Compound, curable resin composition and cured product thereof

Abstract

To provide a 2-pyrone-4,6-dicarboxylic acid derivative that is liquid and has excellent workability when blended with epoxy resin, and also has excellent cured properties, and a curable resin composition comprising the same.SOLUTION: The present invention provides a compound represented by formula (a-1). (In the formula (a-1), R1 and R2 each denote a C1-15 organic group comprising a carboxy group. n is a repeating number to represent an integer of 1-4).SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to 2-pyrone-4,6-dicarboxylic acid (PDC) derivatives and a method for producing the same. [Background technology]

[0002] In recent years, attention has been focused on plant-derived polymers obtained from plant-derived raw materials or through microbial metabolism. These polymers are environmentally friendly materials that do not use petroleum as a raw material, and incineration does not increase atmospheric carbon dioxide, in the sense that the carbon dioxide fixed in plants is returned to the atmosphere. Furthermore, even if they are disposed of in a landfill without incineration, they are decomposed by microorganisms in the soil, so there is no risk of environmental destruction. Examples of such plant-derived polymers include polylactic acid and polyhydroxybutyric acid, and as promising biodegradable environmentally friendly materials, their use in various molded products is being developed.

[0003] On the other hand, lignin, a plant-derived aromatic polymer, is a biomass resource that is ubiquitously contained in plant cell walls. However, because its chemical structure is composed of diverse components and its polymer structure is complex, no effective utilization technology has yet been developed. For example, lignin, which is produced as a by-product in large quantities in the papermaking industry, is incinerated as an alternative fuel to heavy oil, rather than being used effectively.

[0004] In recent years, methods have been developed for producing the single compound 2-pyrone-4,6-dicarboxylic acid by converting plant-derived aromatic components such as lignin into a mixture of several low-molecular-weight compounds by chemical decomposition methods such as hydrolysis, oxidative decomposition, and solvolysis, or by physicochemical decomposition methods using supercritical water or supercritical organic solvents. For example, Patent Document 1 discloses a method for producing the single compound 2-pyrone-4,6-dicarboxylic acid by fermentation production technology from a low-molecular-weight mixture containing vanillin, syringaldehyde, vanillic acid, syringic acid, protocatechuic acid, etc., obtained by a low-molecular-weight reduction technique using plant raw materials containing lignin, through multi-step enzymatic reactions.

[0005] If the single compound obtained in this way, 2-pyrone-4,6-dicarboxylic acid, could be used as a raw material for biodegradable plastics and various chemical products, it would be possible to effectively utilize lignin-containing plant materials (biomass), which do not compete with food supplies. However, little is known about how to utilize 2-pyrone-4,6-dicarboxylic acid derived from lignin-containing biomass. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Patent No. 6674283 Summary of the Invention [Problem to be solved by the invention]

[0007] Patent Document 1 reports an epoxy resin composition using 2-pyrone-4,6-dicarboxylic acid as an epoxy resin curing agent. However, 2-pyrone-4,6-dicarboxylic acid is a solid with poor solubility, which makes it difficult to work with epoxy resins. Furthermore, the compounds have poor compatibility and are difficult to mix, making it impossible to form a uniform cured film and making it difficult to achieve the inherent cured physical properties of the resin. Therefore, there is a need for a new 2-pyrone-4,6-dicarboxylic acid derivative that has good solubility and compatibility with resins, is liquid, and is easy to work with when blending with epoxy resins.

[0008] The present invention has been made in view of the above-mentioned problems, and aims to provide a 2-pyrone-4,6-dicarboxylic acid derivative that is liquid and has excellent workability when blended with an epoxy resin, and further has excellent cured physical properties, and a curable resin composition containing the same. [Means for solving the problem]

[0009] That is, the present invention relates to the following (1) to (8): In the present invention, "(Numerical value 1) to (Numerical value 2)" indicates that the upper and lower limit values ​​are included. (1) A compound represented by the following formula (a-1):

[0010] [ka]

[0011] (In formula (a-1), R1 and R2 each represent an organic group containing a carboxy group and having 1 to 15 carbon atoms. n represents the number of repetitions and represents an integer of 1 to 4.) (2) The compound according to the preceding item (1), wherein R1 and R2 in the formula (a-1) are each one selected from the following formulas (2a) to (2c), (3a) to (3i), or (4a) to (4d):

