Chain linker, curable resin composition and cured product thereof, chain linking method, and epoxy resin

Abstract

The present invention addresses the problem of providing a curing agent for use in a curable resin composition capable of forming a cured product having excellent heat resistance and dielectric properties, the curing agent having good handling properties such as solvent solubility. [Solution] Provided is a chain linker for a thermosetting compound and / or a compound having a radically polymerizable substituent, the chain linker being characterized by containing an ester compound represented by general formula (1) (in the formula, R1 each independently represents a C1-6 alkyl group or a C6-12 aryl group, R2 each independently represents a single bond or a C1-10 divalent hydrocarbon group, and R3 each independently represents a single bond or a C1-10 divalent hydrocarbon group; in general formulae (1a), (1b) or (1c), R1 and R2 each independently represent a hydrogen atom or a C1-6 alkyl group, R3 each independently represent a hydrogen atom or a C1-6 alkyl group, X represents a single bond, an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, or a divalent group represented by general formulae (1a), (1b) or (1c), n each independently represent 0 or an integer of 1-4, (2) # imgabs 1 # in general formulae (1a), (1b) and (1c), R4 and R5 each independently represent a hydrogen atom, a C1-10 alkyl group, a C1-10 haloalkyl group, or a C6-12 aryl group, r4 and R5 may be bonded to each other to form as a whole a cycloalkylidene group having 5-20 carbon atoms, Ar1 and Ar2 each represent an aryl group having 6-12 carbon atoms, and * each represents a bonding position.

Description

Technical Field

[0001] The present invention relates to a chain linker for a thermosetting compound and / or a compound having a radically polymerizable substituent, a curable resin composition containing the chain linker, a cured product thereof, a chain linking method, and an epoxy resin. Background Art

[0002] Epoxy resin is one type of thermosetting compound and is applied in various fields such as adhesives, coatings, composite materials, civil engineering and construction materials, and insulating materials for electrical and electronic components because of its excellent heat resistance, adhesiveness, water resistance, mechanical strength, and electrical properties. Especially in the electrical and electronic field, it is widely used in insulating potting, laminates, sealing materials, etc.

[0003] As important properties required for epoxy resins used as materials for electrical and electronic components, high heat resistance, low CTE, low dielectric constant, low dielectric loss tangent, low moisture absorption, etc. can be cited. In addition, in the field of highly integrated semiconductor materials, in recent years, with the continuous development of high multi-layerization, thinning of insulating layers, and complexity of structures, in addition to the above-listed characteristics, it is also required to balance various characteristics such as solvent solubility. Recently, it has been reported that a technique for improving low moisture absorption or dielectric properties by suppressing polarization through esterification of secondary hydroxyl groups generated by the reaction of epoxy groups with a curing agent.

[0004] Patent Document 1 discloses a thermosetting resin composition that uses a thermoplastic resin obtained by esterifying the secondary hydroxyl groups of an epoxy resin in a subsequent process and formulates a thermosetting resin therein, thereby improving the adhesion to a conductor layer while maintaining low moisture absorption and dielectric properties, but its heat resistance is not sufficient.

[0005] Patent Document Patent Document 1: International Publication No. 2005 / 095517 Summary of the Invention In view of the above prior art, an object of the present invention is to provide a curing agent having good processability such as solvent solubility and being used for a curable resin composition capable of forming a cured product having excellent heat resistance and dielectric properties.

[0006] The inventors of the present invention conducted in-depth research to solve the above problems and found that an ester compound formed from a bisphenol compound and a carboxylic acid containing a furan ring can be dissolved in solvents such as methyl ethyl ketone, has good processability, undergoes chain linking by reacting with an epoxy resin, and cures through chain linking. Further, the cured product obtained by esterifying secondary hydroxyl groups has suppressed polarization, and thus has excellent dielectric properties and heat resistance, thereby completing the present invention.

[0007] The present invention is as follows.

[0008] 1. A chain linker for a thermosetting compound and / or a compound having a radically polymerizable substituent, characterized by containing an ester compound represented by the general formula (1), [Chemical Formula 1]

[0009] In the formula, R 1 each independently represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, R 2 each independently represents a single bond or a divalent hydrocarbon group having 1 to 10 carbon atoms, R 3 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, X represents a single bond, an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, or a divalent group represented by the general formula (1a), (1b), or (1c), and n each independently represents 0 or an integer of 1 to 4, [Chemical Formula 2]

[0010] In the general formulas (1a), (1b), and (1c), R 4 and R 5 each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms, R 4 and R 5 may be bonded to each other to form a cycloalkanediyl group having 5 to 20 carbon atoms as a whole, Ar 1 and Ar 2 represent an aryl group having 6 to 12 carbon atoms, and * each represents a bonding position.

[0011] 2. The chain linker for a thermosetting compound and / or a compound having a radically polymerizable substituent according to 1., characterized by further containing an ester compound represented by the general formula (2), [Chemical Formula 3]

[0012] In the formula, R 1 , X, and n have the same definitions as those in the general formula (1), and R 6 each independently represents a monovalent hydrocarbon group having 1 to 20 carbon atoms.

[0013] 3. The chain linker for a thermosetting compound and / or a compound having a radically polymerizable substituent according to 2., characterized in that, based on 100 parts by weight of the ester compound represented by the general formula (1), 0.1 to 400 parts by weight of the ester compound represented by the general formula (2) is contained.

[0014] 4. A curable resin composition, characterized by containing a thermosetting compound and / or a compound having a radically polymerizable substituent as the (A) curable resin component, and an ester compound represented by the general formula (1) as the (B) chain linker, [Chemical Formula 4]

[0015] In the formula, R 1 each independently represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, R 2 each independently represents a single bond or a divalent hydrocarbon group having 1 to 10 carbon atoms, R 3 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, X represents a single bond, an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group or a divalent group represented by the general formula (1a), (1b) or (1c), and n each independently represents 0 or an integer of 1 to 4, [Chemical Formula 5]

[0016] In the general formulas (1a), (1b) and (1c), R 4 and R 5 each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, R 4 and R 5 may be bonded to each other to form a cycloalkanediyl group having 5 to 20 carbon atoms as a whole, Ar 1 and Ar 2 represent an aryl group having 6 to 12 carbon atoms, and * each represents a bonding position.

[0017] 5. The curable resin composition according to 4., characterized in that R 2 of the ester compound represented by the general formula (1) are all single bonds.

[0018] 6. The curable resin composition according to 5., characterized in that further R 3 of the ester compound represented by the general formula (1) are all hydrogen atoms.

[0019] 7. The curable resin composition according to 4., characterized in that the thermosetting compound is one or more compounds selected from epoxy resins, benzoxazine compounds, benzoxazine resins, phenolic resins, bismaleimide compounds and maleimide resins.

[0020] 8. The curable resin composition according to 4., characterized in that the compound having a radically polymerizable substituent is one or more compounds selected from diallyl phthalate resins, diallyl phthalate compounds, polyphenylene ether resins having a radically polymerizable substituent, and vinyl compounds.

[0021] 9. The curable resin composition according to 4., characterized in that it further contains an ester compound represented by the general formula (2) as the (B) chain linker. [Chemical formula 6]

[0022] In the formula, R 1 , X and n have the same definitions as in the general formula (1), and R 6 each independently represents a monovalent hydrocarbon group having 1 to 20 carbon atoms.

[0023] 10. A cured product formed by reacting and chain-linking the curable resin composition according to 4.

[0024] 11. A chain-linking method, characterized in that an ester compound represented by the general formula (1) is used as a chain linker and reacted with a thermosetting compound and / or a compound having a radically polymerizable substituent to perform chain-linking. [Chemical formula 7]

[0025] In the formula, R 1 each independently represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, R 2 each independently represents a single bond or a divalent hydrocarbon group having 1 to 10 carbon atoms, R 3 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, X represents a single bond, an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, or a divalent group represented by the general formula (1a), (1b), or (1c), and n each independently represents 0 or an integer of 1 to 4. [Chemical formula 8]

[0026] In the general formulas (1a), (1b), and (1c), R 4 and R 5 each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms, R 4 and R 5 may be bonded to each other to form a cycloalkanediyl group having 5 to 20 carbon atoms as a whole, Ar 1 and Ar 2Represents an aryl group having 6 to 12 carbon atoms, and * each represents a bonding position.

[0027] 12. The chain-linking method according to 11., characterized in that an ester compound represented by the general formula (2) is further used as the chain-linking agent, [Chemical formula 9]

[0028] In the formula, R 1 , X and n have the same definitions as in the general formula (1), and R 6 each independently represents a monovalent hydrocarbon group having 1 to 20 carbon atoms.

[0029] 13. The chain-linking method according to 12., characterized in that 0.1 to 400 parts by weight of the ester compound represented by the general formula (2) is used relative to 100 parts by weight of the ester compound represented by the general formula (1).

[0030] 14. An epoxy resin, characterized in that it is obtained by reacting any one of an aromatic diglycidyl ether compound, a mixture containing an aromatic dihydroxy compound and epihalohydrin, and a phenoxy resin having an epoxy group obtained by polymerizing an aromatic dihydroxy compound and epihalohydrin, with the ester compound represented by the general formula (1) to perform chain-linking, [Chemical formula 10]

[0031] In the formula, R 1 each independently represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, and R 2 each independently represents a single bond or a divalent hydrocarbon group having 1 to 10 carbon atoms, and R 3 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, X represents a single bond, an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, or a divalent group represented by the general formula (1a), (1b), or (1c), and n each independently represents 0 or an integer of 1 to 4, [Chemical formula 11]

[0032] In the general formulas (1a), (1b), and (1c), R 4 and R 5 each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and R 4 and R 5 may be bonded to each other to form a cycloalkanediyl group having 5 to 20 carbon atoms as a whole, and Ar 1 and Ar 2Represents an aryl group having 6 to 12 carbon atoms, and each * represents a bonding position.

[0033] Since the chain linker of the ester compound of the bisphenol compound and the carboxylic acid having a furan ring in the present invention can be dissolved in a solvent such as methyl ethyl ketone, a curable resin composition with good processability can be provided. In addition, since it can react with a thermosetting compound such as an epoxy resin as a curable resin component and / or a compound having a radically polymerizable substituent, the curable resin component and the molecular chain can be connected, and a cured product can be formed by chain linking, thereby providing a cured product with excellent heat resistance and dielectric properties.

[0034] The curable resin composition of the present invention containing a thermosetting compound such as an epoxy resin as a curable resin component and / or a compound having a radically polymerizable substituent and a chain linker has good processability. The chain linker uses a bisphenol compound as a raw material and contains an ester compound having furan rings at both ends of the bonding group. In addition, by reacting the molecular chain of the curable resin component containing it with the chain linker for chain linking, a cured product of the curable resin composition or a specific epoxy resin can be obtained, thereby providing a material with excellent heat resistance and dielectric properties.

[0035] Therefore, the material obtained by the present invention can be applied to various fields such as adhesives, composite materials, coatings, civil engineering building materials, and insulating materials for electrical and electronic components. In particular, it is useful as insulating potting, laminating materials, and sealing materials in the electrical and electronic fields. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] Figure 1 It is a graph showing the differential scanning calorimetry (DSC) of the ester compound (1-1) (compound (p-151)) obtained in Example 1.

[0037] Figure 2 It is a graph showing the differential scanning calorimetry (DSC) of the ester compound (1-2) (compound (p-28)) obtained in Example 2.

[0038] Figure 3 It is a graph showing the differential scanning calorimetry (DSC) of the ester compound (1-3) (compound (p-148)) obtained in Example 3. DETAILED DESCRIPTION OF THE INVENTION

[0039] <Curable Resin Composition> The curable resin composition of the present invention contains a thermosetting compound and / or a compound having a radically polymerizable substituent as the (A) curable resin component, and an ester compound represented by the general formula (1) as the (B) chain linker.

[0040] That is, as the form of the curable resin composition of the present invention, there are the following forms: a form containing a thermosetting compound as the (A) curable resin component and an ester compound represented by the general formula (1) as the (B) chain linker; a form containing a compound having a radically polymerizable substituent as the (A) curable resin component and an ester compound represented by the general formula (1) as the (B) chain linker; a form containing a thermosetting compound and a compound having a radically polymerizable substituent as the (A) curable resin component and an ester compound represented by the general formula (1) as the (B) chain linker.

[0041] In order to supplement or further improve the physical properties or characteristics of the curable resin composition of the present invention and the products and cured products obtained therefrom, for those skilled in the art who come into contact with the present invention, within the scope disclosed by the present invention and within the obvious scope, the aforementioned forms can be appropriately and suitably selected, or the compounds of the components used can be selected or changed, or their usage amounts can be adjusted, etc.

[0042] Among the compounds contained within the range of the ester compound represented by the general formula (1) used as the (B) chain linker in the curable resin composition of the present invention, only one kind can be used, or two or more kinds can be used in combination.

[0043] [Chemical formula 12]

[0044] (In the formula, R 1 each independently represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, R 2 each independently represents a single bond or a divalent hydrocarbon group having 1 to 10 carbon atoms, R 3 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, X represents a single bond, an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, or a divalent group represented by the general formula (1a), (1b), or (1c), and n each independently represents 0 or an integer of 1 to 4.) [Chemical formula 13]

[0045] (In the general formulas (1a), (1b), and (1c), R 4 and R 5 each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms, R 4 and R 5 may be bonded to each other to form a cycloalkanediyl group having 5 to 20 carbon atoms as a whole, Ar 1 and Ar 2represents an aryl group having 6 to 12 carbon atoms, and * each represents a bonding position.) In the curable resin composition of the present invention, by containing an ester compound represented by the general formula (1) as the (B) chain linker, the curable resin component can react with the ester compound to connect molecular chains, thereby enabling the curable resin composition to cure. Moreover, the resulting cured product has excellent heat resistance and dielectric properties.

