mass or more, 95% by mass or more, or 96% by mass or more. The above proportions can be calculated based on the proportion of peak areas obtained by GC-MS.

[0163] In the above-described curable composition, relative to the total amount (100% by mass) of the compounds shown in formula (1), (a), (b), and (c), the combined proportion of the compounds shown in formula (a), (b), and (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 proportion can be calculated based on the proportion of peak areas obtained by GC-MS.

[0164] The above-described curable composition exhibits rapid curing properties; when using a thermo-cationic polymerization initiator, the curing time (or gel time) at 80°C is, for example, 600 seconds or less, preferably 500 seconds or less. Furthermore, when using an anhydride curing agent, the curing time (or gel time) at 120°C is, for example, 900 seconds or less, preferably 800 seconds or less. Additionally, when using a photo-cationic polymerization initiator, the above-described curable composition exhibits rapid curing properties under ultraviolet irradiation (3000 mJ / cm²). 2The curing time (or gel time) under these conditions is, for example, 300 seconds or less, preferably 150 seconds or less.

[0165] The curing temperature is preferably 45–200°C, more preferably 100–190°C, and even more preferably 100–180°C. Furthermore, the heating time (or curing time) is preferably 30–600 minutes, more preferably 45–540 minutes. If the heating temperature or heating time is below the above range, curing will be insufficient; conversely, if the heating temperature or heating time is above the above range, resin component decomposition may occur, and neither is preferred. The curing conditions depend on various factors; for example, they can be appropriately adjusted by shortening the heating time when the heating temperature is increased, or extending the heating time when the heating temperature is decreased.

[0166] [Cured product]

[0167] A cured product is obtained by curing the above-described curable composition. The cured product exhibits low degassing at high temperatures, is not prone to curing shrinkage, and also possesses excellent transparency and heat resistance.

[0168] The cured product exhibits excellent transparency, with a transmittance (3 mm thickness) of 400 nm light preferably being 40% or more, more preferably 60% or more, even more preferably 70% or more, and also 75% or more, 80% or more, 85% or more, and particularly preferably 90% or more. When using a thermal cationic polymerization initiator, the transmittance of the cured product is preferably 70% or more, more preferably 75% or more. When using an anhydride curing agent, the transmittance of the cured product is preferably 85% or more, more preferably 90% or more. The aforementioned curable composition forms a cured product with excellent transparency; therefore, when used as a sealant for optical semiconductor elements in optical semiconductor devices, a chip mounting paste, etc., there is a tendency to further increase the light intensity emitted from the optical semiconductor device.

[0169] The cured product exhibits 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 using a thermal cationic polymerization initiator, the glass transition temperature of the cured product is preferably 200°C or higher, more preferably 300°C or higher. When using an anhydride curing agent, the glass transition temperature of the cured product is preferably 230°C or higher, more preferably 250°C or higher.

[0170] The cured material exhibits excellent heat resistance, and its 5% weight loss temperature (Td5) is preferably 325°C or higher, more preferably 330°C or higher, and even more preferably 335°C or higher. Furthermore, the 10% weight loss temperature (Td10) of the cured material is preferably 355°C or higher, more preferably 360°C or higher.

[0171] The curing shrinkage rate 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 curing shrinkage rate is determined by measuring the density of the curable composition before curing and the cured product after curing, based on the following formula, and calculated according to the density change.

[0172] Volume shrinkage rate r = {(ds - dl) / dl} × 100

[0173] dl: Specific gravity of the liquid before curing. Measured using a density and hydrometer "DA-640" (manufactured by Kyoto Electronics Industry Co., Ltd.).

[0174] ds: Specific gravity of the cured solid. Measured using the solid specific gravity measurement method.

[0175] The degassing amount of the cured product 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 degassing amount is calculated as the mass reduction rate based on the following formula, obtained by measuring the mass of the cured product before and after heating.