[0012] [ka]

[0013] (The * symbol indicates that the group is bonded to the oxygen atom in formula (a-1).) (3) The compound according to the above (1) or (2), wherein n in the formula (a-1) is 1. (4) A mixture containing the compound according to any one of (1) to (3) above and a carboxylic acid anhydride compound. (5) A curable resin composition containing the compound according to any one of (1) to (3) above or the mixture according to (4) above. (6) A curable resin composition according to the above (5), further comprising an epoxy resin. (7) The curable resin composition according to (5) or (6) above, further comprising a curing agent. (8) The curable resin composition according to any one of (5) to (7) above, which is a semiconductor encapsulant. [Effects of the Invention]

[0014] The compound of the present invention is liquid and has good compatibility with epoxy resins, and is not only excellent in workability but also suitable for use as a material that requires heat resistance (Tg) and low water absorption, particularly as a semiconductor encapsulant. [Brief explanation of the drawings]

[0015] [Figure 1] The 1H-NMR charts of compounds 1 and 2 are shown below. DETAILED DESCRIPTION OF THE INVENTION

[0016] The present invention will be described in detail below. The compound of the present invention is represented by the following formula (a-1).

[0017] [ka]

[0018] (In formula (a-1), R1 and R2 each represent an organic group containing a carboxy group and having 1 to 15 carbon atoms. n represents the number of repetitions and represents an integer of 1 to 4.)

[0019] In the formula (a-1), n ​​is preferably 1 or 2, and 1 is particularly preferred.

[0020] In the formula (a-1), R1 and R2 may be the same or different, but it is more preferable that they are the same.

[0021] Specific examples of R1 and R2 in the formula (a-1) include organic groups having an aromatic ring represented by the following formulas (2a) to (2c), organic groups having an alicyclic ring represented by the following formulas (3a) to (3i), and organic groups having an alicyclic ring represented by the following formulas (4a) to (4d). Among these, organic groups represented by the following formulas (3a) to (3e) are preferred.

[0022] [ka]

[0023] (The * symbol indicates that the group is bonded to the oxygen atom in formula (a-1).)

[0024] The compound represented by the formula (a-1) can be obtained by subjecting an alcohol represented by the following formula (a) to an addition reaction with a carboxylic acid anhydride compound (hereinafter also simply referred to as an acid anhydride):

[0025] [ka]

[0026] (In formula (a), n is the number of repetitions and represents an integer of 1 to 4.)

[0027] The compound in which R1 and R2 in the formula (a-1) are organic groups represented by the formulas (2a) to (2c), (3a) to (3i), or (4a) to (4d) can be obtained by an addition reaction between the compound represented by the formula (a) and an acid anhydride represented by the following formulas (5a) to (5c), (6a) to (6i), or (7a) to (7d).

[0028] [ka]

[0029] Next, a method for synthesizing the compound represented by the formula (a-1) will be described. As described above, the compound represented by the formula (a-1) can be obtained by the reaction of the alcohol represented by the formula (a) with an acid anhydride. This reaction is preferably carried out without a catalyst, but an acid or a base may be used as a catalyst. When a catalyst is used, examples of the catalyst that can be used include acidic compounds such as hydrochloric acid, sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, nitric acid, trifluoroacetic acid, and trichloroacetic acid; metal hydroxides such as sodium hydroxide, potassium hydroxide, calcium hydroxide, and magnesium hydroxide; amine compounds such as triethylamine, tripropylamine, and tributylamine; heterocyclic compounds such as pyridine, dimethylaminopyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, imidazole, triazole, and tetrazole; and quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylpropylammonium hydroxide, trimethylbutylammonium hydroxide, trimethylcetylammonium hydroxide, trioctylmethylammonium hydroxide, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetramethylammonium acetate, and trioctylmethylammonium acetate. These catalysts may be used alone or in combination of two or more. Among these, triethylamine, pyridine and dimethylaminopyridine are preferred. There are no particular restrictions on the amount of catalyst used, but it is generally preferable to use 0.001 to 5 parts by mass, if necessary, per 100 parts by mass of the total weight of the alcohol represented by the formula (a) and the acid anhydride.