[0046] Among them, in particular, the ester compound represented by the general formula (1) acts as a chain linker that is chain-linked by reaction with an epoxy resin and cured, and by esterifying the secondary hydroxyl groups generated by the reaction of the epoxy resin and the chain linker, the polarization of the resulting cured product can be suppressed, thereby enabling excellent dielectric properties. Therefore, the form in which the curable resin composition of the present invention contains an epoxy resin is useful due to the characteristics of the resulting cured product and is thus preferred. In addition, it can be seen from this that using the ester compound represented by the general formula (1) as a chain linker for an epoxy resin, the resulting cured product has the above characteristics and is thus preferred.

[0047] Since the ester compound represented by the general formula (1) has a furan ring, it also reacts with a compound having a radically polymerizable substituent in the curable resin component to be chain-linked, thereby enabling the production of a cured product thereof.

[0048] The ester compound represented by the general formula (1) has excellent solubility in solvents such as methyl ethyl ketone, cyclohexanone, N-methylpyrrolidone, toluene, propylene glycol monomethyl ether acetate, and ethyl acetate, and in particular, has excellent solubility in methyl ethyl ketone, which is one of the solvents widely used in the manufacture of electronic components such as semiconductors, and thus has excellent processability.

[0049] <(B) Chain Linker> The ester compound represented by the general formula (1) acts as a chain linker that reacts with a curable resin component of a thermosetting compound and / or a compound having a radically polymerizable substituent to be chain-linked, and in the curable resin composition of the present invention, it is used as the component (B) chain linker.

[0050] R in the general formula (1) 1 is preferably independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, more preferably independently a methyl group or a phenyl group, and particularly preferably a methyl group.

[0051] R in the general formula (1) 2Each is independently a single bond or a divalent hydrocarbon group having 1 to 10 carbon atoms. When it is a divalent hydrocarbon group, specifically, for example, it may include: methylene, ethylene, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, a linear or branched alkylene group having 1 to 10 carbon atoms such as cyclohexane-1,3-diyl or cyclohexane-1,4-diyl, or an alkylene group containing a cycloalkane; ethylidene, propylidene, isopropylidene, butylidene, cyclopentylidene, cyclohexylidene and other alkylidene groups having 1 to 10 carbon atoms; a divalent group having 1 to 10 carbon atoms containing a benzene ring such as a phenylene group or a group represented by the following formula.

[0052] [Chemical formula 14]

[0053] (In the formula, * represents the bonding position.) Among these, R 2 is preferably independently a single bond or a linear or branched alkylene group having 1 to 10 carbon atoms, an alkylene group containing a cycloalkane, or an alkylidene group having 1 to 10 carbon atoms, more preferably independently a single bond or a linear or branched alkylene group having 1 to 10 carbon atoms or an alkylene group containing a cycloalkane, and further preferably independently a single bond or a linear or branched alkylene group having 1 to 6 carbon atoms or an alkylene group containing a cycloalkane, and particularly preferably all are single bonds. R 2 The ester compound represented by the general formula (1) in which all are single bonds is obtained from a biomass-derived raw material, and thus it is also preferred in terms of a curable resin composition having an improved biomass yield.

[0054] R in the general formula (1) 3 is preferably independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably independently a hydrogen atom or a methyl group, and particularly preferably all are hydrogen atoms.

[0055] X in the general formula (1) is preferably a single bond, a sulfonyl group, a carbonyl group, or a divalent group represented by the general formula (1a), (1b), or (1c), more preferably a single bond or a divalent group represented by the general formula (1a) or the general formula (1b), and further preferably a single bond or a divalent group represented by the general formula (1a). Among the single bond or the divalent group represented by the general formula (1a), particularly preferably, R 4 and R 5 are bonded to each other and form a divalent group of an alkylidene group having 5 to 20 carbon atoms as a whole.

[0056] When X in the general formula (1) is the general formula (1a), R 4 and R 5More preferably, they are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms. Even more preferably, they are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a trifluoromethyl group, or an aryl group having 6 to 8 carbon atoms. Particularly preferably, they are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group.

[0057] In addition, R 4 and R 5 may be bonded to each other to form a cycloalkanediyl group having 5 to 20 carbon atoms as a whole. R 4 and R 5 are more preferably in this form. The cycloalkanediyl group having 5 to 20 carbon atoms may also contain an alkyl group as a side chain. The cycloalkanediyl group is preferably having 5 to 15 carbon atoms, more preferably having 6 to 12 carbon atoms, and particularly preferably having 6 to 9 carbon atoms. As the cycloalkanediyl group, specifically, for example, cyclopentanediyl (5 carbon atoms), cyclohexanediyl (6 carbon atoms), 3-methylcyclohexanediyl (7 carbon atoms), 4-methylcyclohexanediyl (7 carbon atoms), 3,3,5-trimethylcyclohexanediyl (9 carbon atoms), cycloheptanediyl (7 carbon atoms), cyclododecanediyl (12 carbon atoms), etc. may be mentioned. Preferred are cyclohexanediyl (6 carbon atoms), 3-methylcyclohexanediyl (7 carbon atoms), 4-methylcyclohexanediyl (7 carbon atoms), 3,3,5-trimethylcyclohexanediyl (9 carbon atoms), cyclododecanediyl (12 carbon atoms), etc., and more preferred are cyclohexanediyl (6 carbon atoms), 3,3,5-trimethylcyclohexanediyl (9 carbon atoms), cyclododecanediyl (12 carbon atoms).

[0058] When X in the general formula (1) is of the general formula (1b), Ar 1 and Ar 2 are preferably each independently a benzene ring or a naphthalene ring. More preferably, Ar 1 and Ar 2 are both benzene rings. For example, when Ar 1 and Ar 2 are both benzene rings, the group represented by the general formula (1b) is a fluorenediyl group.

[0059] When X in the general formula (1) is of the general formula (1c), it is preferably a divalent group of 1,3-bis(isopropyl-2-yl)benzene or 1,4-bis(isopropyl-2-yl)benzene.

[0060] The bonding positions of X in the general formula (1) to the two benzene rings with respect to the oxygen atom bonded to the benzene ring are preferably each independently ortho or para, and more preferably para.

[0061] In the general formula (1), n is preferably each independently 0, 2, or 3. In addition, when n is an integer of 1 to 4, R 1Relative to the oxygen atom bonded to the benzene ring, it is preferably bonded preferentially to the ortho position.

[0062] As specific examples of the ester compound represented by the general formula (1), compounds (p-1) to (p-171) having the following chemical structures are shown.

[0063] [Chemical formula 15]

[0064] [Chemical formula 16]

[0065] [Chemical formula 17]

[0066] [Chemical formula 18]

[0067] [Chemical formula 19]

[0068] [Chemical formula 20]

[0069] [Chemical formula 21]

[0070] [Chemical formula 22]

[0071] [Chemical formula 23]

[0072] [Chemical formula 24]

[0073] [Chemical formula 25]

[0074] [Chemical formula 26]

[0075] [Chemical formula 27]

[0076] [Chemical formula 28]

[0077] [Chemical formula 29]

[0078] <Method for producing the ester compound represented by the general formula (1)> For the ester compound represented by the general formula (1), there are no particular limitations on the starting materials and production methods in its production. For example, as exemplified by the following reaction formula, the following production methods can be cited: In an esterification step of synthesizing the ester compound represented by the general formula (2) by reacting the bisphenol compound represented by the general formula (5) with the acid anhydride represented by the general formula (6), after synthesizing the ester compound represented by the general formula (2), an ester exchange reaction step of obtaining the ester compound represented by the general formula (1) by reacting the ester compound represented by the general formula (2) with the furan carboxylic acid-containing compound represented by the general formula (8) is used to obtain the production method of the ester compound represented by the general formula (1).

[0079] [Chemical formula 30]

[0080] (R in the general formula (5) 1 , X and n and R in the general formula (8) 2 and R 3 , have the same definitions as those in the general formula (1), and R in the general formulas (6) and (7) 6 has the same definition as that of the following general formula (2).) (Esterification step) The reaction method of the esterification step in the above production method can be an esterification reaction method known in the past.

[0081] As the bisphenol compound represented by the general formula (5), specifically, for example, bisphenol F (bis(2-hydroxyphenyl)methane, 2-hydroxyphenyl-4-hydroxyphenylmethane, bis(4-hydroxyphenyl)methane), bisphenol E (1,1-bis(4-hydroxyphenyl)ethane), bisphenol A (2,2-bis(4-hydroxyphenyl)propane), bisphenol C (2,2-bis(4-hydroxy-3-methylphenyl)propane), 2,2-bis(4-hydroxyphenyl)-4-methylpentane, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxy-3,3'-dimethylbiphenyl, 4,4'-dihydroxy-3,3',5,5'-tetramethylbiphenyl, 4,4'-dihydroxy-2,2',3,3',5,5'-hexamethylbiphenyl, bis(4-hydroxyphenyl)ether, 4,4'-dihydroxybenzophenone, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)sulfide, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,1-bis(4-hydroxyphenyl)-1-naphthylethane, 2,2-bis(4-hydroxyphenyl)hexafluoropropane, bisphenol Z (1,1-bis(4-hydroxyphenyl)cyclohexane), bisphenol TMC (1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane), 1,1-bis(4-hydroxyphenyl)-3-methylcyclohexane, 1,1-bis(4-hydroxyphenyl)-4-methylcyclohexane, 1,1-bis(4-hydroxyphenyl)cyclododecane, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene).

[0082] As the acid anhydride represented by the general formula (6), specifically, for example, acetic anhydride and benzoic anhydride. Regarding R in the general formula (6) 6 , its definition and preferred form are the same as those of the general formula (2) described later.

[0083] In the above manufacturing method, as the usage amount of the acid anhydride represented by the general formula (6), relative to 1 mole of the bisphenol compound represented by the general formula (5), it is preferably in the range of 2.0 to 10.0 moles, more preferably in the range of 2.0 to 8.0 moles, and further preferably in the range of 2.0 to 4.0 moles.

[0084] The reaction temperature is usually in the range of 50 to 150 °C, preferably in the range of 80 to 140 °C. The reaction pressure can be either under normal pressure or reduced pressure.

[0085] Through the above esterification step, the ester compound represented by the general formula (2) can be manufactured.

[0086] (Ester compound represented by the general formula (2)) [Chemical formula 31]

[0087] (In the formula, R 1 , X and n have the same definitions as those in the general formula (1), R6 each independently represents a monovalent hydrocarbon group having 1 to 20 carbon atoms.) R in the general formula (2) 1 , X and n are the same as defined in the general formula (1), and preferably have the same forms.

[0088] R in the general formula (2) 6 is preferably each independently a monovalent hydrocarbon group having 1 to 10 carbon atoms, more preferably each independently an alkyl group or a phenyl group having 1 to 6 carbon atoms, still more preferably each independently a methyl group or a phenyl group, and particularly preferably a methyl group.

[0089] As the monovalent hydrocarbon group having 1 to 20 carbon atoms of R in the general formula (2) 6 , specifically, for example, there can be mentioned: chain-like monovalent hydrocarbon groups such as methyl, ethyl, propyl, isobutyl, butyl, hexyl, octyl, decyl; cyclic monovalent hydrocarbon groups such as cyclohexyl; monovalent aromatic hydrocarbon groups such as phenyl and naphthyl.

[0090] The ester compound represented by the general formula (2) obtained in the esterification step can be directly used in the state of being contained in the reaction solution of the esterification reaction as a raw material for the subsequent transesterification reaction step, or can be refined by distilling off the carboxylic acid represented by the general formula (7) generated in the esterification reaction and then used, or can be refined by performing a crystallization operation by mixing a solvent into the esterification reaction solution and then used.

[0091] (Transesterification step) The reaction method of the transesterification reaction step in the above manufacturing method can apply the methods of transesterification reaction known in the past.

[0092] R in the general formula (8) 2 and R 3 are the same as defined in the general formula (1), and preferably have the same forms or specific examples.

[0093] As the furan carboxylic acid represented by the general formula (8), specifically, for example, there can be mentioned: 2-furan carboxylic acid, 3-furan carboxylic acid, 2-methyl-3-furan carboxylic acid, 3-methyl-2-furan carboxylic acid.

[0094] As the usage amount of the furan carboxylic acid represented by the general formula (8), relative to 1 mole of the ester compound represented by the general formula (2), it is preferably in the range of 2.0 to 10.0 moles, more preferably in the range of 2.0 to 8.0 moles, still more preferably in the range of 2.0 to 4.0 moles.

[0095] As a catalyst in the reaction of the ester compound represented by the general formula (2) with the furan carboxylic acid represented by the general formula (8), a base is preferably used. Specific examples of these bases include organic bases such as amine bases, inorganic alkali metal compounds such as hydroxides, carbonates, and bicarbonates of alkali metals, organic alkali metal compounds such as alkoxides, phenoxides, and salts with organic carboxylic acids of alkali metals, etc. In addition, mixtures thereof, etc. may be mentioned, but are not limited thereto.

