Process for the production of epoxide compounds

Abstract

The present disclosure provides a method for efficiently producing 1,3,5-tris(3,4-epoxycyclohexanecarbonyloxy) cyclohexane having a small chlorine content. The method for producing an epoxy compound of the present disclosure includes: Step 1, producing a compound represented by the following formula (2) through an ester exchange reaction of a compound represented by the following formula (1) and 1,3,5-cyclohexanetriol; and Step 2, obtaining an epoxy compound represented by the following formula (3) by reacting a peracid with the compound represented by the formula (2) produced.

Description

Technical Field

[0001] This disclosure relates to a method for manufacturing an epoxy compound and a composition comprising the epoxy compound. This disclosure claims priority to Japanese Patent Application No. 2019-172124, filed on September 20, 2019, 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. Therefore, they are extremely useful as raw materials for encapsulation materials, coating agents, adhesives, inks, and sealants.

[0003] As a method for manufacturing such an epoxy compound, Patent Document 1 describes the following method: reacting cyclohexene carboxylic acid chloride with 1,3,5-cyclohexanetriol to generate 1,3,5-tris(3-cyclohexene carbonyloxy)cyclohexane, and reacting m-chloroperbenzoic acid with the generated compound in the presence of a chlorine-based solvent to obtain 1,3,5-tris(3,4-epoxycyclohexane carbonyloxy)cyclohexane.

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Application Publication No. 11-71363 Summary of the Invention

[0007] The problem the invention aims to solve

[0008] However, in the aforementioned method, it is unavoidable to mix chlorine compounds into the epoxy compound. For example, if a substance containing chlorine compounds mixed with epoxy compounds is used as a packaging material for a printed circuit board, the wiring (especially copper wiring) of the printed circuit board will be corroded due to the chlorine compounds, resulting in a long-term decrease in reliability. Furthermore, this problem becomes more pronounced with the miniaturization and increasing density of electronic components.

[0009] Therefore, the object of this disclosure is to provide an efficient method for producing 1,3,5-tris(3,4-epoxycyclohexanecarbonyloxy)cyclohexane with low chlorine content.

[0010] Technical solution

[0011] In order to solve the above-mentioned problems, the inventors conducted in-depth research and found that if 1,3,5-tris(3-cyclohexene carbonyloxy)cyclohexane (the compound shown in formula (2) below) is generated by transesterification, and peracetic acid is reacted with the generated 1,3,5-tris(3-cyclohexene carbonyloxy)cyclohexane, then 1,3,5-tris(3,4-epoxycyclohexane carbonyloxy)cyclohexane (the epoxy compound shown in formula (3) below) can be produced efficiently. No chlorine compound is needed in the reaction, thus producing an epoxy compound with low chlorine content. This disclosure is based on these insights.

[0012] That is, this disclosure provides a method for manufacturing an epoxy compound, comprising:

[0013] Step 1 involves the transesterification reaction of the compound shown in formula (1) with 1,3,5-cyclohexanetriol to generate the compound shown in formula (2); and

[0014] [Chemical Formula 1]

[0015]

[0016] (In equation (1), R) 1 (representing alkyl)

[0017] [Chemical Formula 2]

[0018]

[0019] Step 2 involves reacting the peracid with the compound represented by formula (2) to obtain the epoxy compound represented by formula (3).

[0020] [Chemical Formula 3]

[0021]

[0022] Furthermore, this disclosure provides a method for manufacturing the epoxy compound, wherein the peracid is formic acid and / or peracetic acid.

[0023] Furthermore, this disclosure provides a method for manufacturing the epoxy compound, wherein the reaction of step 2 is carried out in the presence of an acetate-based solvent.

[0024] Furthermore, this disclosure provides a method for manufacturing the epoxy compound, wherein the reaction of step 1 is carried out in the presence of an alkali metal amide and / or an alkyl alkali metal.

[0025] Furthermore, this disclosure provides a method for manufacturing the epoxy compound, wherein the chlorine content of the epoxy compound represented by formula (3) is less than 1000 ppm.

[0026] Furthermore, this disclosure provides a composition comprising a compound represented by formula (e) and an epoxy compound represented by formula (3) in a weight ratio of 90 / 10 to 1 / 99.

