Reactant, curable composition, and reaction method of epoxy compound

Abstract

Disclosed is a reactant for reacting with an epoxy compound, the reactant including an active ester compound that has a structure in which an acyloxy group is bonded to a carbon atom that constitutes a 1,3,5-triazine ring.

Description

Reactant, curable composition, and method for reacting epoxy compounds

[0001] The present invention relates to a reactant, a curable composition, and a method for reacting an epoxy compound.

[0002] Epoxy compounds are highly reactive and are used as intermediates in various reactions and as raw materials for introducing functional groups. Epoxy compounds are also used as materials that give cured products by reacting with curing agents.

[0003] For example, a known method for curing an epoxy compound involves reacting the epoxy compound with a compound having active hydrogen, such as an amine-based curing agent. In the reaction with the compound having active hydrogen, an active hydrogen group, such as an amino group, is added to the epoxy group of the epoxy compound, thereby opening the epoxy group and generating a hydroxyl group. This can result in increased moisture absorption and dielectric constant of the resulting cured product.

[0004] In response to this, a method of reacting an epoxy compound with an active ester compound has been investigated. In this reaction, no hydroxyl group is generated after the epoxy group of the epoxy compound is ring-opened, so that the moisture absorption and dielectric constant of the resulting cured product can be suppressed. Known active ester compounds include benzyl acetate, p-substituted phenyl acetate esters, methyl benzoate, and benzyl thioacetate (see Non-Patent Document 1).

[0005] Journal of the Chemical Society of Japan 1991 No. 11 Addition reactions of cyclic ethers with various esters

[0006] However, conventional active ester compounds do not yet have sufficient reactivity with epoxy compounds, and therefore, in order to react with epoxy compounds, the reaction temperature must be increased.

[0007] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a reactant that can react with an epoxy compound at a low reaction temperature and suppress the generation of hydroxyl groups, a curable composition, and a method for reacting an epoxy compound.

[0008] [1] A reactant for reacting with an epoxy compound, the reactant being an activated ester compound having a structure in which an acyloxy group is directly bonded to a carbon atom constituting a 1,3,5-triazine ring. [2] A modifying agent for reacting with an epoxy compound, the reactant according to [1], being a compound represented by the following formula (1): (In formula (1), R １ ~R ３ are each a monovalent organic group, and X and Y are each an oxygen atom, —NR— (R is a substituent), or a sulfur atom. [3] The reactant according to [1], which is a curing agent for an epoxy compound, and the active ester compound is a compound represented by the following formula (2): (In formula (2), R ２ and R ３ are each a monovalent organic group, R ４ is an m-valent organic group, m is an integer of 1 or more, when m = 1, at least two of X, Y, and Z are carbonyloxy bonds, and the remaining is an oxygen atom, -NR- (R is a substituent), or a sulfur atom, and when m = 2 or more, at least one of X, Y, and Z is a carbonyloxy bond, and the remaining is an oxygen atom, -NR- (R is a substituent), or a sulfur atom.) [4] The reactant according to [3], wherein m is an integer of 2 or more, Z is a carbonyloxy bond, and X and Y are each an oxygen atom, -NR-, or a sulfur atom. [5] The reactant according to [3], wherein m is an integer of 2 or more, X and Y are each a carbonyloxy bond, and Z is an oxygen atom, -NR-, or a sulfur atom. [6] The reactant according to [1], wherein the reactant is a curing agent for an epoxy compound, and the active ester compound is a polymer having a structure represented by any of the following formulas (3) to (6): (In formulas (3) and (4), R ２、 R ３ and R ６ are each a monovalent organic group, R ５is a divalent organic group, R is a group that constitutes a repeating unit of a polymer, X and Y are each an oxygen atom, —NR— (R is a substituent) or a sulfur atom, and n is an integer of 2 or more. (In formulas (5) and (6), R ２、 R ３ and R ７ are each a monovalent organic group, R ８ is a divalent organic group, R is a group constituting a repeating unit of a polymer, X is an oxygen atom, -NR- (R is a substituent) or a sulfur atom, and n is an integer of 2 or more.) [7] A curable composition comprising an epoxy compound and the reacting agent described in any one of [3] to [6]. [8] The curable composition described in [7], wherein the epoxy compound is an alicyclic epoxy compound. [9] A method for reacting an epoxy compound, comprising reacting an epoxy compound with the reacting agent described in any one of [1] to [6].

[10] The reaction method described in [9], wherein the epoxy compound is an alicyclic epoxy compound.

[0009] According to the present invention, it is possible to provide a reactant, a curable composition, and a method for reacting an epoxy compound, which can react with an epoxy compound at a low reaction temperature and suppress the generation of hydroxyl groups.

[0010] Fig. 1 is a graph showing the results of DSC measurement of a monofunctional active ester compound. Fig. 2 is a graph showing the results of DSC measurement of a polyfunctional active ester compound. Fig. 3A is a graph showing the results of DSC measurement of compound F, and Fig. 3B is a graph showing the results of DSC measurement of compound H. Fig. 4 is a graph showing the results of DSC measurement of TAB. Fig. 5 is a graph showing the results of DSC measurement of compound H with different types of epoxy compounds. Fig. 6 is a photograph of each curable composition after drying, taken from directly above the bottom of the vial.

[0011] The present inventors have found that an activated ester compound having a structure in which an acyloxy group is directly bonded to a carbon atom of a triazine ring, unlike conventional activated ester compounds, exhibits high reactivity with epoxy compounds, and specifically, undergoes an addition reaction with the epoxy group of an epoxy compound even at a low reaction temperature.

[0012] That is, one embodiment of the present invention relates to a reactant for reacting with an epoxy group. The reactant is for reacting with an epoxy compound and includes an activated ester compound having an acyloxy group bonded to a carbon atom constituting a 1,3,5-triazine ring. The reactant preferably includes an activated ester compound having a structure in which an acyloxy group is directly bonded to a carbon atom constituting a 1,3,5-triazine ring in one molecule.