[0096] The reaction is usually carried out in the presence of a solvent. For reasons such as improving the operability during industrial production or the reaction rate, a reaction solvent is preferably used during the reaction. The solvent to be used is not particularly limited as long as it does not distill out of the reaction vessel at the following reaction temperature and is inactive with respect to the transesterification reaction. Specifically, for example, there may be mentioned aromatic hydrocarbon ether solvents such as alkyl aryl ethers like phenetole and butyl phenyl ether, or diaryl ethers like diphenyl ether and di-p-tolyl ether; aromatic hydrocarbons such as biphenyl and terphenyl; alkyl-substituted naphthalenes such as diisopropylnaphthalene; aliphatic hydrocarbons such as decalin and kerosene; polyalkylene glycol ethers such as tetraethylene glycol dimethyl ether and diethylene glycol dibutyl ether; organic solvents such as Therm-S series (manufactured by Nippon Steel Chemical Co., Ltd.), KSK-OIL series (manufactured by Soken Chemical & Engineering Co., Ltd.), or NeoSK-OIL series (manufactured by Soken Chemical & Engineering Co., Ltd.). In addition, the amount of the solvent used is not particularly limited as long as it does not hinder the reaction, and is usually used in a range of 0.5 to 20 times by weight, preferably 1 to 10 times by weight, relative to the ester compound represented by the general formula (2).

[0097] The reaction temperature is usually carried out in the range of 40 to 260 °C, preferably in the range of 80 to 255 °C, more preferably in the range of 120 to 250 °C, further preferably in the range of 160 to 245 °C, and particularly preferably in the range of 180 to 240 °C.

[0098] The reaction pressure can be carried out under normal pressure conditions. In addition, it can also be carried out under pressure or reduced pressure.

[0099] As another method, it may also include the step of discharging the carboxylic acid represented by the general formula (7) generated in the reaction out of the system. The step of removing the generated carboxylic acid represented by the general formula (7) from the reaction solution is not particularly limited, and can be carried out by distilling the generated carboxylic acid represented by the general formula (7) together with the solvents in the reaction solution. The generated carboxylic acid represented by the general formula (7) can be discharged out of the reaction system, for example, using an isobaric dropping funnel equipped with a stopcock, a Dimroth condenser, a Dean-Stark apparatus, etc.

[0100] Regarding the obtained reaction-terminated mixture, after the reaction is completed, the ester compound represented by the general formula (1) can be obtained from the mixture by known methods. For example, after the reaction, it is conceivable to cool and crystallize the reaction mixture and obtain the target product in the form of powder or granules by filtration. In addition, it is also conceivable to add the reaction mixture to a poor solvent to obtain the precipitated target product, or to add a solvent to the reaction mixture for crystallization and then obtain the target product in the form of powder or granules by filtration.

[0101] The ester compound represented by the general formula (1) extracted by the above method can be made into a high-purity product by ordinary purification methods such as washing or recrystallization with a solvent or water. As the solvent that can be used for crystallization and slurrying, there is no particular limitation as long as it is an inactive solvent for the ester compound represented by the general formula (1). Specifically, examples include alcohol solvents such as methanol, ethanol, isopropyl alcohol, and 1-butanol; or carbonyl solvents such as acetic anhydride, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone; ether solvents such as tetrahydrofuran, methyl isobutyl ether, methyl isopropyl ether, and diphenyl ether; aromatic non-polar solvents such as toluene, xylene, and ethylbenzene; γ-butyrolactone, γ-valerolactone, acrylonitrile, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and the like. Among them, 1-butanol, isopropyl alcohol, diphenyl ether, etc. are preferred.

[0102] The conditions for crystallization vary depending on the solvent used and cannot be generalized. For example, when using 1-butanol, the amount of this solvent used is in the range of 1 to 50 parts by weight, more preferably in the range of 2 to 30 parts by weight, and particularly preferably in the range of 2 to 10 parts by weight, relative to 1 part by weight of the total amount of the composition containing the ester compound represented by the general formula (1) to be refined and other impurities. The temperature during dissolution is in the range of 50 to 250 °C, more preferably in the range of 70 to 230 °C, further preferably in the range of 80 to 200 °C, and particularly preferably in the range of 90 to 180 °C. The cooling temperature is in the range of 0 °C to 50 °C, more preferably in the range of 10 to 40 °C, and further preferably in the range of 15 to 35 °C. The pressure during crystallization can be carried out under normal pressure conditions. In addition, it can also be carried out under pressure.

[0103] When using other solvents, various conditions can be appropriately changed in consideration of the boiling point of the solvent, or the solubility of the ester compound represented by the general formula (1) to be refined, other impurities, and the composition containing these.

[0104] Since the refined product obtained by these refining processes sometimes contains the solvent used, it is preferable to remove the solvent and carry out drying. The method for removing the solvent is not particularly limited, and examples include heating under normal pressure or reduced pressure to distill off the solvent.

[0105] The (B) chain linker in the curable resin composition of the present invention can also be used in the form of further containing an ester compound represented by the general formula (2) in the ester compound represented by the general formula (1).

[0106] In this case, relative to 100 parts by weight of the ester compound represented by the general formula (1), the ester compound represented by the general formula (2) is preferably contained in an amount of 0.1 to 400 parts by weight, more preferably 0.1 to 200 parts by weight, still more preferably 0.1 to 150 parts by weight, even more preferably 0.1 to 100 parts by weight, and particularly preferably 0.1 to 10 parts by weight.

[0107] It can also be produced by mixing the ester compound represented by the general formula (1) and the ester compound represented by the general formula (2) separately produced in a desired amount, or the ester compound represented by the general formula (2) can be used as an intermediate for producing the ester compound represented by the general formula (1), and the reaction rate of the transesterification reaction with the furan carboxylic acid-containing ester represented by the general formula (8) can be adjusted to reach the desired amount for production.

[0108] <(A) Curable resin component: thermosetting compound> As the thermosetting compound used as the (A) curable resin component in the curable resin composition of the present invention, conventionally known thermosetting compounds can be used. When specific examples are listed, they are one or more compounds selected from epoxy resins, benzoxazine compounds, benzoxazine resins, phenolic resins, bismaleimide compounds, and maleimide resins.

[0109] For epoxy resins, benzoxazine compounds, benzoxazine resins, phenolic resins, bismaleimide compounds, and maleimide resins, various compounds including conventionally known compounds can be used respectively.

[0110] (Epoxy resin) Regarding epoxy resins, glycidyl ether compounds, aromatic diglycidyl ether compounds (such as compounds obtained by glycidylating the hydroxyl groups of hydroquinone, resorcinol, catechol, bisphenol compounds represented by the general formula (5), etc.), mixtures of aromatic dihydroxy compounds (such as hydroquinone, resorcinol, catechol, bisphenol compounds represented by the general formula (5), etc.) and epihalohydrin, or phenoxy resins having epoxy groups formed by polymerizing aromatic dihydroxy compounds (such as hydroquinone, resorcinol, catechol, bisphenol compounds represented by the general formula (5), etc.) and epihalohydrin with or without using active ester curing agents are also included in epoxy resins. Various epoxy resins including conventionally known compounds can be used. Epoxy resins formed by reacting and chain-linking with the ester compound represented by the general formula (1) of the present invention as the active ester curing agent can also be used, and this epoxy resin is preferably used. These can be used alone or as a mixture of two or more.

[0111] As the conventionally known epoxy resins used, those having two or more epoxy groups in the molecule are preferred. For example, various epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, bisphenol Z type epoxy resin, naphthalene type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, phenol aralkyl type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, dicyclopentadiene type epoxy resin, and phenoxy resin can be used.

[0112] When using the epoxy resin formed by reacting and chain-linking with the ester compound represented by the general formula (1) and other epoxy resins together, in the total epoxy resin component, the blending amount of other epoxy resins is preferably 1% by weight or more, more preferably 5% by weight or more, further preferably 10% by weight or more, and on the other hand, preferably 99% by weight or less, more preferably 95% by weight or less, further preferably 90% by weight or less. By making the proportion of other epoxy resins above the above lower limit value, the effect of improving physical properties brought by blending other epoxy resins can be fully obtained. On the other hand, by making the proportion of other epoxy resins below the above upper limit value, the effect of the epoxy resin of the present invention can be fully exerted, which is preferred from the perspective of obtaining film-forming properties.

[0113] When using the epoxy resin formed by reacting and chain-linking with the ester compound represented by the general formula (1) or other epoxy resins, in the case of containing a solvent, it is based on the amount after removing the solvent.

[0114] (Epoxy resin formed by reacting and chain-linking with the ester compound represented by the general formula (1)) The epoxy resin formed by chain-linking through reaction with the ester compound represented by the general formula (1) of the present invention can be obtained, for example, by reacting an aromatic diglycidyl ether compound (for example, a compound obtained by glycidylating the hydroxyl groups of hydroquinone, resorcinol, catechol, a bisphenol compound represented by the general formula (5), etc.) with the ester compound represented by the general formula (1) for chain-linking. In the state of having epoxy groups at the molecular terminals, in order to facilitate high molecular weightization, the reaction is preferably carried out using an amount in the range of (epoxy group):(ester group)=1 to 1.2:1 in terms of the compounding equivalent ratio.

[0115] As another method, there may also be mentioned: a method for producing an epoxy resin by reacting a mixture containing an aromatic dihydroxy compound and an epihalohydrin with the ester compound represented by the general formula (1) for chain-linking; or a method for producing an epoxy resin by polymerizing an aromatic dihydroxy compound and an epihalohydrin to obtain a phenoxy resin having epoxy groups and then reacting it with the ester compound represented by the general formula (1) for chain-linking.

[0116] That is, the epoxy resin formed by chain-linking through reaction with the ester compound represented by the general formula (1) may include: an epoxy resin formed by reacting any one selected from an aromatic diglycidyl ether compound, a mixture containing an aromatic dihydroxy compound and an epihalohydrin, and a phenoxy resin having epoxy groups formed by polymerizing an aromatic dihydroxy compound and an epihalohydrin with the ester compound represented by the general formula (1) for chain-linking.

[0117] The molecular weight of the produced epoxy resin formed by chain-linking through reaction with the ester compound represented by the general formula (1) is not particularly limited, and preferably has a weight average molecular weight in the range of 1,000 or more and 50,000 or less, more preferably in the range of 2,000 or more and 30,000 or less, further preferably in the range of 3,000 or more and 20,000 or less, and particularly preferably in the range of 3,000 or more and 15,000 or less.

[0118] In the synthesis of the epoxy resin formed by chain-linking through reaction with the ester compound represented by the general formula (1), a catalyst can be used. As this catalyst, any compound can be used as long as it has the catalyst ability to promote the reaction between the epoxy group and the ester group. For example, there may be mentioned: tertiary amines, cyclic amines, imidazoles, organophosphorus compounds, quaternary ammonium salts, etc.

[0119] Specific examples of the tertiary amines may include: triethylamine, tri-n-propylamine, tri-n-butylamine, triethanolamine, benzyldimethylamine, pyridine, 4-(dimethylamino)pyridine, etc.

[0120] As specific examples of the cyclic amines, the following can be mentioned: 1,4-diazabicyclo[2,2,2]octane, 1,8-diazabicyclo[5,4,0]-7-undecene, 1,5-diazabicyclo[4,3,0]-5-nonene, etc.

[0121] As specific examples of the imidazoles, the following can be mentioned: 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, etc.

[0122] As specific examples of the organophosphorus compounds, the following can be mentioned: tri-n-propylphosphine, tri-n-butylphosphine, triphenylphosphine, tris(p-tolyl)phosphine, tricyclohexylphosphine, tris(tert-butyl)phosphine, tris(p-methoxyphenyl)phosphine, tetramethylphosphonium bromide, tetramethylphosphonium iodide, tetramethylphosphonium hydroxide, tetrabutylphosphonium hydroxide, trimethylcyclohexylphosphonium chloride, trimethylcyclohexylphosphonium bromide, trimethylbenzylphosphonium chloride, trimethylbenzylphosphonium bromide, tetraphenylphosphonium bromide, triphenylmethylphosphonium bromide, triphenylmethylphosphonium iodide, triphenylethylphosphonium chloride, triphenylethylphosphonium bromide, triphenylethylphosphonium iodide, triphenylbenzylphosphonium chloride, triphenylbenzylphosphonium bromide, etc.

[0123] Among the catalysts listed above, 4-(dimethylamino)pyridine, 1,4-diazabicyclo[2,2,2]octane, 1,8-diazabicyclo[5,4,0]-7-undecene, 1,5-diazabicyclo[4,3,0]-5-nonene, 2-ethyl-4-methylimidazole, tris(p-tolyl)phosphine, tricyclohexylphosphine, tris(tert-butyl)phosphine, tris(p-methoxyphenyl)phosphine are preferred, and 4-(dimethylamino)pyridine, 1,8-diazabicyclo[5,4,0]-7-undecene, 1,5-diazabicyclo[4,3,0]-5-nonene, 2-ethyl-4-methylimidazole are particularly preferred. In addition, the catalyst may be used alone or in combination of two or more.