[0030] This reaction is preferably carried out without a solvent, but an organic solvent may be used. The amount of organic solvent used is 0.005 to 1 part by weight, preferably 0.005 to 0.7 parts, and more preferably 0.005 to 0.5 parts (i.e., 50% by weight or less), per 1 part by mass of the total amount of the acid anhydride and the alcohol represented by formula (a) as reaction substrates. If the amount of organic solvent used exceeds 1 part by weight per 1 part by mass of the reaction substrates, the reaction proceeds extremely slowly, which is not preferred. Specific examples of usable organic solvents include alkanes such as hexane, cyclohexane, and heptane; aromatic hydrocarbon compounds such as toluene and xylene; ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and anone; ethers such as diethyl ether, tetrahydrofuran, and dioxane; and ester compounds such as ethyl acetate, butyl acetate, and methyl formate.

[0031] This reaction proceeds sufficiently even at a temperature of about 20°C. In consideration of reaction time, the reaction temperature is preferably 30 to 200°C, more preferably 40 to 200°C, and particularly preferably 40 to 150°C. In particular, when this reaction is carried out without a solvent, the reaction is preferably carried out at 120°C or lower, and particularly preferably at 30 to 120°C or 40 to 120°C, due to the volatilization of the acid anhydride.

[0032] Theoretically, the reaction ratio of the acid anhydride and the alcohol represented by formula (a) is preferably equimolar, but this can be changed as necessary. The specific ratio of the two components used during the reaction is preferably such that, in terms of functional group equivalents, 1 equivalent of the acid anhydride group is charged with 0.001 to 2 equivalents, more preferably 0.01 to 1.5 equivalents, and even more preferably 0.1 to 1.2 equivalents of the alcohol represented by formula (a), in terms of hydroxyl group equivalents. In the present invention, the compound represented by formula (a-1) is preferably liquid. To obtain a liquid compound represented by formula (a-1), ideally, an equimolar or greater amount of the alcohol represented by formula (a) is used. However, fluidity is important when a filler is added, and to ensure this fluidity, it is acceptable to slightly disrupt the viscosity balance within the range that maintains solidity (softening point 50°C or higher). Specifically, the molar ratio of the alcoholic hydroxyl group to the acid anhydride equivalent is preferably 0.85 to 1.20 molar equivalents, and particularly preferably 0.90 to 1.1.0 molar equivalents.

[0033] The reaction time depends on the reaction temperature, the amount of catalyst, etc., but from the viewpoint of industrial production, a long reaction time is not preferable because it consumes a large amount of energy. Also, a reaction time that is too short means that the reaction is rapid, which is undesirable from the viewpoint of safety. The preferred range is 1 to 48 hours, preferably 1 to 36 hours, more preferably 1 to 24 hours, and even more preferably about 2 to 10 hours.

[0034] After the reaction is complete, if a catalyst is used, the catalyst is removed by neutralization, washing with water, adsorption, or the like, and the solvent is distilled off to obtain the target compound represented by formula (a-1). On the other hand, if the reaction is carried out without a catalyst, the solvent is distilled off as needed to obtain the compound represented by formula (a-1). Furthermore, if a solvent is used, the compound represented by formula (a-1) is obtained by removing the solvent. Furthermore, if no solvent or catalyst is used, the target compound represented by formula (a-1) can be obtained by directly extracting the product.

[0035] The most suitable production method is a method in which the acid anhydride and the alcohol represented by formula (a) are reacted at 40 to 150° C. in the absence of a catalyst, and the solvent is removed and the resulting product is then isolated.

[0036] The method for synthesizing the alcohol represented by formula (a) is not particularly limited, and examples thereof include a known method involving the reaction of PDC with ethylene glycol. Specifically, PDC and ethylene glycol are reacted in the presence of an acid catalyst, and the resulting reaction solution is cooled and crystallized, followed by suction filtration to obtain the compound represented by formula (a). The method for purifying the compound represented by formula (a) is not particularly limited, and simple washing with a solvent or the like may be sufficient, but a crystallization method is preferred, as the resulting compound has high crystallinity.

[0037] The mixture of the present invention contains a compound represented by the formula (a-1) and a carboxylic acid anhydride compound. As described above, the compound represented by the formula (a-1) can be obtained by reacting an alcohol represented by the formula (a) with an acid anhydride. However, the mixture of the present invention can be obtained by adding an excess amount of the acid anhydride without a separation step or the like. Therefore, in the mixture of the present invention, preferred acid anhydrides are those represented by the formulas (5a) to (5c), (6a) to (6i), or (7a) to (7d), and particularly preferred are those represented by the formulas (6a) to (6e).