[0013] An acyloxy group (R-CO-O-) refers to a functional group in which an acyl group (R-CO-) and an oxy group (-O-) are bonded (both R in R-CO-O- and R-CO- represent a substituent). A structure in which an acyloxy group is directly bonded to a carbon atom constituting a 1,3,5-triazine ring is represented, for example, by R-CO-O-* (* represents the bond site to the carbon atom constituting the triazine ring). The number of acyloxy groups directly bonded to a carbon atom constituting a 1,3,5-triazine ring in one molecule of an active ester compound may be one (monofunctional) or two or more (polyfunctional).

[0014] An active ester compound having such a structure can be added to the epoxy group of an epoxy compound even at a low reaction temperature and can suppress the generation of hydroxyl groups in the reaction product. Therefore, the active ester compound having the above structure can be used as a modifying agent for introducing various functional groups by reacting with a reactant, for example, an epoxy group, or as a curing agent for crosslinking an epoxy compound.

[0015] In this specification, the term "reactant" refers to a chemical substance that reacts with the epoxy group of the epoxy compound to form a chemical bond. While amine compounds, alcohol compounds, phenol compounds, and thiol compounds react nucleophilically with the epoxy group, the above-mentioned active ester compounds react electrophilically, similar to acid anhydrides and isocyanates.

[0016] The epoxy compound to be reacted with the reactant is not particularly limited as long as it contains an epoxy group in the molecule. The epoxy compound may be a compound having a glycidyl group or a compound containing an alicyclic epoxy structure. For example, an alicyclic epoxy compound is particularly preferred because it can react with the reactant at a lower temperature.

[0017] The use of these compounds as a modifying agent or a curing agent will be described below. In this specification, unless otherwise specified, the expression "to" means a numerical range including the lower and upper limits, which are the endpoints.

[0018] [First Embodiment] 1. Modifying Agent One embodiment of the present invention relates to a chemical substance for reacting with an epoxy group, and this chemical substance is referred to as a modifying agent. A modifying agent refers to a chemical substance used to change the properties of an epoxy compound by chemically bonding with the epoxy group of the epoxy compound to introduce various functional groups into the epoxy compound. The modifying agent includes an activated ester compound having a structure in which an acyloxy group is bonded to a carbon atom constituting a 1,3,5-triazine ring in one molecule. For example, the activated ester compound is preferably a compound represented by the following formula (1):

[0019] In formula (1), R １ ~R ３ are each a monovalent organic group. The monovalent organic group is a monovalent aliphatic group or a monovalent aromatic group, and the monovalent aliphatic group or monovalent aromatic group may contain elements other than C and H, such as N, O, F, Cl, Br, S, P, or Si.

[0020] A monovalent aliphatic group which may contain other elements refers to a residue obtained by removing one hydrogen atom from a carbon atom of an aliphatic compound, and the aliphatic compound also includes compounds in which multiple aliphatic chains are bonded via a linking group such as an ether bond, and saturated heterocycles. That is, the monovalent aliphatic group may be linear, branched, or cyclic, and includes not only residues consisting of C and H, but also residues containing elements other than C and H. Examples of monovalent aliphatic groups include linear alkyl groups having 1 to 18 carbon atoms such as methyl, ethyl, and propyl groups, branched alkyl groups having 3 to 10 carbon atoms such as isopropyl, sec-butyl, and isobutyl groups, cycloalkyl groups having 3 to 10 carbon atoms such as cyclohexyl groups, and heterocyclic groups such as tetrahydrofuran. These monovalent aliphatic groups may further have a substituent such as an aryl group or a halogen atom.

[0021] A monovalent aromatic group that may contain other elements refers to a residue obtained by removing one hydrogen atom from a carbon atom of an aromatic ring of an aromatic compound, and the above aromatic compounds also include compounds in which multiple aromatic rings are bonded or fused together, such as biphenyl and naphthalene. That is, the monovalent aromatic group includes not only residues consisting of C and H, but also residues containing elements other than C and H. The number of carbon atoms in the monovalent aromatic group may be, for example, 5 to 20. Examples of the aromatic group include aryl groups such as a phenyl group and a naphthalene group, and heteroaryl groups such as a pyridinyl group. These monovalent aromatic groups may further have a substituent such as an alkyl group, an alkoxy group, or a halogen atom.

[0022] Among these, R １ ~R ３ is preferably an alkyl group or an aryl group, and more preferably an alkyl group having 3 or less carbon atoms such as a methyl group, an ethyl group, or a propyl group, or a phenyl group. １ is preferably a phenyl group. ２ and R ３ is preferably an alkyl group having 3 or less carbon atoms such as a methyl group, an ethyl group, or a propyl group, and a methyl group is particularly preferred.

[0023] In formula (1), X and Y are each an oxygen atom, -NR-, or a sulfur atom. Of these, an oxygen atom or a sulfur atom is preferred, and an oxygen atom is more preferred. R in -NR- is a hydrogen atom or a substituent, and is preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an aryl group having 6 to 10 carbon atoms. When R is an alkyl group, R and R ２ or R ３ may be bonded to each other to form a ring (for example, a nitrogen-containing aliphatic six-membered ring).

[0024] Preferred examples of the compound represented by formula (1) include compounds represented by formula (1) １ is an aliphatic group or an aryl group, R ２ and R ３ are each an alkyl group or an aryl group, and X and Y are each an oxygen atom or a sulfur atom; １ is a cycloalkyl group or a phenyl group, R ２ and R ３ are each an alkyl group having 3 or less carbon atoms such as a methyl group, an ethyl group, a propyl group, or a phenyl group, and X and Y are each an oxygen atom; １ is a phenyl group, and R ２ and R ３ is an alkyl group having 3 or less carbon atoms, such as a methyl group, an ethyl group, or a propyl group, and X and Y are oxygen atoms; １ is a phenyl group, and R ２ and R ３ Particularly preferred are compounds in which X is a methyl group and X and Y are oxygen atoms.

[0025] Specific examples of the compound represented by formula (1) include the following.

[0026] 2. Reaction Method of Epoxy Compounds As described above, the compound represented by formula (1) is an activated ester compound, and the ester group constituting the activated ester compound is added to the ring-opened epoxy group of the epoxy compound. The type of epoxy compound is not particularly limited, and the epoxy compounds described below can be used. In addition, different optional functional groups can be introduced into the 2-, 4-, and 6-positions of the triazine ring of the activated ester compound. Therefore, the above compound can be used as a modifying agent for introducing new functional groups into epoxy compounds.