[0124] Relative to the amount of the reaction substrate used in the reaction for obtaining the epoxy resin formed by chain-linking with the ester compound represented by the general formula (1), the amount of the above catalyst used is in the range of 0.001 to 3% by weight. When using these compounds as the catalyst, there is a risk that catalyst residues remain in the obtained curable resin composition, deteriorating the insulation characteristics of the printed circuit board or shortening the pot life of the composition. Therefore, when using a nitrogen-containing compound as the catalyst, the nitrogen content in the curable resin composition is preferably 2000 ppm or less, more preferably 1000 ppm or less. In addition, when using a phosphorus-containing compound as the catalyst, the phosphorus content in the curable resin composition is preferably 2000 ppm or less, further preferably 1000 ppm or less.

[0125] In the process of the synthesis reaction for manufacturing an epoxy resin formed by chain-linking through reaction with an ester compound represented by the general formula (1), a solvent for the reaction can be used. As this solvent, any substance can be used as long as it can dissolve the epoxy resin. For example, aromatic hydrocarbon solvents, ketone solvents, amide solvents, glycol ether solvents, etc. can be cited. Only one type of solvent can be used, or two or more types can be used in combination.

[0126] As specific examples of aromatic hydrocarbon solvents, benzene, toluene, xylene, etc. can be cited. As specific examples of ketone solvents, acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, 2-heptanone, 4-heptanone, 2-octanone, cyclohexanone, acetylacetone, dioxane, etc. can be cited.

[0127] As specific examples of amide solvents, formamide, N-methylformamide, N,N-dimethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, 2-pyrrolidone, N-methylpyrrolidone, etc. can be cited.

[0128] As specific examples of glycol ether solvents, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monon-butyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monon-butyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monon-butyl ether, propylene glycol monomethyl ether acetate, etc. can be cited.

[0129] In the synthesis reaction for manufacturing an epoxy resin formed by chain-linking through reaction with an ester compound represented by the general formula (1), the solid content concentration is preferably 10 to 95% by weight. In addition, when a highly viscous product is generated during the reaction, a solvent can be additionally added to continue the reaction. After the reaction is completed, the solvent can be removed as needed, or further added.

[0130] When manufacturing an epoxy resin formed by chain-linking through reaction with an ester compound represented by the general formula (1), the polymerization reaction is carried out at a reaction temperature at which the catalyst used does not decompose. When the reaction temperature is too high, there is a risk that the catalyst decomposes and the reaction stops, or the generated epoxy resin deteriorates. On the contrary, when the temperature is too low, the reaction may not proceed sufficiently. For these reasons, the reaction temperature is preferably 50 to 250 °C, more preferably 120 to 230 °C. In addition, the reaction time is usually 1 to 12 hours, preferably 3 to 10 hours. When using a low-boiling solvent such as acetone or methyl ethyl ketone, by using an autoclave and carrying out the reaction under high pressure, a reaction temperature higher than the boiling point at normal pressure can be ensured.

[0131] <(A) Curing resin component: Compound having a radically polymerizable substituent> In the curable resin composition of the present invention, as the compound having a radically polymerizable substituent used as the (A) curable resin component, conventionally known compounds can be used. When specific examples are listed, it is one or more compounds selected from diallyl phthalate resins, diallyl phthalate compounds, polyphenylene ether resins having a radically polymerizable substituent, and vinyl compounds.

[0132] For diallyl phthalate resins, diallyl phthalate compounds, polyphenylene ether resins having a radically polymerizable substituent, and vinyl compounds, various compounds including conventionally known compounds can be used.

[0133] ((Content of the (A) curable resin component)) In the curable resin composition of the present invention, relative to 100 parts by weight of the ester compound represented by the general formula (1) as the (B) chain linker, the content of the (A) curable resin component is preferably contained in the range of 50 to 500 parts by weight, more preferably in the range of 50 to 400 parts by weight, further preferably in the range of 50 to 300 parts by weight, and particularly preferably in the range of 50 to 200 parts by weight.

[0134] That is, in the form of the curable resin composition of the present invention, when it is in the form containing the ester compound represented by the general formula (1) as the (B) chain linker and the thermosetting compound as the (A) curable resin component, it means that relative to 100 parts by weight of the ester compound represented by the general formula (1) as the (B) chain linker, the thermosetting compound is contained in the above range. When it is in the form containing the ester compound represented by the general formula (1) as the (B) chain linker and the compound having a radically polymerizable substituent as the (A) curable resin component, it means that relative to 100 parts by weight of the ester compound represented by the general formula (1), the compound having a radically polymerizable substituent is contained in the above range. When it is in the form containing the ester compound represented by the general formula (1) as the (B) chain linker and the thermosetting compound and the compound having a radically polymerizable substituent as the (A) curable resin component, it means that relative to 100 parts by weight of the ester compound represented by the general formula (1), the total amount of the thermosetting compound and the compound having a radically polymerizable substituent is contained in the above range.

[0135] In addition, when the ester compound represented by the general formula (2) is used in combination as the (B) chain linker, it can be renamed as the content relative to 100 parts by weight of the total amount of the ester compound represented by the general formula (1) and the ester compound represented by the general formula (2).

[0136] <(C) Additive> The curable resin composition of the present invention may further contain various additives such as an ultraviolet absorber, an antioxidant, a coupling agent, a plasticizer, a soldering flux, a flame retardant, a colorant, a dispersant, an emulsifier, a low elasticizer, a diluent, an antifoaming agent, an ion scavenger, an inorganic filler, and an organic filler, as needed. The type or amount of the additives used can be appropriately adjusted according to their intended uses.

[0137] <(D) Curing Agent> The curable resin composition of the present invention may further contain a curing agent.

[0138] When an epoxy resin is used as a component of the curable resin composition of the present invention, the so-called curing agent refers to a substance that contributes to the crosslinking reaction and / or chain length extension reaction between the epoxy groups of the epoxy resin. In this case, as long as it is a substance generally called a "curing accelerator" and contributes to the crosslinking reaction and / or chain length extension reaction between the epoxy groups of the epoxy resin, it is included in the curing agent.

[0139] The amount of the curing agent used is preferably 0.1 to 100 parts by weight, more preferably 80 parts by weight or less, and still more preferably 60 parts by weight or less, based on 100 parts by weight of the total amount of the ester compound represented by the general formula (1) as the (B) chain linker and the thermosetting resin and / or the compound having a radically polymerizable substituent as the (A) curable resin component used.

[0140] The curing agent used is not particularly limited, and all types known as curing agents for thermosetting resins or compounds having a radically polymerizable substituent can be used.

[0141] Specific examples of the curing agent used in the curable resin composition of the present invention when an epoxy resin is used include, from the viewpoint of improving heat resistance, phenolic curing agents, amide curing agents, imidazoles, and active ester curing agents, etc. Examples of phenolic curing agents, amide curing agents, imidazoles, active ester curing agents, and other usable curing agents are listed below.

[0142] (Phenolic Curing Agents) When a phenolic curing agent is used as the curing agent, it is preferably used from the viewpoints of improving the processability of the resulting curable resin composition and the heat resistance of the cured product after curing. Specific examples of the phenolic curing agent include: bisphenol A, bisphenol F, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl ether, 1,4-bis(4-hydroxyphenoxy)benzene, 1,3-bis(4-hydroxyphenoxy)benzene, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, phenol novolac, bisphenol A novolac, o-cresol novolac, m-cresol novolac, p-cresol novolac, xylenol novolac, poly(p-hydroxystyrene), hydroquinone, resorcinol, catechol, tert-butylcatechol, tert-butylhydroquinone, fluoroethanolamine, pyrogallol, tert-butylpyrogallol, allylated pyrogallol, polyallylated pyrogallol, 1,2,4-benzenetriol, 2,3,4-trihydroxybenzophenone, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,4-dihydroxynaphthalene, 2,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,8-dihydroxynaphthalene, allylated or polyallylated products of the above dihydroxynaphthalenes, allylated bisphenol A, allylated bisphenol F, allylated phenol novolac, allylated pyrogallol, etc.

[0143] The above-listed phenolic curing agents may be used alone or in combination of two or more in any combination and ratio. In addition, when the curing agent is a phenolic curing agent, it is preferably used in a range of 0.8 to 1.5 in terms of the equivalent ratio of the functional groups in the curing agent to the epoxy groups in the epoxy resin. When it is within this range, it is preferred because unreacted epoxy groups or functional groups of the curing agent are not likely to remain.

[0144] (Amide curing agent) When an amide curing agent is used as the curing agent, it is preferably used from the viewpoints of improving heat resistance and the like. By using an amide curing agent as the curing agent, it is preferably used from the viewpoint of improving the heat resistance of the resulting curable resin composition. Examples of the amide curing agent include dicyandiamide and its derivatives, polyamide resins, etc.

[0145] Specific examples of the amide curing agent include "LUCKAMIDE" N-153-IM-65, EA-330, TD-960 (manufactured by DIC Corporation), etc.

[0146] The above-listed amide curing agents may be used alone, or two or more of them may be used in any combination and ratio. In addition, the amide curing agent is preferably used in the range of 0.1 to 20% by weight based on the total of the epoxy resin and the amide curing agent used in the curable resin composition.

[0147] (Imidazole-based) When an imidazole-based compound is used as the curing agent, it is preferred from the viewpoint of enabling sufficient curing reaction and improving heat resistance. Examples of the imidazole-based compound include: 2-phenylimidazole, 2-ethyl-4(5)-methylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyano-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and adducts of epoxy resins and the above-mentioned imidazole-based compounds. In addition, since imidazole-based compounds have catalytic ability, they are generally classified as curing accelerators described later, but in the present invention, they are classified as curing agents.

[0148] The above-listed imidazole-based compounds may be used alone, or two or more of them may be used in any combination and ratio. In addition, the imidazole-based compound is preferably used in the range of 0.1 to 20% by weight based on the total of the epoxy resin and the imidazole-based compound used in the curable resin composition.

[0149] (Active ester curing agent) When using an active ester curing agent as the curing agent, it is preferred from the perspective of reducing the water absorption of the resulting cured product. As the active ester curing agent, compounds having two or more highly reactive ester groups in one molecule, such as phenolic esters, thiophenol esters, N-hydroxyamine esters, esters of heterocyclic hydroxy compounds, etc., are preferred. Among them, phenolic esters obtained by reacting a carboxylic acid compound with an aromatic compound having a phenolic hydroxyl group are more preferred. Specific examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, etc. Examples of the aromatic compound having a phenolic hydroxyl group include catechol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, benzenetriol, dicyclopentadienyl diphenol, phenol novolac, etc. In addition, the ester compound represented by the general formula (2) according to the present invention can also be used.

[0150] The above-listed active ester curing agents can be used alone or in combination of two or more in any combination and ratio. In addition, in terms of the equivalent ratio of the active ester group in the curing agent to the epoxy group in the epoxy resin used in the curable resin composition, the active ester curing agent is preferably used in the range of 0.2 to 2.0.

[0151] (Other curing agents) As the curing agent that can be used in the curable resin composition of the present invention, substances other than phenolic curing agents, amide curing agents, and imidazoles, for example, include amine curing agents (excluding tertiary amines), acid anhydride curing agents, tertiary amines, organic phosphines, phosphonium salts, tetraphenylborate salts, organic acid dihydrazides, boron halide amine complexes, polythiol curing agents, isocyanate curing agents, blocked isocyanate curing agents, etc. The above-listed other curing agents can be used alone or in combination of two or more in any combination and ratio.

[0152] In addition, as the curing agent that can be used when using a compound having a radically polymerizable group, for example, imidazoles, tertiary amines, quaternary ammonium salts, boron trifluoride amine complexes, organic phosphines, organic phosphonium salts and other ionic catalysts, organic peroxides such as di-tert-butyl peroxide, dilauroyl peroxide, dibenzoyl peroxide, diisopropylbenzene peroxide, tert-butyl peroxybenzoate, hydroperoxides, radical polymerization initiators such as azobisisobutyronitrile, etc. can be cited.

[0153] In the curable resin composition of the present invention, as one component of the thermosetting compound, when an epoxy resin and other compounds (a thermosetting compound other than the epoxy resin formed by chain-linking through reaction with the ester compound represented by the general formula (1) or a compound having a radically polymerizable substituent) formed by chain-linking through reaction with the ester compound represented by the general formula (1) are used, in the total epoxy resin component based on the solid content, the blending amount of the other compound is preferably 1% by weight or more, more preferably 5% by weight or more, still more preferably 10% by weight or more. On the other hand, it is preferably 99% by weight or less, more preferably 95% by weight or less, still more preferably 90% by weight or less. By setting the proportion of the other compound to be above the above lower limit value, the effect of improving the physical properties brought about by blending the other compound can be fully obtained. On the other hand, by setting the proportion of the other compound to be below the above upper limit value, the effect of the epoxy resin of the present invention can be fully exerted, which is preferable from the viewpoint of obtaining film-forming properties.

[0154] <Solvent> In the curable resin composition of the present invention, during the treatment at the time of film formation, in order to appropriately adjust the viscosity of the curable resin composition, a solvent may be further blended for dilution. In the curable resin composition of the present invention, the solvent is used to ensure the processability and workability during shaping, and its usage amount is not particularly limited.

[0155] Examples of the solvent that can be contained in the curable resin composition of the present invention include: ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, and cyclohexanone; esters such as ethyl acetate; ethers such as ethylene glycol monomethyl ether; amides such as N,N-dimethylformamide and N,N-dimethylacetamide; alcohols such as methanol and ethanol; alkanes such as hexane and cyclohexane; and aromatics such as toluene and xylene. The solvents listed above may be used alone, or two or more of them may be mixed in any combination and ratio.