[0176] Mass reduction rate = {(mass of cured product before heating - mass of cured product after heating) / mass of cured product before heating} × 100

[0177] The flexural strength of the cured material, after being shaped into a form with a thickness of 4 mm × width of 10 mm × length of 80 mm, is preferably 45 MPa or more, more preferably 50 MPa or more, and even more preferably 55 MPa or more. Furthermore, there is no particular upper limit, and it can be 300 MPa or less. It should be noted that the above-mentioned flexural strength can be measured, for example, by the method described in the embodiments described later.

[0178] The flexural modulus of the cured material, after being shaped into a form with a thickness of 4 mm × width of 10 mm × length of 80 mm, is preferably 2500 MPa or more, more preferably 3000 MPa or more, and even more preferably 3300 MPa or more. Furthermore, there is no particular upper limit, and it can be 5000 MPa or less. It should be noted that the above-mentioned flexural modulus can be measured, for example, by the method described in the embodiments described later.

[0179] The flexural elongation after the cured material is molded into a shape with a thickness of 4 mm × width of 10 mm × length of 80 mm is preferably 1.0%GL or more, more preferably 1.2%GL or more, and even more preferably 1.4%GL or more. Furthermore, as an upper limit, there is no particular limitation, and it can be 5.0%GL or less. It should be noted that the above-mentioned flexural elongation can be measured, for example, by the method described in the embodiments described later.

[0180] The aforementioned curable compositions can be used for various applications such as sealants, adhesives, coatings, hard coatings, electrical insulating materials (automotive insulating materials, etc.), laminates, inks (inkjet printing inks, UV inks, etc.), sealants, photoresists, composite materials, transparent substrates, transparent sheets, transparent films, optical elements, optical lenses, light models, electronic paper, touch panels, solar cell substrates, optical waveguides, light guide plates, holographic memories, etc.

[0181] [Sealant]

[0182] The sealant described above comprises the curable composition described above. The sealant is preferably used for sealing optical semiconductors (optical semiconductor elements) in optical semiconductor devices. Using the sealant allows for the sealing of optical semiconductor elements using a cured material (=sealing material) with excellent transparency and heat resistance, and which is less prone to curing shrinkage. Furthermore, it is less prone to degassing in high-temperature environments, thus reducing the likelihood of cracking and maintaining the reliability of components such as semiconductor elements sealed by the sealing material.

[0183] The curable composition is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more, relative to the total amount (100% by mass) of the sealant. The sealant may also be formed solely from the curable composition.

[0184] [Adhesive]

[0185] The adhesive described above comprises the curable composition described above. The adhesive can be used for bonding / fixing components to substrates, and more specifically, for various applications requiring excellent transparency, heat resistance, and minimal curing shrinkage: chip mounting pastes for bonding and fixing optical semiconductor elements to metal electrodes in optical semiconductor devices; lens adhesives for fixing lenses of cameras to substrates or bonding lenses together; and optical film adhesives for fixing optical films (e.g., polarizers, polarizer protective films, retardation films, etc.) to substrates or bonding optical films to each other or to other films. Furthermore, it is less prone to degassing in high-temperature environments, thus reducing the likelihood of cracking and maintaining the reliability of the bonded components.

[0186] The aforementioned adhesive is particularly preferred for use as a chip mounting paste (or chip bonding agent). By using the aforementioned adhesive as a chip mounting paste, it is possible to obtain an optical semiconductor device formed by bonding optical semiconductor elements to electrodes using a cured material with excellent transparency and heat resistance. Furthermore, it is not prone to degassing in high-temperature environments, thus reducing the likelihood of cracking and maintaining the reliability of the bonded components.

[0187] The curable composition is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more, relative to the total amount (100% by mass) of the adhesive. The adhesive may also be formed solely from the curable composition.

[0188] [Coating Agent]

[0189] The above-mentioned coating agent comprises the above-mentioned curable composition. The above-mentioned coating agent can be used in various applications, particularly those requiring excellent workability, transparency, and heat resistance. Furthermore, it is less prone to curing shrinkage and curling during the application and curing of the coating agent.