[0027] For example, A.W.C. Lin et al.; J. Electroanal. Chem., 84, pp. 411-419 (1977) and S. Shibata et al.; Seni Gakkaishi Journal, vol. 69, No. 12 (2013) report a method for imparting functionality or new physical properties to the surface of a material by reacting a functional group having active hydrogen present on the surface of the material with cyanuric chloride and then substituting the remaining chlorine atoms for the functional group.

[0028] As a specific example of the use of a triazine compound as a modifying agent (functional compound) for introducing a new functional group, a chlorotriazine compound containing cyclodextrin has been reported, and materials are known in which the inclusion ability of cyclodextrin is imparted by modifying fibers with this compound (see, for example, Japanese Patent Application Laid-Open No. 2002-65839). Furthermore, the functional compound is not limited thereto, and examples include a reaction product of bis(2,2,6,6-tetramethyl-4-piperidyl)amine and cyanuric chloride that imparts antioxidant functionality (Japanese Patent Application Laid-Open No. 63-69203), a reaction product of acetoxime and cyanuric chloride that imparts radical-generating functionality (Japanese Patent Application Laid-Open No. 2015-538399), and a reaction product of an aminocyaniso dye and cyanuric chloride that imparts fluorescent functionality (Japanese Patent Application Laid-Open No. 9-104825).

[0029] The active ester compound of the present embodiment also has a substituent other than an acyloxy group bonded to a triazine ring (-X-R ２ Ya-Y-R ３) has various functional groups. As a result, by reacting the acyloxy group of the active ester compound with the epoxy group of the epoxy compound, it is possible to suppress the generation of active hydrogen inside or on the surface of the epoxy compound. In other words, it is possible to introduce functional groups while suppressing the generation of hydroxyl groups.

[0030] The following reaction scheme shows an example of a reaction using 2,4-dimethoxy-6-benzoyloxy-1,3,5-triazine as the compound represented by formula (1) and glycidyl phenyl ether (GPE) as the epoxy compound. As shown in the reaction scheme below, when the compound represented by formula (1) is added to an epoxy group, the oxygen atom of the epoxy ring forms an ester. Therefore, unlike when the compound is reacted with a functional group having an active hydrogen, such as an amine, no hydroxyl group is generated. This makes it possible to impart functionality derived from the triazine ring and the functional group bonded to it without increasing the hygroscopicity or dielectric constant of the reaction product.

[0031] [Second Embodiment] 1. Curing Agent One embodiment of the present invention relates to a curing agent for crosslinking an epoxy compound. The curing agent contains an active ester compound (a polyfunctional active ester compound) having two or more acyloxy groups directly bonded to carbon atoms constituting a 1,3,5-triazine ring in one molecule. The polyfunctional active ester compound can react with the epoxy compound at an even lower reaction temperature than the monofunctional active ester compound described above. The active ester compound may be a low molecular weight compound or a high molecular weight compound.

[0032] 1-1. Low Molecular Weight Compound The active ester compound is preferably a compound represented by the following formula (2):

[0033] R in formula (2) ２ and R ３ is R in formula (1). ２ and R ３ When m is an integer of 2 or more, a plurality of R ２ may be the same or different. ３may be the same as or different from each other.

[0034] R in formula (2) ４ is an m-valent organic group. The m-valent organic group is an m-valent aliphatic group or an m-valent aromatic group, and the m-valent aliphatic group or the m-valent aromatic group may contain elements other than C and H, such as N, O, F, Cl, Br, S, P, or Si.

[0035] An m-valent aliphatic group which may contain other elements refers to a residue obtained by removing m hydrogen atoms from different carbon atoms of an aliphatic compound, and the aliphatic compound also includes compounds in which multiple aliphatic chains are bonded via a linking group such as an ether bond, and saturated heterocyclic rings. That is, the m-valent aliphatic group may be linear, branched, or cyclic, and includes not only residues consisting of C and H, but also residues containing elements other than C and H. Examples of m-valent aliphatic groups include linear alkyl residues having 1 to 18 carbon atoms such as methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, and octylene; branched alkyl residues having 3 to 10 carbon atoms such as isopropylene, sec-butylene, and isobutylene; cycloalkyl residues having 6 to 8 carbon atoms such as cyclohexylene; and heterocyclic residues such as piperazinyl. These m-valent aliphatic groups may further have the substituents described above.

[0036] The m-valent aromatic group, which may contain other elements, refers to a residue obtained by removing m hydrogen atoms from different carbon atoms in the aromatic ring of an aromatic compound, and the aromatic compound also includes compounds in which multiple aromatic rings are bonded or condensed, such as biphenyl and naphthalene. That is, the m-valent aromatic group includes not only residues consisting of C and H, but also residues containing elements other than C and H. Examples of the m-valent aromatic group include residues of benzene, biphenyl, diphenyl ether, diphenyl sulfone, diphenyl ketone, naphthalene, etc., and residues of heterocyclic compounds such as pyridine and pyrimidine. These m-valent aromatics may further have the above-mentioned substituents.

[0037] From the viewpoint of further increasing reactivity, R ４ An aromatic group is preferred as R. ２ or R ３Although it depends on the combination with, etc., the aromatic group is more preferably an aromatic group which may have an electron-withdrawing group, particularly preferably a group derived from an aromatic ring selected from the group consisting of benzene, naphthalene, diphenyl ether, hexafluoro-2,2-diphenylpropane, benzenesulfonic acid, chlorobenzene, bromobenzene, and iodobenzene, and most preferably a group derived from an aromatic ring selected from the group consisting of diphenyl ether and hexafluoro-2,2-diphenylpropane.

[0038] In formula (2), m is an integer of 1 or more. In particular, from the viewpoint of further increasing the reactivity with the epoxy compound, m is preferably 2 or more, and more preferably 3 or more. The upper limit of m is, for example, 6.