[0156] <Cured Product> The cured product obtained by curing the curable resin component through chain-linking the curable resin composition of the present invention via reaction is excellent in dielectric properties and heat resistance. Here, the so-called "curing" means intentionally curing the curable resin composition by heat and / or light, etc., and the degree of curing can be controlled according to the desired physical properties and uses. The degree of progress can be in a state of complete curing or semi-curing, and there is no particular limitation. As the reaction rate of the curing reaction, it is usually 5 to 95%.

[0157] <Chain-Linking Method> The chain connection methods of the curable resin composition of the present invention include the following methods: (i) the chain connection method when obtaining the epoxy resin formed by chain connection through reaction with the ester compound represented by the general formula (1), and (ii) the chain connection method when obtaining the cured product of the curable resin composition.

[0158] In the chain connection method (ii) when obtaining the cured product of the curable resin composition, the (A) curable resin component in the curable resin composition reacts with the (B) chain linker to connect molecular chains, and a cured product is generated through the chain connection. In the curing of the curable resin component, when the aforementioned (D) curing agent is used, it also participates in the reaction for curing.

[0159] Generally, heating conditions of performing heating at 80 to 280 °C for 60 to 360 minutes can be cited, but it also varies depending on the formulation components or formulation amounts in the curable resin composition. This heating is preferably a two-stage treatment of performing one-time heating at 80 to 160 °C for 10 to 90 minutes and two-time heating at 120 to 200 °C for 60 to 150 minutes. In addition, in a formulation system where the glass transition temperature (Tg) exceeds the two-time heating temperature, it is further preferred to perform three-time heating at 150 to 280 °C for 60 to 120 minutes. Performing two-time heating and three-time heating in this way is preferred from the perspective of reducing curing defects of the curable resin or solvent residues caused by unperformed chain connection.

[0160] When producing a resin prepreg, it is preferred to perform the reaction of connecting the chains of the curable resin composition by heating or the like to a degree that can maintain the shape, thereby curing it. When the curable resin composition contains a solvent, generally, most of the solvent is removed by methods such as heating, reduced pressure, and air drying, but the resin prepreg may also contain 5% by mass or less of the solvent remaining.

[0161] <Usage> The epoxy resin formed by chain connection through reaction with the ester compound represented by the general formula (1) according to the present invention has excellent film-forming properties. Therefore, it can be applied to various fields such as adhesives, coatings, civil engineering and building materials, and insulating materials for electrical and electronic components. In particular, it is useful as insulating potting, laminating materials, and sealing materials in the electrical and electronic fields.

[0162] As an example of the use of the epoxy resin formed by chain-linking reaction with the ester compound represented by the general formula (1), the curable resin composition of the present invention, and the cured product thereof, there may be mentioned: film adhesives, liquid adhesives, composite materials, coatings, civil engineering building materials, insulating materials for electrical and electronic components, multilayer printed wiring boards, laminates for electrical and electronic circuits such as capacitors, semiconductor encapsulation materials, underfill materials, chip filling materials for 3D-LSI, insulating sheets, prepregs, heat dissipation substrates, insulating potting, etc., but are not limited thereto.

[0163] (Laminates for electrical and electronic circuits) As described above, the curable resin composition of the present invention is suitably used for the purpose of laminates for electrical and electronic circuits. In the present invention, the "laminates for electrical and electronic circuits" refers to those in which a layer containing the curable resin composition of the present invention and a conductive metal layer are laminated. As long as a layer containing the curable resin composition of the present invention and a conductive metal layer are laminated, even if it is not an electrical and electronic circuit, it can be used in the concept including, for example, capacitors. In addition, in the laminates for electrical and electronic circuits, a layer composed of two or more curable resin compositions may be formed, and the curable resin composition of the present invention may be used in at least one layer. In addition, two or more conductive metal layers may be formed.

[0164] The thickness of the layer composed of the curable resin composition in the laminates for electrical and electronic circuits is usually about 10 to 200 μm. In addition, the thickness of the conductive metal layer is usually about 0.2 to 70 μm.

[0165] (Conductive metal) As the conductive metal in the laminates for electrical and electronic circuits, there may be mentioned: metals such as copper and aluminum, or alloys containing these metals. In the conductive metal layer of the laminates for electrical and electronic circuits in the present invention, metal foils of these metals or metal layers formed by plating or sputtering may be used.

[0166] (Manufacturing method of laminates for electrical and electronic circuits) As the manufacturing method of the laminates for electrical and electronic circuits in the present invention, for example, the following methods may be mentioned.

[0167] (1) Impregnate the curable resin composition of the present invention into a non-woven fabric or cloth made of inorganic and / or organic fiber materials such as glass fiber, polyester fiber, aramid fiber, cellulose, and nanocellulose to make a prepreg, then set a conductive metal layer by a conductive metal foil and / or plating, form a circuit using a photoresist, etc., and overlap the required number of the above layers to make a laminate.

[0168] (2) The prepreg of the above (1) is used as the core material, and a layer composed of a curable resin composition and a conductive metal layer are laminated above it (on one side or both sides). The layer composed of the curable resin composition may also contain organic and / or inorganic fillers.

[0169] (3) Without using a core material, only the layer composed of the curable resin composition and the conductive metal layer are alternately laminated to produce a laminate for an electric and electronic circuit.

[0170] According to the present invention, a cured product having excellent heat resistance and dielectric properties can be provided.

[0171] Therefore, the curable resin composition of the present invention can be applied to various fields such as film adhesives, liquid adhesives, composite materials, coatings, civil engineering building materials, insulating materials for electric and electronic components, etc., laminates for electric and electronic circuits such as multilayer printed wiring boards and capacitors, semiconductor sealing materials, underfill materials, chip filling materials for 3D-LSI, insulating sheets, prepregs, heat dissipation substrates, insulating potting, etc., and is particularly useful as an insulating potting, laminating material, sealing material, etc. in the electric and electronic fields.

[0172] <Ester compound represented by general formula (3)> In the curable resin composition of the present invention, among the ester compounds represented by general formula (1) used as the (B) chain linker, the ester compound represented by general formula (3) has more excellent heat resistance when a cured product is obtained using the curable resin composition of the present invention, and is therefore preferred.

[0173] Among them, in particular, the same as the ester compound represented by general formula (1), the ester compound represented by general formula (3) acts as a chain linker that cures by reacting with an epoxy resin, and by esterifying the secondary hydroxyl group generated by the reaction of the epoxy resin and the chain linker, the polarization of the obtained cured product can be suppressed, thereby having excellent dielectric properties. In addition, it can be seen from this that by using the ester compound represented by general formula (3) as a curing agent for an epoxy resin, the obtained cured product has the above characteristics, and is therefore preferred.

[0174] Since the ester compound represented by general formula (3) has a furan ring in the same way as the ester compound represented by general formula (1), in the curable resin component, it also reacts with a compound having a radically polymerizable substituent to form a chain connection, thereby obtaining a cured product thereof.

[0175] The ester compound represented by general formula (3) has excellent solubility in solvents such as methyl ethyl ketone, cyclohexanone, N-methylpyrrolidone, toluene, propylene glycol monomethyl ether acetate, and ethyl acetate, and in particular has excellent solubility in methyl ethyl ketone, which is one of the solvents widely used in the manufacture of electronic components such as semiconductors, and therefore has excellent processability.

[0176] [Chemical Formula 32]

[0177] (In the formula, R 2 each independently represents a single bond or a divalent hydrocarbon group having 1 to 10 carbon atoms, and R 3 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Y represents a divalent group represented by the general formula (3a) or general formula (3b).) [Chemical Formula 33]

[0178] (In general formulas (3a) and (3b), R 1 each independently represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, and * each represents a bonding position. In general formula (3a), m each independently represents an integer of 1 to 4. In general formula (3b), n each independently represents 0 or an integer of 1 to 4, and Z represents a cycloalkanediyl group having 7 to 20 carbon atoms.) R in general formula (3) 2 and R 3 specific examples or preferred forms of are the same as those of R 2 and R 3 in general formula (1). That is, R 2 in general formula (3) each independently is a single bond or a divalent hydrocarbon group having 1 to 10 carbon atoms. When it is a divalent hydrocarbon group, specifically, for example, it may include linear or branched alkylene groups having 1 to 10 carbon atoms such as methylene, ethylene, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, cyclohexane-1,3-diyl, cyclohexane-1,4-diyl, etc., or alkylene groups containing cyclic alkanes; alkylidene groups having 1 to 10 carbon atoms such as ethylidene, propylidene, isopropylidene, butylidene, cyclopentylidene, cyclohexylidene, etc.; divalent groups having 1 to 10 carbon atoms containing a benzene ring such as phenylene or a group represented by the following formula.

[0179] [Chemical Formula 34]

[0180] (In the formula, * represents a bonding position.) Among these, R 2Preferably, each is independently a single bond or a linear or branched alkylene group having 1 to 10 carbon atoms, an alkylene group containing a cycloalkane, or an alkylidene group having 1 to 10 carbon atoms. More preferably, each is independently a single bond or a linear or branched alkylene group having 1 to 10 carbon atoms or an alkylene group containing a cycloalkane. Even more preferably, each is independently a single bond or a linear or branched alkylene group having 1 to 6 carbon atoms or an alkylene group containing a cycloalkane. Particularly preferably, all are single bonds. R 2 The ester compound represented by the general formula (3) in which all are single bonds is obtained from a biomass-derived raw material, and thus is also preferable in terms of a curable resin composition having an increased biomass yield.

[0181] R in the general formula (3) 3 Preferably, each is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. More preferably, each is independently a hydrogen atom or a methyl group. Particularly preferably, all are hydrogen atoms.

[0182] When Y in the general formula (3) is of the general formula (3a), the preferred form of R 1 is the same as that of R in the general formula (1). 1 That is, when Y in the general formula (3) is of the general formula (3a), R 1 is preferably independently an alkyl group having 1 to 4 carbon atoms or a phenyl group. More preferably, each is independently a methyl group or a phenyl group. Particularly preferably, it is a methyl group.

[0183] When Y in the general formula (3) is of the general formula (3a), each m independently represents an integer of 1 to 4, preferably each is independently 1 to 3, more preferably each is independently 2 or 3, and particularly preferably all are 3. In addition, R 1 is preferably preferentially bonded to the ortho position with respect to the oxygen atom bonded to the benzene ring.

[0184] As a more preferred form when Y in the general formula (3) is of the general formula (3a), it is preferably a structure selected from the general formulas (3a-1) to (3a-4). More preferably, it is a structure selected from the general formulas (3a-2) to (3a-4). Even more preferably, it is the general formula (3a-3) or (3a-4). Particularly preferably, it is the general formula (3a-4).

[0185] [Chemical formula 35]

[0186] (In the formula, each R 1 independently represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, and * represents the bonding position.) When Y in the general formula (3) is of the general formula (3b), the preferred form of R 1 is the same as the preferred form of R in the general formula (1). 1 That is, when Y in the general formula (3) is of the general formula (3b), R1 Preferably, each is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, more preferably each is independently a methyl group or a phenyl group, and particularly preferably a methyl group.

[0187] When Y in the general formula (3) is of the general formula (3b), n is preferably 0, 1 or 2, more preferably 0 or 1, and particularly preferably both are 0. In addition, R 1 The substitution position of is preferably the ortho position relative to the oxygen atom.

[0188] Z in the general formula (3b) represents a cycloalkanediyl group having 7 to 20 carbon atoms, and may also contain an alkyl group as a side chain. This cycloalkanediyl group is preferably having 7 to 15 carbon atoms, more preferably having 7 to 12 carbon atoms, and particularly preferably having 7 to 9 carbon atoms. Specific examples of such cycloalkanediyl groups include: 3-methylcyclohexanediyl (7 carbon atoms), 4-methylcyclohexanediyl (7 carbon atoms), 3,3,5-trimethylcyclohexanediyl (9 carbon atoms), cyclododecanediyl (12 carbon atoms). It is preferably 3-methylcyclohexanediyl (7 carbon atoms), 4-methylcyclohexanediyl (7 carbon atoms) or 3,3,5-trimethylcyclohexanediyl (9 carbon atoms), more preferably 3-methylcyclohexanediyl (7 carbon atoms) or 3,3,5-trimethylcyclohexanediyl (9 carbon atoms), and particularly preferably 3,3,5-trimethylcyclohexanediyl (9 carbon atoms).

[0189] As specific examples of the ester compound represented by the general formula (3), compounds (p-139) to (p-177) having the following chemical structures are shown.

[0190] The ester compound represented by the general formula (3) is preferably one compound selected from compounds (p-139) to (p-177), and among these, compounds (p-139), (p-142), (p-145), (p-148), (p-151), (p-154) or (p-172) are particularly preferred.

[0191] [Chemical formula 36]

[0192] [Chemical formula 37]

[0193] [Chemical formula 38]

[0194] [Chemical formula 39]

[0195] The ester compound represented by the general formula (3) of the present invention can be produced in the same manner as the production method of the ester compound represented by the general formula (1).

[0196] Specifically, for the ester compound represented by the general formula (3), there are no particular limitations on the starting materials and manufacturing methods in its production. For example, as exemplified by the following reaction formula, the following manufacturing methods can be listed: In the esterification step of synthesizing the ester compound represented by the general formula (10) by reacting the bisphenol compound represented by the general formula (9) with the acid anhydride represented by the general formula (6), after synthesizing the ester compound represented by the general formula (10), an ester exchange reaction step of reacting the ester compound represented by the general formula (10) with the furan carboxylic acid-containing compound represented by the general formula (8) is carried out to obtain the manufacturing method of the ester compound represented by the general formula (3).