[0027] [Chemical Formula 4]

[0028]

[0029] (In formula (e), X represents a single bond or a linking group)

[0030] [Chemical Formula 5]

[0031]

[0032] Furthermore, this disclosure provides the composition, wherein the composition is for transfer molding.

[0033] Invention Effects

[0034] According to the method for manufacturing epoxy compounds disclosed herein, 1,3,5-tris(3,4-epoxycyclohexanecarbonyloxy)cyclohexane can be manufactured more efficiently than conventional methods.

[0035] Furthermore, in the method for manufacturing the epoxy compound, there is no need to use chlorine-containing compounds such as chlorine-based solvents, thus allowing the chlorine content of the obtained epoxy compound to be set to an extremely low value. Therefore, the epoxy compound can be preferably used as a packaging material for semiconductors, etc. With regard to semiconductors packaged using the epoxy compound, corrosion of wiring caused by chlorine is suppressed, and the occurrence of wire breakage, poor insulation, etc., caused by wiring corrosion is suppressed.

[0036] Therefore, if the epoxy compound obtained by the manufacturing method of the epoxy compound is used, it is possible to achieve further miniaturization, high density, high reliability, and long lifespan of electronic components. Detailed Implementation

[0037] [Methods for manufacturing epoxy compounds]

[0038] The method for manufacturing the epoxy compound disclosed herein includes:

[0039] Step 1 involves the transesterification reaction of a compound represented by formula (1) (hereinafter sometimes referred to as "compound (1)") with 1,3,5-cyclohexanetriol to generate a compound represented by formula (2); and

[0040] [Chemical Formula 6]

[0041]

[0042] (In equation (1), R) 1 (representing alkyl)

[0043] [Chemical Formula 7]

[0044]

[0045] Step 2 involves reacting the peracid with the compound (hereinafter sometimes referred to as "compound (2)") shown in the formula (2) to obtain the epoxy compound (hereinafter sometimes referred to as "compound (3)") shown in the formula (3).

[0046] [Chemical Formula 8]

[0047]

[0048] In equation (1), R 1 The alkyl group is represented by an alkyl group. Examples of such alkyl groups include straight-chain or branched alkyl groups with about 1 to 8 carbon atoms (preferably 1 to 6, particularly preferably 1 to 3), such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, and hexyl.

[0049] (Process 1)

[0050] Step 1 is as follows: through the transesterification reaction of the above compound (1) with 1,3,5-cyclohexanetriol, the compound shown in formula (2) is generated.

[0051] The amount of the above compound (1) used relative to 1 mol of 1,3,5-cyclohexanetriol is, for example, 3 to 7 mol, preferably 4 to 6 mol.

[0052] The transesterification reaction is preferably carried out in the presence of a strongly basic catalyst. Examples of strongly basic catalysts include alkali metal amides and alkyl alkali metals.

[0053] The alkali metal amide is represented, for example, by the following formula (c1).

[0054] [Chemical Formula 9]

[0055]

[0056] (In the formula, M represents an alkali metal, R) 2 R 3 Same or different, indicating hydrogen atom, alkyl, or trialkylsilyl. In R 2 R 3 In the case of alkyl groups, these groups can also link together to form a ring with the adjacent nitrogen atom.

[0057] M represents alkali metals, such as Li, Na, K, Cs, etc.

[0058] As R2 R 3 Alkyl groups, for example, include straight-chain or branched alkyl groups with about 1 to 20 carbon atoms (preferably 1 to 10, particularly preferably 1 to 3), such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, decyl, and dodecyl.

[0059] As R 2 R 3 The trialkylsilyl group in the text can be exemplified by, for example, trimethylsilyl, tert-butyldimethylsilyl, and other straight-chain or branched alkyl-substituted silyl groups with about 1 to 20 carbon atoms (preferably 1 to 10, particularly preferably 1 to 3).

[0060] As R 2 R 3 They can also be linked together to form rings with adjacent nitrogen atoms, such as five- to six-membered rings containing nitrogen atoms as heteroatoms, such as tetrahydropyrrole rings and piperidine rings.

[0061] Examples of alkali metal amides include lithium amide, lithium diisopropylamide, lithium 2,2,6,6-tetramethylpiperidine, and lithium hexamethyldisilazide. They can be used alone or in combination of two or more.

[0062] The alkyl alkali metal is represented, for example, by the following formula (c2).