[0039] When m = 1, at least two of X, Y, and Z are carbonyloxy bonds, and the remaining are oxygen atoms, -NR-, or sulfur atoms, preferably oxygen atoms or sulfur atoms, and more preferably oxygen atoms. All of X, Y, and Z may be carbonyloxy bonds. When m = 2 or more, at least one of X, Y, and Z is a carbonyloxy bond, and the remaining are oxygen atoms, -NR-, or sulfur atoms, preferably oxygen atoms or sulfur atoms, and more preferably oxygen atoms. The carbonyloxy bond is represented by *-O-C(=O)- (* is the site bonding to the carbon atom constituting the triazine ring).

[0040] Furthermore, R in -NR- is a hydrogen atom or a substituent, and is preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an aryl group having 6 to 10 carbon atoms. When R is an alkyl group, R and R ２ , R ３ or R ４ may be bonded to each other to form a ring (for example, a nitrogen-containing aliphatic six-membered ring). ４ When m is an m-valent aliphatic group (for example, an alkyl group), and Z is -NR-, the Rs of two -NR- may be bonded to each other to form a ring (for example, a nitrogen-containing aliphatic six-membered ring). For example, when m is 2, R ４ is an alkylene group, and Z is —NR—, then —Z—R４ -Z- may form a piperazinyl ring as shown in the following formula:

[0041] When m is 2 or more, for example, X may be a carbonyloxy bond, and Y and Z may each be an oxygen atom, —NR—, or a sulfur atom. Alternatively, X and Y may each be an oxygen atom, —NR—, or a sulfur atom, and Z may be a carbonyloxy bond (see formula (2A)). Alternatively, X and Y may each be a carbonyloxy bond, and Z may be an oxygen atom, —NR—, or a sulfur atom (see formula (2B)).

[0042] That is, the active ester compound may be a compound having, in the molecule, a plurality of structures in which one acyloxy group is bonded to a triazine ring (low molecular weight compound A), or may be a compound having, in the molecule, a plurality of structures in which two acyloxy groups are bonded to a triazine ring (low molecular weight compound B).

[0043] 1-1-1. Low Molecular Weight Compound A The compound represented by formula (2) may be a compound represented by formula (2A).

[0044] R in formula (2A) ２ ~R ４ , X and Y are R in formula (2) ２ ~R ４ , X, and Y. When m is an integer of 2 or more, a plurality of R ２ may be the same or different. ３ may be the same as or different from each other.

[0045] In formula (2A), m is an integer of 2 or greater. From the viewpoint of further enhancing the curability of the epoxy compound, m is preferably 2 or greater, and more preferably 3 or greater. The upper limit of m is not particularly limited, but can be, for example, 6 or less.

[0046] Preferred examples of the compound represented by formula (2A) include those in which m is an integer of 2 to 4 and R ４ is an aromatic group, and R ２ and R ３are each an alkyl group or an aryl group, and X and Y are each an oxygen atom or a sulfur atom; m is an integer of 2 to 3, and R ４ is an aromatic group, and R ２ and R ３ are each an alkyl group having 3 or less carbon atoms, such as a methyl group, an ethyl group, or a propyl group, or a phenyl group, and X and Y are oxygen atoms; m is an integer of 2 to 3, and R ４ is a group derived from a benzene ring, and R ２ and R ３ is an alkyl group having 3 or less carbon atoms, such as a methyl group, an ethyl group, or a propyl group, and X and Y are oxygen atoms; ４ is a group derived from a benzene ring, and R ３ and R ４ Particularly preferred are compounds in which X is a methyl group and X and Y are oxygen atoms.

[0047] Specific examples of the compound represented by formula (2A) include the following:

[0048]

[0049] 1-1-2. Low Molecular Weight Compound B The compound represented by formula (2) may be a compound represented by formula (2B).

[0050] R in formula (2B) ２ ~R ４ and Z is R in formula (2). ２ ~R ４ and Z. When m is an integer of 2 or more, a plurality of R ２ may be the same or different. ３ may be the same as or different from each other.

[0051] In formula (2B), m is an integer of 2 or greater. The upper limit of m is not particularly limited, but can be, for example, 6 or less.

[0052] Among them, preferred examples of the compound represented by formula (2B) include those in which m is an integer of 2 to 4 and R ２ and R ３ are each an alkyl group or an aryl group, R ４ is an aliphatic group or an aromatic group, and Z is an oxygen atom or a sulfur atom; m is an integer of 2 to 3, and R ２ and R ３ are each an alkyl group having 3 or less carbon atoms, such as a methyl group, an ethyl group, or a propyl group, or a phenyl group, and R ４ is an aliphatic group or an aromatic group, and Z is an oxygen atom; m is an integer of 2 to 3, and R ２ and R ３ is a phenyl group, and R ４ is an aromatic group and Z is an oxygen atom; ２ and R ３ is a phenyl group 、 R ４ Particularly preferred are compounds in which is an aromatic group and Z is an oxygen atom.

[0053] Specific examples of the compound represented by formula (2B) include the following:

[0054]

[0055] 1-2. Polymer Compounds The polymer compound may be a polymer (polymer compound A) containing a structural unit having a structure in which one acyloxy group is directly bonded to a triazine ring, or a polymer (polymer compound B) containing a structural unit having a structure in which two acyloxy groups are bonded to a triazine ring. For example, in the case of a curable composition containing a multifunctional epoxy compound and a curing agent, the physical properties of the cured product depend not only on the multifunctional epoxy compound as the main component but also on the curing agent. Therefore, when the above polymer is used as the curing agent, a cured product that reflects the physical properties of the polymer can be obtained. For example, using a polymer having a rigid structure as the curing agent can increase the glass transition temperature and mechanical strength of the cured product. Furthermore, using a polymer containing fluorine atoms as the curing agent can reduce the dielectric constant of the cured product. Using a polymer containing sulfur, chlorine, or bromine atoms as the curing agent can increase the flame retardancy of the cured product.

[0056] 1-2-1. Polymer Compound A The active ester compound may be a polymer having a structure represented by formula (3) or (4).