[0197] [Chemical formula 40]

[0198] (Y in the general formulas (9) and (10) has the same definition as that in the general formula (3), R in the general formula (8) 2 and R 3 have the same definition as those in the general formula (1), and R in the general formulas (6), (7) and (10) 6 has the same definition as that in the general formula (2).) (Esterification step) The reaction method of the esterification step in the above manufacturing method can be applied to the methods of esterification reactions known in the past.

[0199] As the bisphenol compound represented by the general formula (9), for the compound when Y is the general formula (3a), specifically, for example, 4,4'-dihydroxy-3,3'-dimethylbiphenyl, 4,4'-dihydroxy-3,3',5,5'-tetramethylbiphenyl, 4,4'-dihydroxy-2,2',3,3',5,5'-hexamethylbiphenyl can be listed. For the compound when Y is the general formula (3b), for example, bisphenol TMC (1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane), 1,1-bis(4-hydroxyphenyl)-3-methylcyclohexane, 1,1-bis(4-hydroxyphenyl)-4-methylcyclohexane, 1,1-bis(4-hydroxyphenyl)cyclododecane can be listed, and these compounds are preferred.

[0200] As the acid anhydride represented by the general formula (6), specifically, for example, acetic anhydride, benzoic anhydride can be listed. For R in the general formula (6) 6 its definition and preferred form are the same as those in the general formula (2).

[0201] In the above manufacturing method, the amount of the acid anhydride represented by the general formula (6) is preferably in the range of 2.0 to 10.0 moles, more preferably in the range of 2.0 to 8.0 moles, and still more preferably in the range of 2.0 to 4.0 moles, relative to 1 mole of the bisphenol compound represented by the general formula (9).

[0202] The reaction temperature is generally in the range of 50 to 150 °C, preferably in the range of 80 to 140 °C. The reaction pressure can be either under normal pressure or reduced pressure.

[0203] Through the above esterification step, the ester compound represented by the general formula (10) can be manufactured.

[0204] Y in the general formula (10) has the same definition as that in the general formula (3), and preferably has the same form.

[0205] R in the general formula (10) 6 has the same definition as that in the general formula (2), and its specific examples and preferred forms are also the same.

[0206] The ester compound represented by the general formula (10) obtained from the esterification step can be directly used in the state of being contained in the reaction solution of the esterification reaction as a raw material for the subsequent transesterification reaction step, or can be used after being refined by distilling off the carboxylic acid represented by the general formula (7) generated in the esterification reaction, or can be used after being refined by a crystallization operation by mixing a solvent into the esterification reaction solution.

[0207] (Transesterification reaction step) The reaction method of the transesterification reaction step in the above manufacturing method can apply the methods of transesterification reaction known in the past.

[0208] R in the general formula (8) 2 and R 3 have the same definition as that in the general formula (1), and preferably have the same form or specific examples.

[0209] Specific examples of the furan carboxylic acid represented by the general formula (8) include, for example: 2-furan carboxylic acid, 3-furan carboxylic acid, 2-methyl-3-furan carboxylic acid, 3-methyl-2-furan carboxylic acid.

[0210] The amount of the furan carboxylic acid represented by the general formula (8) is preferably in the range of 2.0 to 10.0 moles, more preferably in the range of 2.0 to 8.0 moles, and still more preferably in the range of 2.0 to 4.0 moles, relative to 1 mole of the ester compound represented by the general formula (10).

[0211] As a catalyst in the reaction of the ester compound represented by the general formula (10) with the furan carboxylic acid represented by the general formula (8), a base is preferably used. Specific examples of these bases include organic bases such as amine bases, inorganic alkali metal compounds such as hydroxides, carbonates, and hydrogencarbonates of alkali metals, organic alkali metal compounds such as alcoholates, phenolates, and salts with organic carboxylic acids of alkali metals, etc. In addition, mixtures thereof, etc. may be mentioned, but are not limited thereto.

[0212] The reaction is usually carried out in the presence of a solvent. For reasons such as improving the operability during industrial production or the reaction rate, a reaction solvent is preferably used during the reaction. The solvent that can be used is not particularly limited as long as it does not distill out from the reaction vessel at the following reaction temperature and is inactive with respect to the transesterification reaction. Specifically, for example, it may be mentioned: aromatic hydrocarbon ether solvents such as alkyl aryl ethers like phenetole and butyl phenyl ether, or diaryl ethers like diphenyl ether and di-p-tolyl ether; aromatic hydrocarbons such as biphenyl and terphenyl; alkyl-substituted naphthalenes such as diisopropylnaphthalene; aliphatic hydrocarbons such as decalin and kerosene; polyalkylene glycol ethers such as tetraethylene glycol dimethyl ether and diethylene glycol dibutyl ether; organic solvents such as Therm-S series (manufactured by Nippon Steel Chemical Co., Ltd.), KSK-OIL series (manufactured by Soken Chemical & Engineering Co., Ltd.), or NeoSK-OIL series (manufactured by Soken Chemical & Engineering Co., Ltd.). In addition, the amount of the solvent used is not particularly limited as long as it does not hinder the reaction, and it is usually used in a range of 0.5 to 20 times by weight, preferably 1 to 10 times by weight, relative to the ester compound represented by the general formula (10).

[0213] The reaction temperature is usually carried out in the range of 40 to 260 °C, preferably in the range of 80 to 255 °C, more preferably in the range of 120 to 250 °C, further preferably in the range of 160 to 245 °C, and particularly preferably in the range of 180 to 240 °C.

[0214] The reaction pressure can be carried out under normal pressure conditions. In addition, it can also be carried out under pressure or reduced pressure.

[0215] As another method, it may also include the step of discharging the carboxylic acid represented by the general formula (7) generated in the reaction out of the system. The step of removing the generated carboxylic acid represented by the general formula (7) from the reaction solution is not particularly limited, and it can be carried out by distilling the generated carboxylic acid represented by the general formula (7) together with the solvents in the reaction solution. The generated carboxylic acid represented by the general formula (7) can be discharged out of the reaction system, for example, using an isobaric dropping funnel equipped with a stopcock, a Dimroth condenser, a Dean-Stark apparatus, etc.

[0216] Regarding the obtained reaction-terminated mixture, after the reaction is completed, the ester compound represented by the general formula (3) can be obtained from the mixture by known methods. For example, after the reaction, it is conceivable to cool and crystallize the reaction mixture and obtain the target product in the form of powder or granules by filtration. In addition, it is also conceivable to add the reaction mixture to a poor solvent to obtain the precipitated target product, or add a solvent to the reaction mixture for crystallization and then obtain the target product in the form of powder or granules by filtration.

[0217] The ester compound represented by the general formula (3) extracted by the above method can be made into a high-purity product, for example, by ordinary purification methods such as washing or recrystallization with a solvent or water. As the solvent that can be used for crystallization and slurrying, there is no particular limitation as long as it is an inert solvent for the ester compound represented by the general formula (3). Specifically, examples include alcohol solvents such as methanol, ethanol, isopropanol, and 1-butanol; carbonyl solvents such as acetic anhydride, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone; ether solvents such as tetrahydrofuran, methyl isobutyl ether, methyl isopropyl ether, and diphenyl ether; aromatic non-polar solvents such as toluene, xylene, and ethylbenzene; γ-butyrolactone, γ-valerolactone, acrylonitrile, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. Among them, 1-butanol, isopropanol, diphenyl ether, etc. are preferred.

[0218] The crystallization conditions vary depending on the solvent used and cannot be generalized. For example, when using 1-butanol, the amount of the solvent used is in the range of 1 to 50 parts by weight, more preferably in the range of 2 to 30 parts by weight, and particularly preferably in the range of 2 to 10 parts by weight, relative to 1 part by weight of the total amount of the composition containing the ester compound represented by the general formula (3) to be refined and other impurities. The temperature during dissolution is in the range of 50 to 250 °C, more preferably in the range of 70 to 230 °C, further preferably in the range of 80 to 200 °C, and particularly preferably in the range of 90 to 180 °C. The cooling temperature is in the range of 0 to 50 °C, more preferably in the range of 10 to 40 °C, and further preferably in the range of 15 to 35 °C. The pressure during crystallization can be carried out under normal pressure conditions. In addition, it can also be carried out under pressure.

[0219] When using other solvents, various conditions can be appropriately changed in consideration of the boiling point of the solvent, the solubility of the ester compound represented by the general formula (3) to be refined, other impurities, and the composition containing these.

[0220] Since the refined product obtained by these refining processes sometimes contains the solvent used, it is preferable to remove the solvent and perform drying. The method for removing the solvent is not particularly limited, and examples include heating under normal pressure or reduced pressure to distill off the solvent.

[0221] <Crystallization of Compound (p-148)> In the ester compound of the present invention, the crystal of the compound represented by formula (p-148) can be treated as a crystalline solid, and is very useful because of its excellent processability.

[0222] The maximum endothermic peak temperature obtained by differential scanning calorimetry of the crystal is preferably in the range of 234 to 240 °C, more preferably in the range of 235 to 240 °C, and particularly preferably in the range of 236 to 239 °C.

[0223] <Method for producing crystal of compound (p-148)> The crystal of the compound (p-148) produced by the method for producing an ester compound represented by the above general formula (3) can be produced by crystallization using an alcohol solvent such as methanol, ethanol, isopropanol, 1-butanol, etc., especially an alcohol solvent having 1 to 4 carbon atoms, and an ether solvent such as tetrahydrofuran, methyl isobutyl ether, methyl isopropyl ether, diphenyl ether, etc., especially an ether solvent having 4 to 12 carbon atoms.

[0224] As the alcohol solvent having 1 to 4 carbon atoms, 1-butanol and isopropanol are particularly preferred, and as the ether solvent having 4 to 12 carbon atoms, diphenyl ether is particularly preferred.

[0225] Regarding the crystallization conditions, the total amount of the alcohol solvent and the ether solvent used is in the range of 1 part by weight to 50 parts by weight, more preferably in the range of 2 parts by weight to 30 parts by weight, and particularly preferably in the range of 2 to 10 parts by weight, based on 1 part by weight of the total amount of the composition containing the compound (p-148) and other reaction impurities.

[0226] Regarding the use ratio of the alcohol solvent to the ether solvent, the amount of the ether solvent used is preferably 0.3 to 3.0 times by weight, more preferably 0.5 to 2.5 times by weight, further preferably 1.0 to 2.2 times by weight, and particularly preferably 1.4 to 2.2 times by weight, based on the amount of the alcohol solvent used.

[0227] The temperature during dissolution is in the range of 50 to 250 °C, more preferably in the range of 70 to 230 °C, further preferably in the range of 80 to 200 °C, and particularly preferably in the range of 90 to 180 °C. The cooling temperature is in the range of 0 °C to 50 °C, more preferably in the range of 10 to 40 °C, and further preferably in the range of 15 to 35 °C. The pressure during crystallization can be carried out under normal pressure conditions, and in addition, it can also be carried out under pressure.

[0228] The crystal obtained by crystallization sometimes contains the solvent used, so it is preferably to remove the solvent and dry it. The method for removing the solvent is not particularly limited, and for example, heating under normal pressure or reduced pressure to distill off the solvent can be cited.

[0229] <Crystallization of compound (p-151)> Among the ester compounds of the present invention, the crystal of the compound represented by the formula (p-151) can be handled as a crystalline solid and is very useful because of its excellent handleability.

[0230] The maximum endothermic peak temperature of the crystal as determined by differential scanning calorimetry is preferably in the range of 180 to 188°C, more preferably in the range of 181 to 187°C, and particularly preferably in the range of 182 to 186°C.

[0231] <Method for producing crystals of compound (p-151)> The crystals of compound (p-151) produced by the method for producing an ester compound represented by the above general formula (3) can be produced by crystallization in a solvent containing an alcohol solvent such as methanol, ethanol, isopropanol, 1-butanol, etc., especially an alcohol solvent having 1 to 4 carbon atoms.

[0232] As the alcohol solvent having 1 to 4 carbon atoms, 1-butanol and isopropanol are particularly preferred.

[0233] Regarding the crystallization conditions, the amount of the alcohol solvent used is in the range of 1 part by weight to 50 parts by weight, more preferably 2 parts by weight to 30 parts by weight, and particularly preferably 2 parts by weight to 10 parts by weight, relative to 1 part by weight of the total amount of the composition containing compound (p-151) and other impurities after the reaction.

[0234] The temperature during dissolution is in the range of 50 to 250° C., more preferably in the range of 70 to 230° C., further preferably in the range of 80 to 200° C., and particularly preferably in the range of 90 to 180° C. The cooling temperature is in the range of 0 to 50° C., more preferably in the range of 10 to 40° C., and further preferably in the range of 15 to 35° C. The crystallization pressure may be carried out under normal pressure conditions or under pressure.

[0235] The crystals obtained by crystallization may contain the solvent used, and therefore, it is preferred to remove the solvent and dry. The method for removing the solvent is not particularly limited, and examples thereof include a method of heating under normal pressure or reduced pressure to distill off the solvent.

[0236] Since the ester compound represented by the general formula (3) contains the ester compound represented by the general formula (1), it can be used in the same manner as the method for using the ester compound represented by the general formula (1). In the present application, an invention is also disclosed in which the ester compound represented by the general formula (3) is substituted in the method for using the ester compound represented by the general formula (1).