[0190] The curable composition is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more, relative to the total amount of the coating agent (100% by mass). The coating agent may also be formed solely from the curable composition.

[0191] [Hard coating]

[0192] The aforementioned hard coating agent comprises the aforementioned curable composition. This hard coating agent can be used in various applications, particularly those requiring excellent workability, transparency, surface hardness, and heat resistance. Furthermore, when the hard coating agent is applied and cured to form a hard coating layer, curing shrinkage and curling are less likely to occur.

[0193] The curable composition is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more, relative to the total amount of the hardening agent (100% by mass). The hardening agent may also be formed solely from the curable composition.

[0194] [Optical components]

[0195] Optical components can be obtained using the aforementioned cured material. The optical component comprises a cured product of the aforementioned curable composition. Examples of such optical components include: an optical semiconductor device formed by sealing an optical semiconductor element using the aforementioned cured material; an optical semiconductor device formed by bonding an optical semiconductor element to an electrode using the aforementioned cured material; and an optical semiconductor device formed by bonding an optical semiconductor element to an electrode using the aforementioned cured material and sealing the optical semiconductor element using the aforementioned cured material. The aforementioned optical component, having a structure formed by sealing and bonding using the aforementioned cured material, exhibits excellent heat resistance and high light extraction efficiency. Furthermore, it is less prone to degassing under high-temperature environments, thus reducing the likelihood of cracking and maintaining the reliability of the optical semiconductor element and the optical component.

[0196] The various solutions disclosed in this specification can also be combined with any other features disclosed in this specification. The various configurations and combinations of configurations in each embodiment are merely examples, and appropriate additions, omissions, substitutions, and other modifications to the configurations can be made without departing from the spirit of this disclosure. Furthermore, the inventions of this disclosure are not limited to the embodiments or the following examples, but only to the claims.

[0197] Example

[0198] The following describes one embodiment of the present disclosure in more detail based on examples, but the present disclosure is not limited to these examples.

[0199] Example 1

[0200] (Epoxidation process)

[0201] 1000g of 2,2-bis(3',4'-cyclohexenyl)propane and 3000g of ethyl acetate were added to a 10L jacketed flask. While blowing nitrogen into the gas phase, the temperature of the reaction system was maintained at 35°C. Over approximately 5 hours, 3072g of an ethyl acetate solution of peracetic acid (peracetic acid concentration: 29.2%, water content: 0.31%) was added dropwise. After the peracetic acid addition was complete, the mixture was allowed to mature at 35°C for 3 hours to terminate the reaction.

[0202] (Cleaning process)

[0203] The crude reaction solution obtained above was neutralized and washed with water and sodium hydroxide aqueous solution at 15°C.

[0204] (First step of removing low-boiling point, second step of removing high-boiling point)

[0205] The crude reaction liquid, after the above cleaning process, was subjected to a first low-boiling step in a WFE-type thin-film evaporator at a heating temperature of 150°C and a pressure of 70 Torr. Then, a high-boiling step was performed at a heating temperature of 150°C and a pressure of 0.3 Torr to obtain 609.0g of epoxy compound.

[0206] (Second step of removing low-boiling point)

[0207] 609.0 g of the obtained epoxy compound was added to a 1 L four-necked flask and precision distilled using an Oldershaw distillation column with 20 actual trays. The bottom of the column was heated to 220 °C, and the distillate was recovered at a reflux ratio of 2, a top pressure of 0.3 kPa, a top temperature of 155–165 °C, and a residence time at the bottom of the distillate of less than 10 hours, to obtain product 1 (295 g) of the alicyclic epoxy compound of Example 1.

[0208] Example 2

[0209] In the second de-boiling step, the distilled components were recovered at a tower top temperature of 160-165°C. Otherwise, the alicyclic epoxy compound product 2 of Example 2 was obtained in the same manner as in Example 1.