[0057] R in formulas (3) and (4) ２ , R ３ and R ６ is R in formula (2). ２ or R ３ and have the same meanings as above. In formula (4), R is a group constituting the repeating unit of the polymer, and is an aliphatic group or an aromatic group. The aliphatic group or aromatic group may contain elements other than C and H, such as N, O, F, Cl, Br, S, P, or Si. That is, R is derived from a polymer having a carboxy group in the repeating unit. There is no limit to the number of (COO-) groups in the repeating unit. Examples of such polymers include poly(meth)acrylic acid and polyamic acid. X and Y in formulas (3) and (4) have the same meanings as X and Y in formula (2).

[0058] In formula (3), R ５ is a divalent organic group. The divalent organic group is R ４In this case, m=2.

[0059] In formulas (3) and (4), n is an integer of 2 or more. n is preferably an integer of 2 to 10,000, and more preferably an integer of 10 to 100.

[0060] Specific examples of polymers having the structure represented by formula (3) include the following:

[0061] Specific examples of polymers having the structure represented by formula (4) include the following:

[0062] 1-2-2. Polymer Compound B The active ester compound may be a polymer having a structure represented by formula (5) or (6).

[0063] R in formula (5) ７ is R in formula (2). ２ or R ３ R in formula (6) is the same as ２ and R ３ is R in formula (2). ２ and R ３ X in formulas (5) and (6) has the same meaning as X in formula (2). In formula (5), R ８ is a divalent organic group. The divalent organic group is R ４In formula (6), m is defined as 2. R in formula (6) is a group constituting the repeating unit of the polymer and is an aliphatic or aromatic group. The aliphatic or aromatic group may contain elements other than C and H, such as N, O, F, Cl, Br, S, P, or Si. That is, -[R(X)]n- is derived from a polymer having active hydrogens, such as hydroxyl groups or amino groups, in the repeating unit. There is no limit to the number of active hydrogens in the repeating unit. Examples of such polymers include polyphenols (including phenol novolac, cresol novolac, etc.), polyamines, etc. Furthermore, -[R(X)]n- may be a polymer derived from the polymerization of vinyl groups. In formulas (5) and (6), n is an integer of 2 or greater. n is preferably an integer of 2 to 10,000, and more preferably an integer of 10 to 100.

[0064] Specific examples of polymers having the structure represented by formula (5) include the following:

[0065] Specific examples of polymers having the structure represented by formula (6) include the following:

[0066] 1-3. Synthesis Method The activated ester compound can be synthesized, for example, by reacting a chlorotriazine compound with a carboxylic acid compound in the presence of a tertiary amine compound in an organic solvent.

[0067] Reaction scheme (A) can be used to synthesize a compound having a structure in which one acyloxy group is bonded to a triazine ring (e.g., a compound represented by formula (2A) or a polymer having a structure represented by formula (3) or (4)). Reaction scheme (B) can be used to synthesize a compound having a structure in which two or more acyloxy groups are bonded to a triazine ring (e.g., a compound represented by formula (2B) or a polymer having a structure represented by formula (5) or (6)). Each case will be explained below.

[0068] (1) Synthesis of a compound represented by formula (2A) and a polymer having a structure represented by formula (3) or (4) First, a chlorotriazine compound is prepared (see the raw materials in reaction scheme (A)).

[0069] A chlorotriazine compound is obtained by reacting some of the three chlorine atoms of cyanuric chloride (2,4,6-trichloro-1,3,5-triazine) with a compound having a functional group containing active hydrogen (e.g., an amine, alcohol, thiol, etc.; represented by R-XH in the above reaction scheme). Reaction scheme (A) uses a compound in which two of the three chlorine atoms have been substituted with functional groups.

[0070] Examples of chlorotriazine compounds in which two of the three chlorine atoms have been substituted with functional groups include 2-chloro-4,6-dimethoxy-1,3,5-triazine, 2-chloro-4,6-diethoxy-1,3,5-triazine, 2-chloro-4-ethoxy-6-methoxy-1,3,5-triazine, and 2-chloro-4,6-diphenoxy-1,3,5-triazine.

[0071] Next, the remaining chlorine atoms of the chlorotriazine compound are reacted with a carboxylic acid compound in the presence of a tertiary amine compound to be substituted with acyloxy groups (see reaction scheme (A)).

[0072] Specifically, when N-methylmorpholine is used as the tertiary amine compound, the chlorotriazine compound and N-methylmorpholine readily react at 0°C to form an intermediate, 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride (DMT-MM), which is then reacted with a carboxylic acid compound, thereby introducing an acyloxy group.

[0073] In the reaction scheme (A), for convenience, the carboxylic acid compound is represented by R ４ The compound represented by formula (2A) is obtained by reacting a polycarboxylic acid with a chlorotriazine compound in an amount equal to the molar equivalent of the carboxyl group of the polycarboxylic acid.

[0074] The polycarboxylic acid can be a polycarboxylic acid having a number of carboxy groups corresponding to m in formula (2A). For example, when m = 2, a dicarboxylic acid can be used, and when m = 3, a tricarboxylic acid can be used. Examples of dicarboxylic acids include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, biphenyldicarboxylic acid, naphthalenedicarboxylic acid, oxydibenzoic acid, thiodibenzoic acid, dithiodibenzoic acid, carbonyldibenzoic acid, sulfonyldibenzoic acid, methylenedibenzoic acid, isopropylidenedibenzoic acid, and hexafluoroisopropylidenedibenzoic acid, and aliphatic dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid, and dodecanedicarboxylic acid. Examples of tricarboxylic acids include trimesic acid and tricarballylic acid.

[0075] Examples of tertiary amine compounds include N-methylmorpholine and pyridine. These tertiary amine compounds not only react well with chlorotriazine compounds but also activate carboxylic acid compounds. A tertiary amine compound for activating carboxylic acid compounds may be used in combination with these tertiary amine compounds. Examples of such tertiary amine compounds include triethylamine.

[0076] Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; aprotic polar solvents such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N-methylcaprolactam, N,N-dimethylimidazolidone, tetramethylurea, pyridine, and γ-butyrolactone; nonpolar solvents such as toluene, hexane, and heptane; ether solvents such as tetrahydrofuran, diglyme, dioxane, and trioxane; and mixed solvents thereof.