[0038] In the mixture of the present invention, the content of the compound represented by formula (a-1) and the acid anhydride is preferably 20% to 100% of the compound represented by formula (a-1). The content can be appropriately changed depending on the compatibility with the thermosetting resin composition and the physical properties of the cured product, and is not particularly limited. 1 It can be calculated from the area ratio of H-NMR.

[0039] Next, the curable resin composition of the present invention will be described. The curable resin composition of the present invention may contain the compound represented by formula (a-1) either alone or in combination, and may also contain the acid anhydride used in synthesizing the compound represented by formula (a-1).

[0040] The curable resin composition of the present invention may contain an epoxy resin in addition to the compound represented by formula (a-1). The epoxy resin may be any epoxy resin commonly used in conventional epoxy resin compositions, without particular limitation. Examples include epoxidized novolac resins of phenols and aldehydes, such as phenol novolac epoxy resins and orthocresol novolac epoxy resins; diglycidyl ethers of bisphenol A, bisphenol F, bisphenol S, and alkyl-substituted bisphenols; glycidylamine epoxy resins obtained by reacting epichlorohydrin with polyamines such as diaminodiphenylmethane and isocyanuric acid; alicyclic epoxy resins obtained by oxidizing olefin bonds with peracids such as peracetic acid; diglycidyl isocyanurate, triglycidyl isocyanurate, and silsesquioxane compounds. These may be used alone or in combination. Among these epoxy resins, those with high heat resistance are preferred. Specifically, glycidyl ether epoxy resins and alicyclic epoxy resins are preferred from the standpoints of melt viscosity, coloration of the resulting cured product, and glass transition temperature.

[0041] The curable resin composition of the present invention may contain a curing agent in addition to the compound represented by formula (a-1). Examples of the curing agent that can be used in combination include amine compounds, acid anhydride compounds having an unsaturated ring structure, acid anhydrides having an organosiloxane skeleton, amide compounds, phenolic compounds, and carboxylic acid compounds. Among these, amine compounds, acid anhydride compounds, phenolic compounds, and carboxylic acid compounds are preferred.

[0042] Specific examples of usable curing agents include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, polyamide resin synthesized from a dimer of linolenic acid and ethylenediamine, phthalic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, nadic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride. , butanetetracarboxylic anhydride, bicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenols, terpene diphenols, 4,4'-biphenol, 2,2'-biphenol, 3,3',5,5'-tetramethyl-[1,1'-biphenyl]-4,4'-diol, hydroquinone, resorcinol, naphthalenediol, trimethylsilyl 4-(4-hydroxyphenyl)methane, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, phenols (phenol, alkyl-substituted phenols, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.), formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, dicyclopentadiene, fluoro Examples of the polycondensates include fural, 4,4'-bis(chloromethyl)-1,1'-biphenyl, 4,4'-bis(methoxymethyl)-1,1'-biphenyl, 1,4'-bis(chloromethyl)benzene, and 1,4'-bis(methoxymethyl)benzene, as well as modified products thereof, halogenated bisphenols such as tetrabromobisphenol A, imidazole, trifluoroborane-amine complexes, guanidine derivatives, and condensates of terpenes and phenols. These may be used alone or in combination of two or more.

[0043] The compounding ratio of the epoxy resin and the curing agent containing the compound represented by formula (a-1) is preferably 0.5 to 1.5 equivalents (considering carboxylic acid as monofunctional and acid anhydride as monofunctional) of active groups in the curing agent for thermosetting resins that can react with the epoxy groups per equivalent of epoxy groups in the epoxy resin, and particularly preferably 0.5 to 1.2 equivalents. If the amount is less than 0.5 equivalents or more than 1.5 equivalents per equivalent of epoxy groups, curing may be incomplete and good cured physical properties may not be obtained.