[0210] Example 3

[0211] In a jacketed 20L SUS316 reactor equipped with a stirrer, 5000g of 6-methyl-3-cyclohexenylmethyl (6'-methyl-3',4'-cyclohexenyl) carbamate was added, and the temperature was raised to 25°C. 13790g 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 addition and aging process. This yielded 18790g of a crude reaction solution containing 3,4-epoxy-6-methyl-cyclohexenylmethyl (3',4'-epoxy-6'-methyl) ester. Then, the crude reaction solution was subjected to the same washing, first low-boiling point removal, high-boiling point removal, and second low-boiling point removal processes as in Example 1, to obtain the alicyclic epoxy compound product 3 of Example 3.

[0212] Example 4

[0213] In a jacketed 20L SUS316 reactor equipped with a stirrer, 5000g of 3,4-cyclohexenylmethyl(3,4-cyclohexenyl)carbamate was added, and the temperature was raised to 25°C. 13790g 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 addition and aging process. This yielded 18790g of a crude reaction solution containing 3,4-epoxycyclohexylmethyl(3,4-epoxy)cyclohexylcarbamate. Then, for the above-mentioned crude reaction liquid, the washing process and the first low-boiling point removal process are performed in the same way as in Example 1. The residual liquid obtained after the first low-boiling point removal process is fed into the fifth layer from the bottom of a high-boiling point removal distillation column with a diameter of 40 mm, which is composed of a porous plate column with 10 actual plates. Otherwise, the high-boiling point removal process is performed in the same way as in Example 1. Then, the second low-boiling point removal process is performed in the same way as in Example 1 to obtain the alicyclic epoxy compound product 4 of Example 4.

[0214] Comparative Example 1

[0215] Without performing the second de-boiling step, the alicyclic epoxy compound product 5 of Comparative Example 1 was obtained in the same manner as in Example 1.

[0216] <Evaluation>

[0217] The alicyclic epoxy compound articles of the examples and comparative examples were evaluated as follows. The results are shown in the table.

[0218] (1) 1 H-NMR

[0219] The alicyclic epoxy compound product 1 of Example 1 was tested using an apparatus named "JNM-ECZ400S" (manufactured by Nippon Electron Ltd.), solvent: deuterated chloroform, and test conditions: 20°C. 1 The H-NMR spectrum was determined. The alicyclic epoxide product 1 obtained in Example 1 was... 1 H-NMR spectra are shown in Figure 1 .

[0220] (2) GPC

[0221] As a pretreatment, 0.04 g of the alicyclic epoxy compound product was dissolved in 2 g of tetrahydrofuran (THF) and filtered using a 0.50 μm filter (trade name "DISMIC13JP050AN", manufactured by Toyo Filter Paper Co., 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 shown in formulas (a) to (c) above, after removing the peak area, was taken as the purity [area %] of the alicyclic epoxy compound product. It should be noted that in the case of overlapping shoulders of adjacent peaks, the peak area was calculated by dividing the peak area by a vertical line from the valley to the baseline. The GPC apparatus and various conditions used are shown below.

[0222] Device: HLC-8220GPC (manufactured by Tosoh Co., Ltd.).

[0223] Detector: Differential refractometer (RI detector).

[0224] Pre-column: TSKGUARDCOLUMN SUPER HZ-L 4.6mm×20mm.

[0225] Columns: Sample side TSK-GEL SUPER HZM-N 4.6mm×150mm×4 columns.

[0226] Reference side: TSK-GEL SUPER HZM-N 6.0mm×150mm×1 piece + TSK-GEL SUPER H-RC 6.0mm×150mm.

[0227] Temperature of the constant temperature bath: 40℃.

[0228] Flow layer: THF.

[0229] Flow rate of the fluid layer: 0.35 ml / min.

[0230] Sample injection volume: 10 μl.