[0063] R 4 -M (c2)

[0064] (In the formula, M represents an alkali metal, R) 4 (representing alkyl)

[0065] The M in equation (c2) is the same as the M in equation (c1) above.

[0066] As R 4 Alkyl groups, for example, include straight-chain or branched alkyl groups with 1 to 20 carbon atoms (preferably 1 to 10, particularly preferably 1 to 5), such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, decyl, and dodecyl.

[0067] Examples of alkyl alkali metals include, for example, methyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, etc. They can be used alone or in combination of two or more.

[0068] As a strongly basic catalyst, alkali metal amides are preferred, and lithium amides are particularly preferred, considering their excellent effect in promoting transesterification reactions.

[0069] The amount of strong basic catalyst used relative to 100 mol of the above compound (1) is, for example, about 10 to 50 mol, preferably 15 to 35 mol.

[0070] The transesterification reaction is preferably carried out in the presence of a solvent. As the solvent, from the viewpoint of good solubility of 1,3,5-cyclohexanetriol, a solvent with a boiling point of 140°C or higher at atmospheric pressure (i.e., above the melting point of 1,3,5-cyclohexanetriol) is preferred. Furthermore, the solvent is preferably a hydrophobic solvent (i.e., a low-polarity solvent). Examples of such solvents include: alcohols such as tert-butanol; aliphatic hydrocarbons such as octane; alicyclic hydrocarbons such as cyclohexane; aromatic hydrocarbons such as toluene, xylene, and ethylbenzene; and nitriles such as benzonitrile. These solvents can be used alone or in combination of two or more.

[0071] The amount of solvent used is, for example, 1 to 10 times the total amount of the above compound (1) and 1,3,5-cyclohexanetriol, preferably 1 to 3 times the total amount of solvent used.

[0072] The reaction temperature for transesterification is, for example, 150–250°C, preferably 170–200°C. The reaction time is, for example, about 1–4 hours. The transesterification reaction can be carried out under normal pressure, reduced pressure, or increased pressure. There are no particular restrictions on the atmosphere for the transesterification reaction as long as it does not hinder the reaction; for example, it can be any atmosphere such as air, nitrogen, or argon.

[0073] Furthermore, as the reaction proceeds, R 1 OH(R 1 R in equation (1) above 1 The same (is generated), but in terms of promoting the reaction, it is preferable to generate R. 1 OH is removed from the reaction system.

[0074] After the transesterification reaction is completed, the reaction products are preferably neutralized with acid and then washed with water.

[0075] After the transesterification reaction is completed, the resulting reaction products can be separated and purified by methods such as filtration, concentration, distillation, extraction, crystallization, adsorption, recrystallization, column chromatography, or a combination of these methods. Thus, the compound represented by formula (2) above can be obtained.

[0076] (Process 2)

[0077] Step 2 is the following step (epoxidation reaction step): reacting peracid with the compound shown in formula (2) above to obtain the epoxy compound shown in formula (3) above.

[0078] The peracid is represented, for example, by the following formula (a).

[0079] R 5 -C(=O)OOH (a)

[0080] (where R is in the formula) 5 (Represents a hydrogen atom or a hydrocarbon group)

[0081] In the R 5 The hydrocarbon groups in the text include: aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and groups formed by their bonding.

[0082] As the aliphatic hydrocarbon group, aliphatic hydrocarbon groups with 1 to 20 carbon atoms are preferred, such as: alkyl groups with about 1 to 20 carbon atoms (preferably 1 to 10, particularly preferably 1 to 3), such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, decyl, dodecyl, etc.; alkenyl groups with about 2 to 20 carbon atoms (preferably 2 to 10, particularly preferably 2 to 3), such as vinyl, allyl, 1-butenyl, etc.; alkynyl groups with about 2 to 20 carbon atoms (preferably 2 to 10, particularly preferably 2 to 3), such as ethynyl, propynyl, etc.

[0083] As the alicyclic hydrocarbon group, a three- to twenty-membered alicyclic hydrocarbon group is preferred, such as: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, etc., which are three- to twenty-membered (preferably three- to fifteen-membered, particularly preferably five- to eight-membered) cycloalkyl groups; cyclopentenyl, cyclohexenyl, etc., which are three- to twenty-membered (preferably three- to fifteen-membered, particularly preferably five- to eight-membered) cycloalkenyl groups; decahydronaphthyl-1-yl, norbornel, adamantyl, tricyclic [5.2.1.0] 2,6 ] Decane-8-yl, tetracyclo[4.4.0.1 2,5 .1 7,10 Bridged cyclic hydrocarbon groups such as dodecane-3-yl.