[0044] A curing catalyst can be added to the curable resin composition of the present invention as needed. Examples of the curing catalyst include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 2,4-diamino-6(2'-methylimidazole(1'))ethyl-s-triazine, 2,4-diamino-6(2'-undecylimidazole(1'))ethyl-s-triazine, 2,4-diamino-6(2'-ethyl,4-methylimidazole(1'))ethyl-s-triazine, 2, Various imidazoles, such as 4-diamino-6(2'-methylimidazole(1'))ethyl-s-triazine·isocyanuric acid adduct, 2-methylimidazole / isocyanuric acid 2:3 adduct, 2-phenylimidazole / isocyanuric acid adduct, 2-phenyl-3,5-dihydroxymethylimidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, and 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole, as well as salts of these imidazoles with polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, maleic acid, and oxalic acid; amides such as dicyandiamide; and 1,8-diaza-bicyclo[5.4.0] diaza compounds such as undecene-7 and their salts such as tetraphenylborate and phenol novolac, salts with the above polycarboxylic acids or phosphinic acids, quaternary ammonium salts such as tetrabutylammonium bromide, cetyltrimethylammonium bromide, trioctylmethylammonium bromide, hexadecyltrimethylammonium hydroxide (preferably C1 to C20 alkylammonium salts), triphenylphosphine, tri(toluyl)phosphine, tetraphenylphosphonium bromide, tetraphenylphosphonium tetra Examples of curing accelerators include phosphines such as phenyl borate, phosphonium compounds, phenols such as 2,4,6-trisaminomethylphenol, metal compounds such as amine adducts, tin octoate, zinc octoate, zinc stearate, copper naphthenate, and cobalt naphthenate, as well as microencapsulated curing accelerators obtained by microencapsulating these curing accelerators. Preferable examples in the present invention include imidazole compounds. The curing accelerator is typically used in an amount of 0.001 to 15 parts by mass, preferably 0.01 to 5 parts by mass, per 100 parts by mass of the epoxy resin.

[0045] If necessary, the curable resin composition of the present invention may contain, as additives other than those described above, commonly used additives for epoxy resins, such as dyes, fluorescent brighteners, reinforcing materials, fillers, white pigments or other pigments, nucleating agents, surfactants, plasticizers, viscosity modifiers, flowability modifiers, flame retardants, antioxidants, ultraviolet absorbers, and light stabilizers.

[0046] Examples of the filler include, but are not limited to, crystalline silica, fused silica, antimony oxide, titanium oxide, magnesium oxide, zirconium oxide, aluminum hydroxide, magnesium hydroxide, and alumina. These may be used alone or in combination of two or more. The amount of inorganic filler blended is preferably 1 to 1,000 parts by mass, and more preferably 1 to 800 parts by mass, per 100 parts by mass of the total amount of the curable resin composition.

[0047] The curable resin composition of the present invention can be obtained by uniformly dispersing and mixing the various components described above. While the method is not particularly limited, examples include thoroughly and uniformly stirring and mixing the various components using a mixer or the like, then kneading or melt-kneading them using a mixing roll, extruder, kneader, roll, extruder, or the like, followed by cooling and pulverization. The conditions for kneading or melt-kneading may be determined based on the types and amounts of the components, and are not particularly limited. Kneading at a temperature in the range of 20 to 200°C for 5 to 40 minutes is preferred. If the kneading temperature is lower than 20°C, the dispersibility of the components decreases, making it difficult to thoroughly knead them. However, if the kneading temperature is higher than 200°C, the crosslinking reaction of the resin composition may proceed, resulting in curing of the resin composition.

[0048] The curable resin composition of the present invention is preferably capable of being pressure (tablet) molded at room temperature of 0 to 30°C before heat molding. Pressure molding can be performed, for example, under conditions of 0.01 to 10 MPa and for 1 to 5 seconds. The mold used for pressure (tablet) molding is not particularly limited, but it is preferable to use one consisting of a pestle (upper mold) and a mortar (lower mold) made of a ceramic material, a fluorine-based resin material, or the like.

[0049] The curable resin composition of the present invention is useful in applications such as semiconductor encapsulation materials, which require a high glass transition temperature. [Example]

[0050] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "parts" and "%" in the text are based on mass.

[0051] [Example 1] Synthesis of the compound represented by formula (a-1) of the present invention (Step 1) Synthesis of intermediate compound 1 represented by formula (1) A 1000 ml separable flask was charged with 73.6 parts of PDC (2-pyrone-4,6-dicarboxylic acid), 447 parts of ethylene glycol, and 1.0 parts of 36% hydrochloric acid, and the mixture was heated to 70°C to dissolve. The mixture was then heated to 120°C, the pressure reduced to 4.5 kPa·s, and the reaction was carried out for 6 hours while distilling off water. After confirming the completion of the reaction, the mixture was allowed to cool and then placed in a refrigerator overnight to crystallize. The solid was recovered by suction filtration and purified by recrystallization four times with an excess amount of ethanol. The resulting wet cake was dried at 60°C for 3 hours to obtain intermediate compound 1 represented by the following formula (1) as a white solid in a 35% yield. Compound 1 1 The H-NMR measurement results are shown in Figure 1.