[0231] Data acquisition time: 10 to 26 minutes after sample injection.

[0232] (3) GC-MS

[0233] The alicyclic epoxy compound products of each example were analyzed by gas chromatography according to the following determination conditions. Furthermore, the components contained in the alicyclic epoxy compound products were identified based on molecular weight. It should be noted that the molecular weight of the detected peaks was analyzed using mass spectrometry. The total content of compounds (a) to (c) shown in the following conditions was determined by gas chromatography and calculated as area % (%). The chromatogram of the alicyclic epoxy compound product 1 obtained in Example 1 by GC-MS is shown in the figure.Figure 2 The summit report will be presented to Figure 3 .

[0234] <Measurement Conditions>

[0235] Measurement device: Trade name "Agilent7890GC5977B MSD", manufactured by Agilent Technologies Co., Ltd.

[0236] Column packing agent: (5% phenyl)methylsiloxane.

[0237] Column dimensions: Length 15m × Inner diameter 0.53mmφ × Film thickness 1.5μm.

[0238] Column temperature: 100℃ → (increase at 10℃ / min) → 250℃ (15 minutes).

[0239] Detector: FID.

[0240] (4) Hue (APHA)

[0241] The Hassen color number (APHA) is determined using a spectrophotometer for color difference and turbidity (trade name "TZ6000", manufactured by Nippon Denshoku Kogyo Co., Ltd.) and a glass cell (optical path length 33 × cell width 20 × height 55), and the hue is evaluated accordingly. A value below 105 is considered good, and a value below 15 is considered excellent.

[0242] Example 5

[0243] For every 100 parts by weight of the alicyclic epoxy compound product in each example, 0.6 parts by weight of the product "SAN-AID SI-100L" (manufactured by Sanshin Chemical Industry Co., Ltd.), which is used as a thermal cationic catalyst, were added and stirred using a rotary stirring device (trade name "Awatori Rentaro AR-250", manufactured by THINKY Co., Ltd.) to further defoam and obtain each curable composition.

[0244] Example 6

[0245] Each example of an alicyclic epoxy compound product, the trade name "RIKACID MH-700" (manufactured by Shin Nippon Rikka Co., Ltd.) as an anhydride curing agent, and the trade name "PX-4MP" (manufactured by Nippon Chemical Industry Co., Ltd.) as a curing accelerator were combined with the above-mentioned alicyclic epoxy compound products in such a ratio of epoxy equivalent to anhydride equivalent of 100:90. The mixture was stirred using a rotary stirring device (trade name "Awatori Rentaro AR-250", manufactured by THINKY Co., Ltd.) and defoamed to obtain each curable composition.

[0246] Example 7

[0247] For each example, 100 parts by weight of alicyclic epoxy compound product were mixed with 1 part by weight of "CPI-101A" (manufactured by San-Apro Co., Ltd.), a UV cationic catalyst, and stirred using a rotary stirring device (trade name "Awatori Rentaro AR-250", manufactured by THINKY Co., Ltd.) to further defoam and obtain each curable composition.

[0248] Examples 8 to 11

[0249] The curable composition of Example 8 was prepared by replacing 100 parts by mass of the alicyclic epoxy compound product of Example 1 with 90 parts by mass of the alicyclic epoxy compound product of Example 1 and 10 parts by mass of the bisphenol A type epoxy compound (trade name "JER828", manufactured by Mitsubishi Chemical Co., Ltd.) as another epoxy compound. Furthermore, the hue (APHA) was measured by the above method. Furthermore, using the curable composition of Example 8, the curable compositions of Examples 9 to 11 were obtained by the same method as Examples 5 to 7.