[0077] The amount of the tertiary amine compound is preferably 1.0 to 1.2 molar equivalents relative to the carboxy group of the carboxylic acid compound. The amount of the tertiary amine compound includes both the tertiary amine compound for reacting with the chlorotriazine compound and the tertiary amine compound for activating the carboxylic acid. The amount of the carboxylic acid compound is preferably the same molar equivalent relative to the chloro group of the chlorotriazine compound. The temperature during the reaction between the chlorotriazine compound and the carboxylic acid compound is preferably, for example, −5 to 25° C.

[0078] When synthesizing a polymer having a structure represented by formula (3), for example, a chlorotriazine compound polymerized by polycondensation or the like may be used as a raw material. When synthesizing a polymer having a structure represented by formula (4), chlorotriazine may be introduced into a polymer having a carbonyl group in the side chain, such as polyacrylic acid, polymethacrylic acid, or polyamic acid.

[0079] (2) Synthesis of a compound represented by formula (2B) and a polymer having a structure represented by formula (5) or (6) First, a chlorotriazine compound in which one of the three chlorine atoms of cyanuric chloride is substituted with a functional group is prepared (see the raw materials in reaction scheme (B)).

[0080] Next, in the presence of a tertiary amine compound, the remaining two chlorine atoms of the chlorotriazine compound are each reacted with a carboxylic acid compound to be substituted with an acyloxy group (see reaction scheme (B)).

[0081] As the carboxylic acid compound, a monocarboxylic acid can be used. The monocarboxylic acid may be an aliphatic or aromatic compound, or an unsaturated compound. In addition, other atoms may be bonded to the ring or on the ring. For example, aliphatic saturated monocarboxylic acids (e.g., formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid, lauric acid, myristic acid, palmitic acid, stearic acid), aliphatic unsaturated monocarboxylic or dicarboxylic acids (e.g., acrylic acid, propiolic acid, methacrylic acid, crotonic acid, isocrotonic acid, senecioic acid, tiglic acid, oleic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid), saturated or unsaturated carbocyclic carboxylic acids (e.g., camphoric acid, chrysanthemic acid), heterocyclic carboxylic acids (e.g., furancarboxylic acid, thiophenecarboxylic acid, pyrrolecarboxylic acid, pyrazinecarboxylic acid, nicotinic acid, isonicotinic acid, picolinic acid), aromatic carbocyclic carboxylic acids (e.g., benzoic acid, naphthalenecarboxylic acid, toluene acid), arylaliphatic saturated carboxylic acids, in particular arylpropionic acids (e.g., 2-phenylpropionic acid, 2-[4-(2-butyl)phenyl]propionic acid, 2-(3-benzoylphenyl)propionic acid, 2-(6-methoxy-2-phenyl)propionic acid, -naphthyl)propionic acid) or unsaturated acids (e.g., 2-phenylpropenoic acid, cinnamic acid), aliphatic or aromatic halogenated carboxylic acids (e.g., monofluoroacetic acid, difluoroacetic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, monochloropropionic acid, α-bromopropionic acid, α-bromobutyric acid, trifluoroacetic acid, o-monofluorobenzoic acid, m-monofluorobenzoic acid, p-monofluorobenzoic acid, 2,3-difluorobenzoic acid, 2,4-difluorobenzoic acid, 2,5-difluorobenzoic acid, benzoic acid, 3,4-difluorobenzoic acid, 2,3,6-trifluorobenzoic acid, 2,4,5-trifluorobenzoic acid, 2,3,4,5-tetrafluorobenzoic acid, pentafluorobenzoic acid, α,α,α-trifluoro-o-toluic acid, α,α,α-trifluoro-m-toluic acid, α,α,α-trifluoro-p-toluic acid, o-monochlorobenzoic acid, m-monochlorobenzoic acid, p-monochlorobenzoic acid, 2,3-dichlorobenzoic acid, 2,4-dichlorobenzoic acid, 2,5-dichlorobenzoic acid, 2,6-dichlorobenzoic acid, 3,4-dichlorobenzoic acid, 3,5-dichlorobenzoic acid, 2,3,5-trichlorobenzoic acid, 2,3,6-trichlorobenzoic acid, 2-chloro-4,5-fluorobenzoic acid, 3-chloro-2,4,5-trifluorobenzoic acid, o-monobromobenzoic acid, m-monobromobenzoic acid, p-monobromobenzoic acid), etc.

[0082] The tertiary amine compound and organic solvent may be the same as those described above.

[0083] For convenience, Reaction Scheme (B) shows a chlorotriazine compound having one chlorotriazine ring. When synthesizing the compound represented by Formula (2B), a chlorotriazine compound having multiple chlorotriazine rings, which is obtained by reacting cyanuric chloride with a polyfunctional compound, may be used.

[0084] When synthesizing a polymer having a structure represented by formula (5), a dicarboxylic acid may be used as the carboxylic acid compound. For example, a dichlorotriazine compound may be reacted with a dicarboxylic acid in the presence of a tertiary amine, and polycondensation may be carried out. When synthesizing a polymer having a structure represented by formula (6), a chlorotriazine compound having a polymerizable reactive group such as a vinyl group introduced as a functional group may be used, or a chlorotriazine compound may be reacted with a polymer having an active hydrogen atom such as a hydroxy group or an amino group in a repeating unit. For example, a chlorotriazine structure-containing polymer may be prepared by substituting one of the chlorine atoms of cyanuric chloride for the hydroxy group of a phenol novolak or the like, and then the remaining chlorine atom of the chlorotriazine may be substituted with an acyloxy group.

[0085] Identification of the structure of the active ester compound １ H NMR measurement, １３ It can be measured by C NMR measurement, FT-IR measurement, and MS measurement.

[0086] ( １ H NMR measurement) １H NMR measurement can be performed using an NMR measurement device (e.g., JEOL JNM-ECZ600R / S1). Specifically, 20 mg of white powder and 0.5 mL of deuterated chloroform are added to a vial to prepare a sample for measurement, and measurement is performed under the conditions of a magnetic field strength of 600 MHz and an accumulation number of 8. The obtained results are normalized so that the resonance peak of tetramethylsilane in a deuterated solvent is 0.00 ppm.