[0084] As the aromatic hydrocarbon group, it is preferred to be an aromatic hydrocarbon group with 6 to 14 carbon atoms (preferably 6 to 10), such as phenyl, naphthyl, etc.

[0085] In the peracid shown in equation (a) above, as R 5 A peracid consisting of hydrogen atoms, such as hydrogen peroxide.

[0086] In the peracid shown in equation (a) above, as R 5 These are peracids with aliphatic hydrocarbon groups, such as performic acid and peracetic acid.

[0087] In the peracid shown in equation (a) above, as R 5 Peracids with aromatic hydrocarbon groups, such as perbenzoic acid, are examples.

[0088] As the peracid, considering its excellent oxidizing power and the fact that it eliminates the need for chlorine-based solvents and suppresses the contamination of chlorine-containing compounds into the epoxy compound being the target, R is preferably used in the peracid shown in formula (a) above. 5 Peracids with aliphatic hydrocarbon groups (especially performic acid and / or peracetic acid).

[0089] The amount of peracid used is, for example, about 3 to 6 mol relative to 1 mol of the compound shown in formula (2), preferably 3 to 4.5 mol.

[0090] The epoxidation reaction is preferably carried out in the presence of a solvent. The solvent is preferably a hydrophobic solvent (i.e., a low-polarity solvent). Examples of such solvents include: aliphatic hydrocarbon solvents such as hexane, heptane, and octane; alicyclic hydrocarbon solvents such as cyclohexane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, and ethylbenzene; chain or cyclic ether solvents such as diethyl ether and tetrahydrofuran; and acetate solvents such as ethyl acetate. One of these solvents may be used alone, or two or more may be used in combination.

[0091] As the solvent, an acetate-based solvent is preferred, considering that its boiling point at atmospheric pressure is higher than the reaction temperature, but the boiling point is not too high, so it is easy to remove by distillation and easy to operate.

[0092] The amount used as a solvent is, for example, 1 to 10 times the weight of the compound shown in formula (2), preferably 2 to 5 times the weight.

[0093] The epoxidation reaction is carried out at a temperature of, for example, 20–50°C. The reaction time is, for example, approximately 0.5–12 hours. The transesterification reaction can be carried out under normal pressure, reduced pressure, or increased pressure. The atmosphere for the epoxidation reaction is not particularly limited as long as it does not hinder the reaction; for example, it can be any atmosphere such as air, nitrogen, or argon.

[0094] After the epoxidation reaction is completed, the reaction products are preferably washed with water and then neutralized with alkali.

[0095] After the epoxidation reaction is completed, the resulting reaction products can be separated and purified by methods such as filtration, concentration, distillation, extraction, crystallization, adsorption, recrystallization, column chromatography, etc., or by combining these methods to form a separation method. Thus, compound (3) can be obtained.

[0096] According to the method for manufacturing epoxy compounds disclosed herein, transesterification and epoxidation reactions can be carried out rapidly to manufacture compounds (3) in high yield (e.g., 60% or more, preferably 70% or more, particularly preferably 80% or more, and most preferably 85% or more).

[0097] The compound (3) obtained by the method for manufacturing the epoxy compound has low volatility and excellent workability. In addition, it can be cured to form a cured product with excellent heat resistance.

[0098] Furthermore, according to the method for manufacturing the epoxy compound, epoxy compounds with low chlorine content or low chlorine content can be produced. The chlorine content (or the amount of chlorine mixed in) is, for example, 1000 ppm or less of the epoxy compound, preferably 100 ppm or less, and particularly preferably 10 ppm or less.

[0099] The epoxy compound obtained by the manufacturing method has a low chlorine content, as mentioned above, and is therefore preferably used as an encapsulation material for printed circuit boards.

[0100] Furthermore, if the epoxy compound obtained by the manufacturing method is used as the encapsulation material, there will be no problem of wiring corrosion due to chlorine, thus enabling further miniaturization, high density, high reliability, and long lifespan of electronic components.