[0250] Examples 12 to 15

[0251] The curable composition of Example 12 was prepared by replacing 10 parts by mass of the bisphenol A type epoxy compound (trade name "JER828", manufactured by Mitsubishi Chemical Co., Ltd.) of Example 8 with 10 parts by mass of 3-ethyl-3{[(3-ethyloxetane-3-yl)methoxy]methyl}oxetane as an oxetane compound. Furthermore, the hue (APHA) was measured by the above method. Then, using the curable composition of Example 12, curable compositions of Examples 13 to 15 were obtained by the same method as in Examples 5 to 7.

[0252] (5) Curing properties

[0253] The curability of the curable compositions obtained in Examples 5-7, 9-11, and 13-15 was determined using a gel time measuring device (trade name "Rheometer MCR302", manufactured by Anton Paar Japan Co., Ltd.). Specifically, the curable compositions (thermal cationic catalysts) of Examples 5, 9, and 13 were heated to 80°C, the curable compositions (anhydride curing agent) of Examples 6, 10, and 14 were heated to 120°C, and the curable compositions (UV cationic catalysts) of Examples 7, 11, and 15 were irradiated with ultraviolet light. The curing curves were measured by rheometer method (dynamic viscoelasticity evaluation), and the temperature curve of loss modulus at a fixed frequency was measured. The point where the two elastic modulus curves measuring G' (storage modulus) and G'' (loss modulus) intersect was defined as the gelation point. Then, the curing time was determined at the time the set temperature (80°C or 120°C) was reached or at the time of starting ultraviolet irradiation (illuminance 3000 mJ / cm²). 2 The time taken from the gelation point to the point of gelation is used as the starting point for evaluating reactive gelation time. In Examples 5, 9, and 13, a time of 600 seconds or less is considered good, and a time of 500 seconds or less is considered excellent. In Examples 6, 10, and 14, a time of 900 seconds or less is considered good, and a time of 800 seconds or less is considered excellent. In Examples 7, 11, and 15, a time of 300 seconds or less is considered good, and a time of 150 seconds or less is considered excellent.

[0254] Example 16

[0255] The curable compositions obtained in Examples 5, 6, 9, 10, 13, and 14 were filled into molds and heated in a resin curing oven at 120°C for 5 hours to obtain the cured products of Examples 16 to 21. It should be noted 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.

[0256] (6) Curing shrinkage

[0257] For the cured product obtained in Example 16, the density before and after curing was measured using the density measurement method (JIS K5600 2-4). Based on the following formula, the curing shrinkage rate (volume shrinkage rate) was calculated according to the density change. If it is less than 1.5%, it is judged to be good.

[0258] Volume shrinkage rate r = {(ds - dl) / dl} × 100

[0259] dl: Specific gravity of the liquid before curing. Measured using a density and hydrometer "DA-640" (manufactured by Kyoto Electronics Industry Co., Ltd.).

[0260] ds: Specific gravity of the cured solid. Measured using the solid specific gravity measurement method.

[0261] (7) Light transmittance

[0262] For each cured product (3 mm thick) obtained in Example 16, the transmittance (thickness direction) of light at a wavelength of 400 nm was measured using a spectrophotometer (trade name "UV-2450", 10 mm square quartz cell, 10 mm thick, manufactured by Shimadzu Corporation). In the cured products of the curable compositions of Examples 5, 9, and 13, a transmittance of 70% or more was considered good, and a transmittance of 75% or more was considered excellent. In the cured products of the curable compositions of Examples 6, 10, and 14, a transmittance of 85% or more was considered good, and a transmittance of 90% or more was considered excellent.

[0263] (8) Glass transition temperature (Tg)

[0264] For each cured product obtained in Example 16, the glass transition temperature was determined under the following conditions. For the cured products of the curable compositions of Examples 5, 9, and 13, a temperature of 200°C or higher was considered good, and a temperature of 300°C or higher was considered excellent. For the cured products of the curable compositions of Examples 6, 10, and 14, a temperature of 230°C or higher was considered good, and a temperature of 250°C or higher was considered excellent.

[0265] Sample: Length 4mm × Width 5mm × Thickness 0.5mm.