[0087] ( １３ C NMR measurement) １３ C NMR measurement １ A sample is prepared in the same manner as in the H NMR measurement, and measurement is performed using the same apparatus under conditions of a magnetic field strength of 600 MHz and an accumulation count of 128. The obtained results are normalized so that the chloroform resonance peak is at 77.0 ppm. In the case of an active ester compound in which the X and Y atoms bonded to the triazine ring in the above formulas (1) to (6) are oxygen atoms and a hydrocarbon group is bonded to the oxygen atom, characteristic peaks derived from the triazine ring are observed at 171 and 174 ppm. In addition, one peak derived from the acyloxy group bonded to the triazine ring is observed between 160 and 170 ppm.

[0088] (FT-IR Measurement) Fourier transform infrared spectroscopy (FT-IR) measurement can be performed by the KBr method using an FT-IR device (e.g., FT / IR-4100 manufactured by JASCO). Specifically, 1.0 mg of the white powder and 100 mg of KBr powder are homogeneously mixed, then placed in a tablet press and tableted to prepare a measurement sample. Then, 25 measurements are performed with a resolution of 2 cm. －１ In the above formulas (1) to (6), in the case of an active ester compound in which the X and Y atoms bonded to the triazine ring are oxygen atoms and a hydrocarbon group is bonded to the oxygen atom, the spectrum is measured under the conditions of 1750 cm －１ The stretching vibration of the ester C=O is confirmed around 1360 cm －１ A strong peak due to triazine ring skeletal vibration is observed around this point.

[0089] (MS Measurement) Mass spectrometry (MS) is performed using atmospheric pressure chemical ionization (APCI) and field desorption mass spectrometry (FD-MS). For APCI, the white powder is dissolved in a solvent (acetone) and the sample solution is adjusted to a sample concentration of 10 mg / mL. The sample solution is then filtered and analyzed using a mass analyzer (e.g., Advion CMS expression) under the conditions of mobile phase: acetone, nebulizer gas: nitrogen, and "low temperature, low fragmentation." For FD-MS, the white powder is dissolved in tetrahydrofuran and the sample solution is adjusted to a sample concentration of 2 mg / mL. The sample solution is then filtered, and mass analysis can be performed using a mass spectrometer (e.g., a JEOL GC-TOFMS JMS-T100GCV) under the following conditions: measurement mode: eiFI FD+, cathode (emitter applied) voltage: -10 kV, detector voltage: 2.4 kV, emitter current: 0 mA to 40 mA (increasing rate of 51.2 mA / min). Multifunctional active ester compounds have large molecular weights, and in MS analysis, a peak corresponding to the molecular weight may not be obtained; however, the corresponding triazine oleate is detected as a fragment peak. For example, in the above formulas (1) to (6), if the X and Y atoms bonded to the triazine ring are oxygen atoms and an active ester compound in which a methyl group is bonded to the oxygen atom (an active ester compound in which a methoxy group is bonded to the triazine ring) has an m / z of 158 [2,4-dimethoxy-6-hydroxy-1,3,5-triazine + 1]. ＋ The peaks due to

[0090] 2. Reaction method of epoxy compound The active ester compound according to this embodiment can undergo an addition reaction with the epoxy group of an epoxy compound even at a low temperature, and can impart functionality to the epoxy compound by introducing a functional group into a substituent other than the acyloxy group of the triazine ring. When the epoxy compound and the active ester compound are each polyfunctional compounds, they can be preferably used as a curing agent for the epoxy compound.

[0091] That is, a curable composition containing an epoxy compound and a curing agent containing the active ester compound can be prepared. The resulting cured product does not contain hydroxyl groups that are generated upon ring-opening of the epoxy group, and therefore, the moisture absorption and increase in dielectric constant can be suppressed.

[0092] The curable composition contains an epoxy compound and an active ester compound. The curable composition has the property of curing (solidifying) under specific conditions and is usually in the form of a liquid or varnish.

[0093] (Epoxy Compound) The epoxy compound is not particularly limited as long as it has two or more epoxy groups in the molecule, and may be an alicyclic epoxy compound, a glycidyl type epoxy compound including glycidyl ether, glycidyl amine, or glycidyl ester, or an internal epoxide. The epoxy compound may be a low molecular weight compound or a high molecular weight compound. When the epoxy compound is a high molecular weight compound, it may have an epoxy group at the terminal or one or more epoxy groups in the repeating unit constituting the polymer. The above-mentioned active ester compound exhibits high reactivity, particularly with alicyclic epoxy compounds.

[0094] In general, alicyclic epoxy compounds have lower reactivity than glycidyl-type epoxy compounds. Therefore, in order to cure an alicyclic epoxy compound, a higher reaction temperature is usually required than in the case of a glycidyl-type epoxy compound. In contrast, the above-mentioned active ester compounds have high reactivity and can react with alicyclic epoxy compounds at low temperatures, similar to the case of a glycidyl-type epoxy compound.

[0095] (Active Ester Compound) Among the above-mentioned active ester compounds, from the viewpoint of enhancing the reactivity with epoxy compounds, active ester compounds in which X and Y are —O— or —S— in the above formulas (1) to (5) are preferred. ２ and R ３ Preferably, at least one of R is an alkyl group or an aryl group. ２ and R ３ It is more preferable that at least one of R is an alkyl group having 3 or less carbon atoms, such as a methyl group, an ethyl group, or a propyl group, or a phenyl group. ２ and R ３ It is more preferable that at least one of the groups is a methyl group.

[0096] Thus, the reactivity of an active ester compound depends on the structure of the active ester compound, particularly R １ The reactivity of the above-mentioned active ester compound with the epoxy compound depends to some extent on the structures of R, X and Y. １ The reaction rate largely depends on the electron-withdrawing property of the compound and the stability of the 1,3,5-triazine-2-olate that is eliminated. For example, in the above reaction scheme, the lower the electron donating ability of X and Y of the active ester compound, the less likely it is that the electron density of the triazine ring will increase, and therefore the resulting 1,3,5-triazine-2-olate will be more likely to be stabilized and its reactivity will be more likely to increase. ２ , R ３ The lower the electron donating property of X and Y, the lower the electron donating property of X and Y, and thus the reactivity is likely to be further increased. Specifically, when X and Y are -O- or -S-, the electron donating property of X and Y is lower than when they are -NR-, and therefore the reactivity of the active ester compound with the epoxy compound is likely to be higher. In other words, the reactivity of the active ester compound depends on X and Y.