[0101] [Composition]

[0102] The compositions disclosed herein (e.g., curable compositions) contain a compound represented by formula (e) below (hereinafter sometimes referred to as "compound (e)") and an epoxy compound represented by formula (3) below.

[0103] [Chemical Formula 10]

[0104]

[0105] (In formula (e), X represents a single bond or a linking group)

[0106] [Chemical Formula 11]

[0107]

[0108] (Compound(e))

[0109] Compound (e) in this disclosure is the compound represented by formula (e) above. In formula (e), X represents a single bond or a linking group. The cyclohexyl epoxide in formula (e) may also have substituents, such as C... 1-3 Alkyl groups, etc.

[0110] Examples of such linking groups include: divalent hydrocarbon groups, alkenylene groups formed by partial or complete epoxidation of carbon-carbon double bonds, carbonyl groups (-CO-), ether groups (-O-), ester groups (-COO-), carbonate groups (-O-CO-O-), amide groups (-CONH-), and groups formed by the linkage of these groups.

[0111] Examples of divalent hydrocarbon groups include: straight-chain or branched alkylene groups with 1 to 18 carbon atoms, and divalent alicyclic hydrocarbon groups with 3 to 18 carbon atoms. Examples of straight-chain or branched alkylene groups with 1 to 18 carbon atoms include: methylene, methylmethylene, dimethylmethylene, ethylene, propylene, trimethylene, etc. Examples of divalent alicyclic hydrocarbon groups with 3 to 18 carbon atoms include: 1,2-cyclopentane, 1,3-cyclopentane, 1,2-cyclohexane, 1,3-cyclohexane, 1,4-cyclohexane, etc.

[0112] Examples of alkenyl groups formed by epoxidation of part or all of the carbon-carbon double bond (sometimes called "epoxidized alkenyl groups") 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 formed by epoxidation of the entire carbon-carbon double bond are preferred, and alkenyl groups with 2 to 4 carbon atoms formed by epoxidation of the entire carbon-carbon double bond are more preferred.

[0113] Examples of compounds represented by formula (e) above include: (3,4,3',4'-diepoxy)bicyclohexane, bis(3,4-epoxycyclohexylmethyl) ether, 1,2-epoxy-1,2-bis(3,4-epoxycyclohexane-1-yl)ethane, 2,2-bis(3,4-epoxycyclohexane-1-yl)propane, 1,2-bis(3,4-epoxycyclohexane-1-yl)ethane, and compounds represented by formulas (e-1) to (e-10) below. It should be noted that L in formula (e-5) below 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. Furthermore, n in formulas (e-5), (e-7), (e-9), and (e-10) below... 1 ~n 8 They represent integers from 1 to 30 respectively.

[0114] [Chemical Formula 12]

[0115]

[0116] [Chemical Formula 13]

[0117]

[0118] The weight ratio (of compound (e) to compound (3) in the composition disclosed herein is in the range of 90 / 10 to 1 / 99. From the viewpoint of having a suitable viscosity and obtaining a cured product with excellent heat resistance, this weight ratio is preferably 60 / 40 to 10 / 90, particularly preferably 50 / 50 to 10 / 90, and most preferably 40 / 60 to 20 / 80. If the content of compound (e) is excessive, the viscosity of the composition at 100-150°C is too low and it is prone to leaking out of the mold, resulting in flash. It should be noted that the viscosity of the composition at 100-150°C is preferably, for example, in the range of 100-2500 mPa·s. Furthermore, if the content of compound (e) is excessive, the heat resistance of the obtained cured product tends to decrease. On the other hand, if the content of compound (e) is too low, the viscosity of the composition becomes too high, for example, making it difficult to use for transfer molding.

[0119] The viscosity of the composition at 25°C and a shear rate of 3.1 (1 / s) is, for example, 500–32000 mPa·s, wherein, from the viewpoint of ease of transfer molding, it is preferably 1000–32000 mPa·s, particularly preferably 2000–25000 mPa·s, most preferably 2000–10000 mPa·s, and especially preferably 2000–5000 mPa·s. The viscosity of the slurry can be controlled by adjusting the mixing ratio of the compound (e) and the compound (3).

[0120] In addition to the compounds (e) and (3), the composition may also contain other components, such as curing catalysts, curing agents, curing accelerators, solvents, etc.