[0266] Measuring apparatus: Viscoelasticity measuring apparatus (DMA), trade name "DMS6100", manufactured by Hitachi High-Tech Science Co., Ltd.

[0267] Measurement mode: Tension.

[0268] Temperature range: 25℃ to 320℃.

[0269] Heating rate: 5℃ / minute.

[0270] (9) Curled

[0271] The curable compositions obtained in Examples 7, 11, and 15 were uniformly coated onto a PET film (100 μm thick) to a thickness of 40 μm, and cured using a high-pressure mercury lamp with a cumulative light intensity of 1200 mJ / cm². 2Under ultraviolet irradiation conditions, various cured products were obtained. With the cured product on the top and the outer side floating up, the height of the four sides was measured and the average value was calculated. If the curling height exceeds 5mm, it is judged as defective (×), if it is less than 5mm, it is judged as good (〇), and if it is less than 1mm, it is judged as excellent (◎).

[0272] (10) Degassing volume

[0273] The curable compositions obtained in Examples 7, 11, and 15 were injected into molds with dimensions of 76 mm in length, 26 mm in width, and 0.5 mm in thickness. A UV irradiation device (trade name "LED-UV Irradiator PSCC-60048", manufactured by CCS Corporation) was used at 365 nm and an exposure dose of 2500 mJ / cm². 2 Under UV irradiation conditions using LED lamps, various cured products were obtained. For each cured product, the mass reduction rate relative to the initial mass was calculated under the following conditions and taken as the degassing amount. A degassing amount of 0.1% or less was considered good, and a degassing amount of 0.08% or less was considered excellent.

[0274] Evaluation sample: 5–10 μg.

[0275] Measuring device: Trade name "STA / 7200", manufactured by Hitachi High-Tech Science Co., Ltd.

[0276] (11) Bending strength, flexural modulus of elasticity, and flexural elongation

[0277] In the cured product obtained in Example 16, the cured products of each curable composition obtained in Example 9, Example 10, Example 13 and Example 14 were shaped into a shape with a thickness of 4 mm × width of 10 mm × length of 80 mm. A three-point bending test was performed using a TENSILON universal testing machine (manufactured by ORIENTEC Co., Ltd.) with an edge span of 67 mm and a bending speed of 2 mm / min. The bending strength (MPa), bending modulus of elasticity (MPa) and bending elongation (%GL) of the cured product were then measured.

[0278] [Table 1]

[0279]

[0280] As shown in Table 1, the alicyclic epoxy compound products of the examples, which have a total proportion of more than 1% by mass relative to the compounds shown in formulas (a) to (c), exhibit low degassing. Furthermore, they are evaluated as having good hue and excellent transparency, short reactive gel time, and rapid curing. In addition, the cured products are evaluated as having high light transmittance, excellent transparency, high Tg, and excellent heat resistance. Moreover, the alicyclic epoxy compound products of the examples are evaluated as having less curing shrinkage compared to products made from other alicyclic epoxy compounds.

[0281] [Table 2]

[0282]

[0283] The following describes variations of the invention disclosed herein.

[0284] [Appendix 1] An epoxy compound product, wherein the purity of the compound shown in formula (1) is 80% or more, and the total proportion of the compound shown in formula (a), the compound shown in formula (b) and the compound shown in formula (c) is 1% by mass or less.

[0285] [Chemical Formula 1]

[0286]

[0287] [In the formula, X represents a single bond or a linking group. Optionally, the cyclohexane ring and the benzene ring may have substituents on more than one carbon atom constituting the ring.]

[0288] [Note 2] According to Note 1, the epoxy compound article is wherein the compound represented by formula (1) is an epoxide formed from an aliphatic peroxycarboxylic acid of the compound represented by formula (2) below.

[0289] [Chemical Formula 2]

[0290]

[0291] [In formula (2), X represents a single bond or a linking group, the same as X in formula (1). The cyclohexene ring in formula (2) may optionally have substituents on more than one of the carbon atoms constituting the ring.]