[0237] <Ester compound composition for resin raw material> The ester compound represented by the general formula (3) can also be used in the form of a resin raw material composition further containing the ester compound represented by the general formula (2).

[0238] In addition, the ester compound represented by the general formula (2) further contained in the resin raw material composition may be the ester compound represented by the general formula (10), and this case is more preferred.

[0239] In the resin raw material composition, with respect to 100 parts by weight of the ester compound represented by the general formula (3), it is preferably contained 0.1 to 400 parts by weight of the ester compound represented by the general formula (2), more preferably 0.1 to 200 parts by weight, further preferably 0.1 to 150 parts by weight, more preferably 0.1 to 100 parts by weight, and particularly preferably 0.1 to 10 parts by weight.

[0240] The resin raw material composition of the present invention can also be produced by mixing the ester compound represented by the general formula (3) and the ester compound represented by the general formula (2) separately produced in a desired amount, or the ester compound represented by the general formula (2) can be used as an intermediate for producing the ester compound represented by the general formula (3), and the reaction rate of the transesterification reaction with the furan carboxylic acid-containing ester represented by the general formula (8) can be adjusted to reach the desired amount for production.

[0241] The resin raw material ester compound composition containing the ester compound represented by the general formula (3) and the ester compound represented by the general formula (2) can be used as a chain linker, such as in a curable resin composition described later, for reacting with a thermosetting compound and / or a compound having a radically polymerizable substituent to perform chain linking to produce a cured product. In addition, in the production of an epoxy resin formed by reacting and chain linking with the ester compound represented by the general formula (3) described later, a resin raw material ester compound composition further containing the ester compound represented by the general formula (2) can also be used.

[0242] <Curable Resin Composition> The ester compound represented by the general formula (3) of the present invention, like the ester compound represented by the general formula (1), acts as a chain linker for reacting and chain linking with curable resin components such as a thermosetting compound and / or a compound having a radically polymerizable substituent. Therefore, it can be used as a curable resin composition containing a thermosetting compound and / or a compound having a radically polymerizable substituent as the (A) curable resin component, and the ester compound represented by the general formula (3) as the (B) chain linker.

[0243] That is, as a curable resin composition, there are the following forms: a form containing a thermosetting compound as the (A) curable resin component and an ester compound represented by the general formula (3) as the (B) chain linker; a form containing a compound having a radically polymerizable substituent as the (A) curable resin component and an ester compound represented by the general formula (3) as the (B) chain linker; a form containing a thermosetting compound and a compound having a radically polymerizable substituent as the (A) curable resin component, and an ester compound represented by the general formula (3) as the (B) chain linker.

[0244] In order to supplement or further improve the physical properties or characteristics of the curable resin composition of the present invention and the products and cured products obtained therefrom, for those skilled in the art who come into contact with the present invention, within the scope disclosed in the present invention and within the obvious scope, the above-mentioned forms can be appropriately and preferably selected, or the compounds of the components used can be selected or changed, or their usage amounts can be adjusted, etc.

[0245] Regarding the ester compound represented by the general formula (3) used as the (B) chain linker in the curable resin composition of the present invention, among the compounds included in its range, only one kind can be used, or two or more kinds can be used in combination.

[0246] Regarding other descriptions of the curable resin composition containing a thermosetting compound and / or a compound having a radically polymerizable substituent as the (A) curable resin component and an ester compound represented by the general formula (3) as the (B) chain linker, the description of the ester compound represented by the general formula (1) in the description of the curable resin composition containing a thermosetting compound and / or a compound having a radically polymerizable substituent and an ester compound represented by the general formula (1) as the (B) chain linker can be changed to the ester compound represented by the general formula (3).

[0247] Examples The present invention will be further specifically described below through examples.

[0248] <Analysis method> 1. Analysis of reaction solution composition and purity (Ultra-fast liquid chromatography: UFLC) Weigh 0.01 g of the ester compound synthesized in the example into a 50 mL volumetric flask and dilute it with acetonitrile.

[0249] Perform purity analysis on the prepared sample according to the following high-performance liquid chromatography.

[0250] Purity analysis (the analysis value is the area percentage) Measurement device: High-performance liquid chromatography analysis device Prominence UFLC (manufactured by Shimadzu Corporation) Pump: LC-20AD Column oven: CTO-20A Detector: SPD-20A Chromatographic column: HALO-C18 (inner diameter 3 mm, length 75 mm) Oven temperature: 50 °C Flow rate: 0.7 mL / min. Mobile phase: (A) 0.1 vol% acetic acid aqueous solution, (B) acetonitrile Gradient condition: (A) vol% (time from the start of analysis) 30% (2.0 min.) → 100% (15.0 min.) → 100% (18.0 min.) Sample injection volume: 7 μL Detection wavelength: 254 nm 2. Evaluation of curing characteristics The curing characteristics of the synthesized epoxy resin composition were evaluated by differential scanning calorimetry (DSC) under the following operating conditions. The exothermic peak temperature was set as the curing temperature.

[0251] [Measurement conditions] Apparatus: DSC7020 / manufactured by Hitachi High-Technologies Corporation Heating rate: 10 °C / min. Measurement temperature range: 30 - 350 °C Measurement environment: Nitrogen 50 mL / min. Measurement sample: 3 mg of the synthesized epoxy resin composition 3. Measurement of glass transition temperature (Tg) (dynamic viscoelasticity measurement (DMA)) Apparatus: DMA850 / manufactured by TA Instruments Japan Co., Ltd. Measurement conditions: Three-point bending Measurement temperature: 30 - 310 °C Measurement frequency: 1.0 (Hz) Sample size: (60 mm × 15 mm × 2 mm) Heating rate: 1.0 °C / min. 4. Dielectric property evaluation Using the following apparatus, the relative dielectric constant and dielectric loss tangent were measured for the films (sample size: width 1.5 mm, length 8.0 mm) prepared in the examples and comparative examples.

[0252] Measurement apparatus: PNA network analyzer N522B (manufactured by Keysight Technologies, Inc.) Cavity Resonator: CP531 for 10 GHz (manufactured by Kanto Denpa Kogyo Co., Ltd.) [Measurement Conditions] Test Method: According to International Electrotechnical Commission IEC 62180 (Cavity Resonator Perturbation Method) Test Conditions: Frequency; 10 GHz Number of Measurements: n = 2 <Example 1> (Synthesis of the ester compound (p-151) represented by the following chemical formula (1-1)) [Chemical Formula 41]

[0253] Charge 465 g (1.50 moles) of bisphenol TM and 352 g of acetic anhydride into a 1000 mL four-necked flask equipped with a thermometer, a stirrer, a condenser, and a dropping funnel. After purging the inside of the reaction vessel with nitrogen, set the temperature of the mixed solution to 130°C. Then, stir at 130°C for 6 hours. Analyze the composition of the reaction solution by UFLC using the above analysis method. As a result, the proportion of 1,1-bis(4-acetoxyphenyl)-3,3,5-trimethylcyclohexane present in the reaction solution is 96 area%. After the reaction is completed, remove acetic anhydride and the generated acetic acid by vacuum distillation under the condition of 130°C. The pressure during distillation is slowly reduced, and finally it becomes 1.5 kPa. Obtain 560 g (purity: 99.9%) of a composition containing 1,1-bis(4-acetoxyphenyl)-3,3,5-trimethylcyclohexane.

[0254] From 1 The analysis result of 1H-NMR confirmed the obtainment of 1,1-bis(4-acetoxyphenyl)-3,3,5-trimethylcyclohexane.

[0255] 1 1H-NMR analysis (400 MHz, solvent: CDCl 3 , reference substance: tetramethylsilane) 0.40 (3H, s), 0.85 - 0.89 (1H, t), 0.96 - 0.97 (6H, d), 1.14 - 1.20 (1H, t), 1.37 - 1.40 (1H, d), 1.56 (2H, s), 1.92 - 2.10 (2H, m), 2.25 - 2.27 (6H, d), 2.42 - 2.45 (1H, d), 2.64 - 2.68 (1H, d), 6.90 - 6.92 (2H, d), 6.98 - 7.00 (2H, d), 7.18 - 7.20 (2H, d), 7.31 - 7.34 (2H, d). Into a 3000 mL four-necked flask equipped with a thermometer, a stirrer, a condenser, and a dropping funnel, 300 g (0.76 mol) of 1,1-bis(4-acetoxyphenyl)-3,3,5-trimethylcyclohexane, 213 g of furan carboxylic acid, 4.0 g of 4-dimethylaminopyridine, and 1500 g of diphenyl ether were charged. After purging the inside of the reaction vessel with nitrogen, the temperature of the mixed solution was set to 230 °C. Then, while distilling out the liquid containing diphenyl ether and others, such as acetic acid and the solvent, generated during the reaction, to the outside of the system, the mixture was stirred at 230 °C for 8 hours. The composition of the reaction solution was analyzed by UFLC using the above analytical method, and as a result, the proportion of the target compound present in the reaction solution was 52 area %. After completion of the reaction, acetic acid, diphenyl ether, and furan carboxylic acid generated were removed by vacuum distillation at 210 °C. The pressure during distillation was slowly reduced, and finally set to 5.0 kPa. After cooling the diphenyl ether solution containing the concentrated target compound, 845 g of 1-butanol was added. Then, it was cooled to 70 °C to precipitate crystals. 229 g of 1-butanol was added and it was cooled to 30 °C. The slurry containing the obtained target compound was separated by centrifugal filtration, and the obtained crystals containing the solvent were dried at 80 °C and 2.0 kPa to obtain 337 g of the target compound (1-1) (purity: 99.8%). In addition, from the results of differential scanning calorimetry (DSC) of the target compound, it was found that it was a crystal with a maximum endothermic peak temperature of 183.5 °C. The DSC data is shown in Figure 1 。

[0256] From 1 the analysis results of 1H-NMR, it was confirmed that the target compound having the above structure was obtained.

[0257] 1 1H-NMR analysis (400 MHz, solvent: CDCl 3 , reference substance: tetramethylsilane) 0.39 (3H, s), 0.81 - 0.92 (1H, t), 0.98 - 1.00 (6H, d), 1.18 - 1.24 (1H, t), 1.39 - 1.42 (1H, d), 1.56 (4H, s), 1.96 - 2.10 (2H, m), 2.46 - 2.49 (1H, d), 2.68 - 2.72 (1H, d), 6.57 - 6.59 (2H, m), 7.04 - 7.06 (2H, d), 7.13 - 7.15 (2H, d), 7.24 - 7.33 (1H, m), 7.34 - 7.40 (4H, m), 7.65 - 7.67 (2H, m). Regarding the solvent solubility of the obtained target compound, the solubility is 20 to 40% by weight relative to the weight of each solution of methyl ethyl ketone, cyclohexanone, and N-methylpyrrolidone, and the solubility is 10 to 20% by weight relative to the weight of each solution of toluene, propylene glycol monomethyl ether acetate, and ethyl acetate. Therefore, it is confirmed that the solvent solubility is excellent.

[0258] <Example 2> (Synthesis of the ester compound (p-28) represented by the following chemical formula (1-2)) [Chemical formula 42]

[0259] After acetylating biphenol in the same manner as in Example 1 to synthesize diacetyl biphenol, 70 g (0.26 mol) of diacetyl biphenol, 72 g of furan carboxylic acid, 1.4 g of 4-dimethylaminopyridine, and 431 g of diphenyl ether were charged into a 1000 mL four-necked flask equipped with a thermometer, a stirrer, a condenser, and a dropping funnel. After replacing the inside of the reaction vessel with nitrogen, the temperature of the mixed solution was set to 210 °C. Then, while distilling the liquid containing diphenyl ether and the like including acetic acid and the solvent generated as the reaction proceeded to the outside of the system under reduced pressure, the mixture was stirred at 210 °C for 4 hours. The pressure during distillation was gradually reduced, and finally set to 25.0 kPa. The composition of the reaction solution was analyzed by UFLC using the above analysis method, and as a result, the proportion of the target compound present in the reaction solution was 69 area%. After completion of the reaction, the mixture was cooled to 30 °C to precipitate crystals. The slurry containing the obtained target compound was separated by solid-liquid separation by centrifugal filtration, and the obtained crystals containing the solvent were dried at 80 °C and 2.0 kPa to obtain 81 g of the target compound (1-2) (purity: 99.7%). In addition, from the results of differential scanning calorimetry (DSC) of the target compound, it was found that it was a crystal with a maximum endothermic peak temperature of 240.0 °C. The DSC data is shown in Figure 2 .

[0260] From 1 The analysis result of 1H-NMR confirmed that the target compound having the above structure was obtained.