[0121] The amount of the curing catalyst used is, for example, about 0.1 to 3.0 parts by weight, preferably 0.3 to 1.5 parts by weight, relative to a total of 100 parts by weight of the compound (e) and the compound (3).

[0122] The amount of curing agent used is, for example, about 80 to 130 parts by weight relative to a total of 100 parts by weight of the compound (e) and the compound (3).

[0123] The amount of the curing accelerator used is, for example, about 0.1 to 3.0 parts by weight, preferably 0.3 to 1.5 parts by weight, relative to a total of 100 parts by weight of the compound (e) and the compound (3).

[0124] The composition can be prepared by combining or mixing the compound (e) and the compound (3) with other ingredients as needed.

[0125] The composition can be cured by subjecting the composition to heat treatment and / or light irradiation to cause the polymerization reaction of the compound (e) contained in the composition with the compound (3).

[0126] The cured composition exhibits excellent heat resistance, with a peak temperature of Tg (DMA-tanδ), i.e., tanδ determined by a dynamic viscoelasticity measuring device (DMA), for example, 180°C or higher, preferably 200°C or higher, and particularly preferably 210°C or higher. Furthermore, the inflection point of Tg (TMA), i.e., the coefficient of thermal expansion determined by TMA, is, for example, 190°C or higher, preferably 200°C or higher, particularly preferably 210°C or higher, and most preferably 220°C or higher.

[0127] Furthermore, if the compound (3) is obtained by the above-described method for manufacturing epoxy compounds, a composition with low chlorine content can be obtained. When the composition contains chlorine, the epoxy groups of the compounds (e) and (3) undergo ring-opening due to chlorine, making the curing reaction difficult to proceed and thus making it difficult to obtain a cured product with excellent heat resistance. However, if the composition has low chlorine content, it can exhibit excellent curability and form a cured product with excellent heat resistance.

[0128] The chlorine content of the composition is, for example, less than 1000 ppm, preferably less than 100 ppm, and particularly preferably less than 10 ppm.

[0129] The composition, as described above, can form a cured product with excellent heat resistance. Therefore, the composition is preferably used, for example, as a (transparent) encapsulation material for optical semiconductor devices, or as a raw material for manufacturing reflectors for light reflection.

[0130] The above-described components and combinations thereof are merely examples, and appropriate additions, omissions, substitutions, and modifications can be made to the components without departing from the spirit of this disclosure. Furthermore, this disclosure is not limited by the embodiments, but only by the description in the patent claims.

[0131] Example

[0132] The present disclosure will be described in more detail below through embodiments, but the present disclosure is not limited to these embodiments.

[0133] Example 1

[0134] 51.0 g of 1,3,5-cyclohexanetriol [manufactured by Tokyo Chemical Industry Co., Ltd.], 275.9 g of methyl 3-cyclohexene-1-carboxylate [manufactured by Tokyo Chemical Industry Co., Ltd.], 326.9 g of xylene, and 1.24 g of lithium amide [LiNH2, manufactured by MERCK Corporation] were charged into a 1 L stainless steel reactor, and the reactor temperature was raised to 190 °C. Furthermore, methanol distilled off during the reaction was removed.

[0135] The resulting reaction solution was diluted with 345 g of ethyl acetate and neutralized with 6.4 g of acetic acid. Then, the solution was washed with water and the solvent was removed by distillation to give 170.0 g of compound (2) (yield: 96%).

[0136] Next, 170.0 g of the obtained compound (2) was diluted with 510 g of ethyl acetate, and 364.1 g of 28% peracetic acid was added dropwise over 1 hour at 40°C. After the addition was completed, the reaction was allowed to proceed for 7 hours. The resulting reaction solution was washed with water and then neutralized with a 10% sodium hydroxide aqueous solution. The solvent was then removed by distillation to obtain 177.8 g of compound (3) (yield: 95%). The chlorine content of the obtained compound (3) was below the detection limit (i.e., below 10 ppm).

[0137] Example 2 (Preparation of the Composition)

[0138] The components were mixed uniformly and degassed using a rotary stirring device (trade name "Awatori Rentaro AR-250" manufactured by THINKY Co., Ltd.) according to the formula listed in Table 1 below, resulting in a composition (chlorine content below the detection limit, i.e., below 10 ppm). The viscosity of the obtained composition at 25°C and a shear rate of 3.1 (1 / s) was 31400 mPa·s.