[0292] [Note 3] In the epoxy compound product according to Note 2, the aliphatic peroxycarboxylic acid is peracetic acid.

[0293] [Note 4] A curable composition comprising an epoxy compound article, a curing agent and / or a curing catalyst according to any one of Notes 1 to 3.

[0294] [Note 5] A curable composition comprising an epoxy compound article, other epoxy compounds and / or oxetane compounds according to any one of Notes 1 to 3.

[0295] [Note 6] The curable composition according to Note 4 or 5, wherein the curable composition is an adhesive, sealant, coating agent or hardening agent.

[0296] [Note 7] A cured product, which is a cured product of the curable composition according to any one of Notes 4 to 6.

[0297] [Note 8] An optical component having a cured material as described in Note 7.

[0298] [Appendix 9] A method for manufacturing an epoxy compound article, the method being a method for manufacturing an epoxy compound article according to any one of Appendices 1 to 3, wherein the method manufactures the epoxy compound article by means of the following epoxidation step, the following first de-low boiling point step, the following de-high boiling point step and the following second de-low boiling point step.

[0299] Epoxidation process: The process of reacting the compound shown in formula (2) with an organic peroxy acid to obtain the reaction product.

[0300] [Chemical Formula 2]

[0301]

[0302] [In formula (2), X represents a single bond or a linking group. The cyclohexene ring in formula (2) may optionally have substituents on one or more carbon atoms constituting the ring.]

[0303] The first step is to remove low-boiling-point components through distillation using a thin-film still.

[0304] High-boiling-point removal process: The process of removing high-boiling-point components through distillation.

[0305] The second low-boiling step is a step of removing the compounds shown in formulas (a) to (c) by distillation using a distillation column.

Claims

1. An epoxy compound product, wherein, The compound represented by formula (1) below has a purity of 80% or higher. The total proportion of the compound shown in formula (a), the compound shown in formula (b), and the compound shown in formula (c) is less than 1% by mass. [Chemical Formula 1] ， In the formula, X represents a single bond or a linking group, and the cyclohexane ring and benzene ring optionally have substituents on more than one carbon atom constituting the ring.

2. The epoxy compound article according to claim 1, wherein, The compound represented by formula (1) is an epoxide formed from an aliphatic peroxycarboxylic acid of the compound represented by formula (2) below. [Chemical Formula 2] ， In formula (2), X represents a single bond or linking group, which is the same as X in formula (1). The cyclohexene ring in formula (2) may optionally have substituents on one or more carbon atoms constituting the ring.

3. The epoxy compound article according to claim 2, wherein, The aliphatic peroxycarboxylic acid is peracetic acid.

4. A curable composition comprising the epoxy compound article, curing agent and / or curing catalyst according to claim 1.

5. A curable composition comprising the epoxy compound article according to claim 1, other epoxy compounds and / or oxetane compounds.

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

7. A cured product, said cured product being a cured product of the curable composition according to claim 4 or 5.

8. An optical component comprising the cured material according to claim 7.

9. A method for manufacturing an epoxy compound article, wherein the method for manufacturing an epoxy compound article is according to any one of claims 1 to 3, and the method comprises the following epoxidation step, the following first de-low-boiling step, the following de-high-boiling step, and the following second de-low-boiling step to manufacture the epoxy compound article. Epoxidation process: The process of reacting the compound shown in formula (2) with an organic peroxyacid to obtain the reaction product. [Chemical Formula 2] ， In formula (2), X represents a single bond or a linking group, and the cyclohexene ring in formula (2) may optionally have a substituent on one or more carbon atoms constituting the ring; The first step is to remove low-boiling-point components through distillation using a thin-film still. High-boiling-point removal process: The process of removing high-boiling-point components through distillation; The second low-boiling step is a step of removing the compounds shown in formulas (a) to (c) by distillation using a distillation column.

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