[0261] 1 1H-NMR analysis (400 MHz, solvent: CDCl 3 , reference substance: tetramethylsilane) 6.82 - 6.83 (2H, dd), 7.37 - 7.40 (4H, dt), 7.60 - 7.61 (2H, dd), 7.76 - 7.80 (4H, dt), 8.13 (2H, s). <Example 3> (Synthesis of the ester compound (p-148) represented by the following chemical formula (1-3)) [Chemical Formula 43]

[0262] In the same manner as in Example 1, 4,4'-dihydroxy-2,2',3,3',5,5'-hexamethylbiphenyl was acetylated to synthesize 4,4'-diacetoxy-2,2',3,3',5,5'-hexamethylbiphenyl. Then, 204 g (0.58 mol) of 4,4'-diacetoxy-2,2',3,3',5,5'-hexamethylbiphenyl, 162 g of furan carboxylic acid, 3.8 g of 4-dimethylaminopyridine, and 1267 g of diphenyl ether were charged into a 2000 mL four-necked flask equipped with a thermometer, a stirrer, a condenser, and a dropping funnel. After replacing the inside of the reaction vessel with nitrogen, the temperature of the mixed solution was set to 220 °C. Then, while distilling out the liquid containing acetic acid and the solvent such as diphenyl ether generated during the reaction to the outside of the system, the mixture was stirred at 220 °C for 14 hours. The composition of the reaction solution was analyzed by UFLC using the above analysis method, and as a result, the proportion of the target compound present in the reaction solution was 70 area%. After the reaction was completed, the generated acetic acid, diphenyl ether, and furan carboxylic acid were removed by distillation under reduced pressure at 220 °C. The pressure during distillation was slowly reduced, and finally set to 5.0 kPa. After cooling the concentrated diphenyl ether solution containing the target compound, 88 g of isopropyl alcohol and 149 g of diphenyl ether were added. Then, it was cooled to 30 °C to precipitate crystals. The slurry containing the obtained target compound was subjected to solid-liquid separation by centrifugal filtration, and the obtained crystals containing the solvent were dried at 60 °C and 2.0 kPa to obtain 233 g of the target compound (purity: 99.4%). In addition, from the results of differential scanning calorimetry (DSC) of the target compound, it was found that it was a crystal with a maximum endothermic peak temperature of 237.7 °C. The DSC data is shown in Figure 3 .

[0263] From 1 the analysis results of 1H-NMR, it was confirmed that the target compound having the above structure was obtained.

[0264] 1 1H-NMR analysis (400 MHz, solvent: C 2 D 6 OS, reference substance: tetramethylsilane) 1.94 (3H, s), 2.09 (6H, s), 2.11 (6H, s), 6.84 - 6.85 (2H, dd), 6.93 (2H, s), 7.67 - 7.68 (2H, dd), 8.15 - 8.15 (2H, d). <Example 4> 10.0 g of the compound (1-1) synthesized in Example 1, 10.1 g of dicyclopentadiene-based epoxy resin (XD-1000, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 251 g / eq.), 0.2 g of 4-dimethylaminopyridine, and 16.2 g of methyl ethyl ketone were placed in a 100 mL beaker, heated to 70 °C and dissolved. The dissolved solution was poured onto a release film and air-dried at room temperature. Then, it was dried in a vacuum dryer at 80 °C and 1.5 kPa, and then pulverized to obtain a composition powder containing the compound (1-1) and the epoxy resin. The composition powder was placed in a silicone resin mold and cured at 140 °C / 1 hour, 150 °C / 1 hour, 160 °C / 1.5 hours, 180 °C / 1.5 hours, and 250 °C / 2 hours. The glass transition temperature (Tg) of the obtained cured product was measured by the above analysis method, and the result was 250.0 °C.

[0265] <Example 5> A mixture of 5.1 g of the compound (1-1) synthesized in Example 1 and 5.0 g of 1,1-bis(4-acetoxyphenyl)-3,3,5-trimethylcyclohexane synthesized in Example 1, 11.4 g of dicyclopentadiene-based epoxy resin (XD-1000, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 251 g / eq.), 0.2 g of 4-dimethylaminopyridine, and 11.1 g of methyl ethyl ketone were placed in a 100 mL beaker, heated to 70 °C and dissolved. The dissolved solution was poured onto a release film and air-dried at room temperature. Then, it was dried in a vacuum dryer at 80 °C and 1.5 kPa, and then pulverized to obtain a composition powder containing the compound (1-1), 1,1-bis(4-acetoxyphenyl)-3,3,5-trimethylcyclohexane, and the epoxy resin. The composition powder was placed in a silicone resin mold and cured at 140 °C / 1 hour, 150 °C / 1 hour, 160 °C / 1.5 hours, and 180 °C / 1.5 hours. The glass transition temperature (Tg) of the obtained cured product was measured by the above analysis method, and the result was 206.3 °C.

[0266] It can be seen from Examples 4 and 5 that when the proportion of the compound represented by the general formula (1) is large, the heat resistance is higher.

[0267] <Example 6> 20.0 g of the compound (1-1) synthesized in Example 1, 16.0 g of o-cresol novolak type epoxy resin (manufactured by DIC Corporation: trade name "Epiclon N-673"), and 40.0 g of methyl ethyl ketone were placed in a 100 mL beaker, stirred, and dissolved. 0.72 g of 4-dimethylaminopyridine was added to the solution and further stirred to dissolve 4-dimethylaminopyridine. After complete dissolution, the solution was transferred to a bucket and dried overnight in a ventilation device, and then dried in a vacuum dryer at 60 °C and 1.5 kPa for 5 hours. Thereafter, the obtained composition was put into a mold (φ100 mm press-in type), and heated using a hot press tester under the conditions of 3 MPa, 160 °C for 2 hours, and 180 °C for 2 hours to obtain a cured product.

[0268] <Comparative Example 1> 10.0 g of a novolak type curing agent (manufactured by Aica Kogyo Co., Ltd.: trade name "BRG-555"), 20.0 g of o-cresol novolak type epoxy resin ((manufactured by DIC Corporation: trade name "Epiclon N-673"), and 40.0 g of methyl ethyl ketone were placed in a 100 mL beaker, stirred, and dissolved. 0.60 g of triphenylphosphine was added to the solution and further stirred to dissolve triphenylphosphine. After complete dissolution, the solution was transferred to a bucket and dried overnight in a ventilation device, and then dried in a vacuum dryer at 60 °C and 1.5 kPa for 5 hours. Thereafter, the obtained composition was put into a mold (φ100 mm press-in type), and heated using a hot press tester under the conditions of 3 MPa, 100 °C for 1 hour, and 130 °C for 2 hours. Then, in a hot air circulation oven, the cured product was heated under the conditions of 140 °C for 2 hours, 150 °C for 2 hours, 160 °C for 2 hours, and 180 °C for 2 hours to obtain a cured product.

[0269] By the above analysis method, the glass transition temperature (Tg) of the cured products obtained in Example 6 and Comparative Example 1 was measured and the dielectric properties were evaluated. The results are summarized in Table 1.

[0270] [Table 1]

[0271] As described above, it can be seen that the epoxy resin cured product using the compound of Example 1 of the present invention compound as a curing agent has a high glass transition temperature and exhibits high heat resistance. In addition, it can be seen that excellent dielectric properties are also exhibited.

[0272] The ester compound of the present invention, when formulated in an epoxy resin and cured, can endow the resulting cured product with excellent heat resistance and dielectric properties. Regarding the secondary hydroxyl groups generated in the reaction between the epoxy resin and the curing agent, it is speculated that the ester compound represented by the general formula (1) reacts with the epoxy resin as a curing agent and esterifies the secondary hydroxyl groups. As a result, the polarization of the resulting cured product is suppressed, thereby exhibiting excellent dielectric properties.

[0273] Therefore, the epoxy resin composition containing the ester compound of the present invention can be applied to various fields such as adhesives, coatings, civil engineering and building materials, and insulating materials for electrical and electronic components. In particular, it is useful as insulating potting, laminating materials, and sealing materials in the electrical and electronic fields.

[0274] Examples of the uses of the ester compound of the present invention and the epoxy resin composition containing the same include: laminates for electrical and electronic circuits such as multilayer printed wiring boards and capacitors, adhesives such as film adhesives and liquid adhesives, semiconductor sealing materials, underfill materials, chip filling materials for 3D-LSI, insulating sheets, prepregs, heat dissipation substrates, etc., but are not limited to these.

Claims

1. A chain linker for a thermosetting compound and / or a compound having a radically polymerizable substituent, characterized in that, it contains an ester compound represented by the general formula (1), [Chemical formula 1] In the formula, R 1 each independently represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, R 2 each independently represents a single bond or a divalent hydrocarbon group having 1 to 10 carbon atoms, R 3 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, X represents a single bond, an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group or a divalent group represented by the general formula (1a), (1b) or (1c), and n each independently represents 0 or an integer of 1 to 4, [Chemical formula 2] In general formulas (1a), (1b) and (1c), R 4 and R 5 each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms, R 4 and R 5 may be bonded to each other to form a cycloalkanediyl group having 5 to 20 carbon atoms as a whole, Ar 1 and Ar 2 represent an aryl group having 6 to 12 carbon atoms, and * each represents a bonding position.

2. The chain linker for a thermosetting compound and / or a compound having a radically polymerizable substituent according to claim 1, characterized in that, it further contains an ester compound represented by the general formula (2), [Chemical formula 3] In the formula, R 1 , X and n are the same as defined in the general formula (1), and R 6 each independently represents a monovalent hydrocarbon group having 1 to 20 carbon atoms.

3. The chain linker for a thermosetting compound and / or a compound having a radically polymerizable substituent according to claim 2, characterized in that, relative to 100 parts by weight of the ester compound represented by the general formula (1), it contains 0.1 to 400 parts by weight of the ester compound represented by the general formula (2).

4. A curable resin composition, characterized in that, it contains a thermosetting compound and / or a compound having a radically polymerizable substituent as the (A) curable resin component, and an ester compound represented by the general formula (1) as the (B) chain linker, [Chemical formula 4] In the formula, R 1 each independently represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, R 2 each independently represents a single bond or a divalent hydrocarbon group having 1 to 10 carbon atoms, R 3 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, X represents a single bond, an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group or a divalent group represented by the general formula (1a), (1b) or (1c), and n each independently represents 0 or an integer of 1 to 4. [Chemical formula 5] In general formulas (1a), (1b) and (1c), R 4 and R 5 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms, R 4 and R 5 may be bonded to each other to form a cycloalkanediyl group having 5 to 20 carbon atoms as a whole, Ar 1 and Ar 2 represent an aryl group having 6 to 12 carbon atoms, and * each represents a bonding position.

5. The curable resin composition according to claim 4, characterized in that, R of the ester compound represented by the general formula (1) 2 are all single bonds.

6. The curable resin composition according to claim 5, characterized in that, Further, the Rs in the ester compound represented by the general formula (1) 3 are all hydrogen atoms.

7. The curable resin composition according to claim 4, characterized in that, the thermosetting compound is one or more compounds selected from epoxy resins, benzoxazine compounds, benzoxazine resins, phenolic resins, bismaleimide compounds and maleimide resins.

8. The curable resin composition according to claim 4, characterized in that, the compound having a radically polymerizable substituent is one or more compounds selected from diallyl phthalate resins, diallyl phthalate compounds, polyphenylene ether resins having a radically polymerizable substituent and vinyl compounds.

9. The curable resin composition according to claim 4, characterized in that, it further contains an ester compound represented by the general formula (2) as the (B) chain linker, [Chemical formula 6] In the formula, R 1 , X and n are the same as defined in the general formula (1), and R 6 each independently represents a monovalent hydrocarbon group having 1 to 20 carbon atoms.

10. A cured product formed by reacting and chain-linking the curable resin composition according to claim 4.

11. A chain-linking method, characterized in that, using an ester compound represented by the general formula (1) as a chain linker, and reacting it with a thermosetting compound and / or a compound having a radically polymerizable substituent to carry out chain-linking, [Chemical formula 7] In the formula, R 1 each independently represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, R 2 each independently represents a single bond or a divalent hydrocarbon group having 1 to 10 carbon atoms, R 3 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, X represents a single bond, an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group or a divalent group represented by the general formula (1a), (1b) or (1c), and n each independently represents 0 or an integer of 1 to 4, [Chemical formula 8] In general formulas (1a), (1b) and (1c), R 4 and R 5 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms, R 4 and R 5 may bond to each other to form a cycloalkanediyl group having 5 to 20 carbon atoms as a whole, Ar 1 and Ar 2 represent an aryl group having 6 to 12 carbon atoms, and * each represents a bonding position.

12. The chain-linking method according to claim 11, characterized in that, further using an ester compound represented by the general formula (2) as a chain linker, [Chemical formula 9] In the formula, R 1 , X and n are the same as defined in the general formula (1), and R 6 each independently represents a monovalent hydrocarbon group having 1 to 20 carbon atoms.

13. The chain-linking method according to claim 12, characterized in that, relative to 100 parts by weight of the ester compound represented by the general formula (1), 0.1 to 400 parts by weight of the ester compound represented by the general formula (2) is used.

14. An epoxy resin, characterized in that, It is formed by reacting any one of a selected aromatic diglycidyl ether compound, a mixture containing an aromatic dihydroxy compound and an epihalohydrin, and a phenoxy resin having an epoxy group formed by polymerizing an aromatic dihydroxy compound and an epihalohydrin, with an ester compound represented by the general formula (1) to effect chain connection. [Chemical formula 10] In the formula, R 1 each independently represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, and R 2 each independently represents a single bond or a divalent hydrocarbon group having 1 to 10 carbon atoms, and R 3 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, X represents a single bond, an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, or a divalent group represented by the general formula (1a), (1b), or (1c), and n each independently represents 0 or an integer of 1 to 4. [Chemical formula 11] In general formulas (1a), (1b), and (1c), R 4 and R 5 each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms, R 4 and R 5 may be bonded to each other to form a cycloalkanediyl group having 5 to 20 carbon atoms as a whole, Ar 1 and Ar 2 represent an aryl group having 6 to 12 carbon atoms, and * each represents a bonding position.

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