[0139] It should be noted that the viscosity of the composition was measured using a rheometer (trade name "PHYSICA UDS200", manufactured by Anton Paar) at a temperature of 25°C and a rotation speed of 186 rpm.

[0140] (Cure of the composition)

[0141] The obtained composition was filled into a molding machine and heated at 80°C for 3 hours, followed by heating at 180°C for 2 hours, thereby obtaining a cured product. The heat resistance of the cured product was then evaluated as follows: 1.

[0142] Examples 3-4, Comparative Example 1

[0143] The formulation was modified as described in Table 1 below. Otherwise, the composition and its cured product were obtained in the same manner as in Example 2, and the heat resistance of the obtained cured product was evaluated.

[0144] Example 5 (Preparation of the Composition)

[0145] The components were mixed and degassed using a rotary stirring device according to the formula described in Table 2 below to obtain the composition.

[0146] (Cure of the composition)

[0147] The obtained composition was filled into a molding machine and heated at 100°C for 2 hours, followed by heating at 150°C for 2 hours, and then heating at 180°C for 1 hour to obtain a cured product. Furthermore, the heat resistance of the obtained cured product was evaluated as follows: 1, 2.

[0148] Comparative Example 2 (Preparation of the Composition)

[0149] The formulation was modified as described in Table 2 below. Otherwise, the composition and its cured product were obtained in the same manner as in Example 5, and the heat resistance of the obtained cured product was evaluated.

[0150] (Evaluation of the heat resistance of the cured product 1)

[0151] Test pieces with dimensions of 0.5 mm thickness × 8 mm width × 40 mm length were cut from the obtained cured material. The peak temperature (Tg(DMA-tanδ)) of the loss tangent of the test pieces was measured using a dynamic viscoelasticity measuring apparatus (DMA) (manufactured by Seiko Instruments Co., Ltd.).

[0152] It should be noted that the measurement was performed under the following conditions.

[0153] Measurement atmosphere: Under nitrogen gas flow.

[0154] Measurement temperature range: -50~300℃.

[0155] Heating rate: 2℃ / minute.

[0156] Deformation mode: Stretch mode.

[0157] (Evaluation of the heat resistance of the cured product 2)

[0158] Using a TMA measuring device (trade name "TMA / SS100", manufactured by SII Technology), the thermal expansion coefficient was measured in a nitrogen atmosphere at a heating rate of 5°C / min for a temperature range of 30–300°C, according to the method in JIS K 7197. Tangents were then drawn from the curves below and above the glass transition temperature, and the glass transition temperature (Tg(TMA)) of the cured product was determined from the intersection of these tangents.

[0159] It should be noted that the coefficient of linear expansion (ppm / ℃) below the glass transition temperature is set as α1, and the coefficient of linear expansion (ppm / ℃) above the glass transition temperature is set as α2.

[0160] [Table 1]

[0161]

[0162] [Table 2]

[0163]

[0164] CELLOXIDE 2021P: 3,4-epoxycyclohexylmethyl(3,4-epoxy)cyclohexylcarbamate, manufactured by Daicel Inc.

[0165] SI-100L: Cured catalyst, manufactured by San-Apro Corporation.

[0166] RIKACID MH700F: Curing agent, 4-methylhexahydrophthalic anhydride / hexahydrophthalic anhydride = 70 / 30, manufactured by Shin Nippon Rikka Co., Ltd.

[0167] U-CAT 12XD: Curing accelerator, manufactured by San-Apro Co., Ltd.

[0168] In summary, the following notes outline the composition and changes of this disclosure.

[0169] [1] A method for manufacturing an epoxy compound, comprising: step 1, generating a compound of formula (2) by transesterification reaction of a compound of formula (1) with 1,3,5-cyclohexanetriol; and step 2, reacting a peracid with the generated compound of formula (2) to obtain an epoxy compound of formula (3).

[0170] [2] According to the method for manufacturing the epoxy compound described in [1], the peracid is formic acid and / or peracetic acid.

[0171] [3] The method for manufacturing the epoxy compound according to [1] or [2], wherein the reaction of step 1 is carried out in the presence of an alkali metal amide and / or an alkyl alkali metal.

[0172] [4] The method for manufacturing the epoxy compound according to [1] or [2], wherein the reaction of step 1 is carried out in the presence of an alkali metal amide and / or an alkyl alkali metal, and the amount of the alkali metal amide and the alkyl alkali metal used is 15 to 35 mol relative to 100 mol of the compound shown in formula (1).