[0052] [ka]

[0053] (Step 2) Synthesis of Compound 2 Represented by Formula (2) 5.4 parts of intermediate compound 1 represented by formula (1) synthesized in step 1 and 18.9 parts of Rikacid MH-T were placed in a 500 ml separable flask, heated to 120°C, and reacted for 3 hours. After confirming the completion of the reaction, the flask was stored as is, and 21 parts of compound 2 represented by the following formula (2) were obtained in a liquid state with a yield of 87%. 1 The results of H-NMR measurement are shown in Figure 1. 78% of the reactants was unreacted Rikacid MH-T.

[0054] [ka]

[0055] [Comparative Example 1] Synthesis of comparative compound (Step 3) Synthesis of Compound 3 Represented by Formula (3) Compound 3 represented by the following formula (3) was obtained in a liquid form (45 parts, 87% yield) in the same manner as in step 2, except that TCD alcohol DM (manufactured by OXEA) was used instead of intermediate compound 1. 78% of the reaction product was unreacted Rikacid MH-T.

[0056] [ka]

[0057] [Examples 2 and 3, Comparative Example 2] Preparation of thermosetting resin composition The components were mixed according to the blending amounts (parts by mass) listed in Table 1. The resulting composition was stirred and degassed for 2 minutes at 1200 rpm using a planetary centrifugal mixer ARV-310 (Thinky), and then visually inspected for compatibility. Compatibility was visually inspected, with a ◯ indicating no turbidity in the composition and an × indicating turbidity. The blended thermosetting resin composition was then poured into a 35 mm x 50 mm, 0.8 mm thick Teflon mold and heated at 120°C for 1 hour and 150°C for 3 hours to obtain a cured product.

[0058] (Evaluation of cured properties of thermosetting resin composition) The cured properties of the resulting cured product were evaluated using a dynamic viscoelasticity measuring device. DMA measurement conditions Dynamic viscoelasticity measuring instrument: Hitachi High-Tech Science DMS6100 Measurement temperature range: 15 to 270°C Heating rate: 2°C / min Frequency: 1Hz Measurement mode: Tensile vibration Tg: The peak point of tan δ was taken as Tg.

[0059] (Measurement of water absorption rate of thermosetting resin composition) The resulting cured product was cut into 10 x 10 mm pieces using a laser cutter, dried in an oven at 120°C for 2 hours, and the initial weight was measured.The product was then immersed in Millipore water for 24 hours (25°C, 20% humidity environmental testing room), lightly wiped, and then weighed.The water absorption rate was evaluated from the change in weight before and after the test.

[0060] [Table 1]

[0061] The compound of Example 1 was liquid, had good compatibility with epoxy resins, and was easy to work with, and it was confirmed that the cured products of Examples 2 and 3, which were formed into compositions, had excellent heat resistance (Tg) and low water absorption. [Industrial Applicability]

[0062] The compound of the present invention can be used as a curing agent for, for example, epoxy compounds, and therefore can be suitably used in applications for thermosetting resin compositions that are cured by the action of heat.

Claims

1. A compound represented by the following formula (a-1): 【Chemistry 1】 (In formula (a-1), R １ , R ２ is one selected from the following formulas (2a) to (2c), (3a) to (3i), or (4a) to (4d), and n is the number of repetitions and represents an integer of 1 to 4. 【Chemistry 2】 (The * symbol indicates that the group is bonded to the oxygen atom in formula (a-1).)

2. The compound according to claim 1, wherein n in formula (a-1) is 1.

3. A mixture comprising the compound according to claim 1 or 2 and a carboxylic acid anhydride compound.

4. A curable resin composition comprising the compound according to claim 1 or 2, or the mixture according to claim 3.

5. The curable resin composition according to claim 4, further comprising an epoxy resin.

6. The curable resin composition according to claim 4 or 5, further comprising a curing agent.

7. The curable resin composition according to claim 4 , which is a semiconductor encapsulant.

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