[0173] [5] The method for manufacturing an epoxy compound according to [1] or [2], wherein the reaction of step 1 is carried out in the presence of an alkali metal amide as shown in formula (c1).

[0174] [6] The method for manufacturing the epoxy compound according to [1] or [2], wherein the reaction of step 1 is carried out in the presence of the alkali metal amide shown in formula (c1), and the amount of the alkali metal amide shown in formula (c1) used is 15 to 35 mol relative to 100 mol of the compound shown in formula (1).

[0175] [7] The method for manufacturing an epoxy compound according to any one of [1] to [6], wherein the reaction of step 2 is carried out in the presence of an acetate-based solvent.

[0176] [8] The method for manufacturing an epoxy compound according to any one of [1] to [7], wherein the chlorine content of the epoxy compound represented by formula (3) is less than 1000 ppm.

[0177] [9] A composition comprising the compound shown in formula (e) and the epoxy compound shown in formula (3) in a weight ratio of 90 / 10 to 1 / 99.

[0178]

[10] The composition according to [9], wherein the composition is for transfer molding.

[0179]

[11] A method for manufacturing a light reflector, wherein the composition described in [9] is subjected to transfer molding to manufacture the light reflector.

[0180]

[12] A method for manufacturing an encapsulant, wherein the composition described in [9] is used to manufacture the encapsulant.

[0181]

[13] A method for manufacturing an encapsulant for an optical semiconductor device, wherein the composition described in [9] is used to manufacture the encapsulant for the optical semiconductor device.

[0182]

[14] An optical semiconductor device having a structure in which an optical semiconductor element is encapsulated by a cured composition of the composition described in [9].

[0183]

[15] A reflector for optical semiconductors, which is composed of a cured product of the composition described in [9].

[0184] Industrial availability

[0185] According to the method for manufacturing epoxy compounds disclosed herein, 1,3,5-tris(3,4-epoxycyclohexanecarbonyloxy)cyclohexane can be manufactured more efficiently than conventional methods.

[0186] Furthermore, the method for manufacturing the epoxy compound yields an epoxy compound with extremely low chlorine content. Therefore, this epoxy compound is preferably used as a packaging material for semiconductors and the like.

Claims

1. A composition comprising, in a weight ratio of 90 / 10 to 1 / 99 of the former / the latter, a compound (e) and an epoxy compound of formula (3) thereof, manufactured by the method described below. The compound (e) is at least one compound selected from (3,4,3',4'-diepoxy)bicyclohexane, bis(3,4-epoxycyclohexylmethyl) ether, 1,2-epoxy-1,2-bis(3,4-epoxycyclohexan-1-yl)ethane, 2,2-bis(3,4-epoxycyclohexan-1-yl)propane, 1,2-bis(3,4-epoxycyclohexan-1-yl)ethane, and compounds represented by formulas (e-1) to (e-10) below. ， ， In the above formula, L is an alkylene group with 1 to 3 carbon atoms, and n 1 ~n 8 They represent integers from 1 to 30 respectively. ， The manufacturing method includes: Step 1 involves conducting a transesterification reaction between the compound shown in formula (1) and 1,3,5-cyclohexanetriol in an atmosphere containing 10 to 50 mol of at least one compound selected from lithium amide, lithium diisopropylamide, 2,2,6,6-tetramethylpiperidine lithium, and hexamethyldisilamide lithium relative to 100 mol of the compound shown in formula (1). The resulting product is then neutralized with an acid to generate the compound shown in formula (2), where R in formula (1)... 1 Indicates alkyl; and ， ， Step 2 involves reacting the peracid with the compound represented by formula (2) to obtain the epoxy compound represented by formula (3). ， The reaction temperature for the transesterification reaction is 150–250 °C.

2. The composition according to claim 1, wherein, The peracids are performic acid and / or peracetic acid.

3. The composition according to claim 1 or 2, wherein, The reaction in step 2 is carried out in the presence of an acetate-based solvent.

4. The composition according to claim 1 or 2, wherein, The chlorine content of the epoxy compound shown in formula (3) is less than 1000 ppm.

5. The composition according to claim 1 or 2, wherein, The composition is for transfer molding.

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