[0097] Therefore, R ２ or R ３ Even if different, R １If the active ester compounds have the same X and Y to some extent, they will exhibit the same reactivity. Also, if a low molecular weight compound exhibits a certain level of reactivity, the corresponding high molecular weight compound (polymer compound) will also exhibit almost the same reactivity. In other words, if the R of the active ester compound ２ or R ３ Even if R has a complex structure or a polymer structure, the R of the active ester compound １ When X and Y (particularly X and Y) are equivalent, they exhibit similar reactivity (reaction temperature).

[0098] (Auxiliary Agent) The reaction between the epoxy compound and the active ester compound may be carried out in the presence of an auxiliary agent in order to further increase the reaction efficiency. The auxiliary agent is not particularly limited as long as it promotes the reaction between the epoxy compound and the active ester compound, but is usually a curing accelerator such as a nucleophilic catalyst. Examples of curing accelerators include phosphorus-based curing accelerators, amine-based curing accelerators, and imidazole-based curing accelerators. Among these, amine-based curing accelerators are preferred in terms of further increasing the reactivity between the active ester compound and the epoxy compound. Among the amine-based curing accelerators, those having a heterocyclic structure such as pyridine or pyrimidine are preferred, those having a pyridine structure are more preferred, and 4-dimethylaminopyridine is even more preferred.

[0099] (Regarding reactivity with alicyclic epoxy compounds) As described above, active ester compounds also have high reactivity with alicyclic epoxy compounds. The reaction between an alicyclic epoxy compound and an active ester compound is more likely to be completed at a lower temperature than the reaction between other epoxy compounds and an active ester compound, and the reaction time can be shortened. The reason for this is not clear, but is presumed to be as follows.

[0100] For example, an example of reacting an epoxy compound with an active ester compound in the presence of an auxiliary will be described. When a glycidyl-based epoxy compound is used, the auxiliary not only reacts with the active ester compound but also with the glycidyl-based epoxy compound. On the other hand, when an alicyclic epoxy compound is used, the auxiliary reacts with the active ester compound but not with the alicyclic epoxy compound. As such, the reaction mechanisms differ between the use of an alicyclic epoxy compound and the use of a glycidyl-based epoxy compound, and the reaction scheme is simpler when an alicyclic epoxy compound is used than when a glycidyl-based epoxy compound is used. Therefore, the reaction between the alicyclic epoxy compound and the active ester compound is more likely to be completed at a lower temperature, allowing for a shorter reaction time.

[0101] 3. Method for Producing Curable Composition The curable composition can be produced by any method, for example, by dissolving and mixing the epoxy compound, the active ester compound, and, if necessary, the auxiliary and other components in a solvent, and then removing the solvent.

[0102] Here, the curable composition obtained by the above-mentioned production method is in the form of a varnish, and from the viewpoints of workability and storage stability, it is preferable that the varnish remains uniform even after the solvent is distilled off. Therefore, in order to obtain a uniform varnish, it is desirable to further increase the compatibility between the active ester compound and the epoxy compound.

[0103] In order to enhance the compatibility between the active ester compound and the epoxy compound, it is preferable to heat the active ester compound and the epoxy compound to a temperature equal to or higher than the reaction initiation temperature when producing a curable composition, thereby partially reacting them. This can further enhance the compatibility between the active ester compound and the epoxy compound, thereby more effectively preventing the precipitation of solids when, for example, distilling off the solvent. According to the above production method, a more highly compatible and uniform curable composition can be obtained, and therefore separation of the components of the curable composition can be more effectively prevented even when stored for a long period of time.

[0104] The heating temperature for partially reacting the active ester compound with the epoxy compound need only be equal to or higher than the temperature at which the epoxy compound and the active ester compound react. When the reaction temperature measured by DSC described below is Tp, the heating temperature is preferably, for example, Tp-30°C or higher and Tp+30°C or lower. A temperature of Tp-30°C or higher can further enhance the compatibility between the epoxy compound and the active ester compound. A temperature of Tp+30°C or lower can prevent the epoxy compound from curing too much and the composition from becoming gelatinous (gelation). Note that high heating temperatures tend to cause gelation, so if the heating temperature is high, gelation can be prevented by shortening the heating time. The heating temperature can be, for example, 70°C or higher and 190°C or lower.

[0105] The reaction temperature Tp can be measured by the following method: The epoxy compound and active ester compound to be used are mixed in a mortar until homogeneous. The resulting composition is subjected to DSC measurement, and the temperature is raised from 0°C to 200°C at a rate of 10°C / min. The peak top temperature of the first exothermic peak observed is read and taken as the reaction temperature Tp.

[0106] As described above, the active ester compound has a low reaction temperature with the epoxy compound, and therefore can react with the epoxy compound even at a low temperature at which the solvent does not volatilize, making the above method particularly effective.

[0107] 4. Uses of the Curable Composition The cured product of the curable composition does not generate active hydrogen and therefore has excellent dielectric properties. Therefore, it can be used in electronic materials such as semiconductor package substrates, printed wiring boards, build-up films, and semiconductor encapsulation materials. It can also be used in other applications such as adhesives and paints.

[0108] 5. Others In this embodiment, the structure of the active ester compound that is preferable for increasing the reactivity with the epoxy compound, and the type of epoxy compound and auxiliary to be combined have been described, but these contents also apply to the first embodiment.

[0109] Furthermore, in this embodiment, as a method for producing a curable composition, a method in which an active ester compound and an epoxy compound are heated to a temperature equal to or higher than the reaction temperature to cause a part of them to react has been described, but the above method may be applied to the method for producing the composition of the first embodiment.

[0110] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0111] 1. Preparation of Monofunctional Active Ester Compound (Synthesis of Compound A) 10 mL of tetrahydrofuran (THF) (dehydrated) and 1.76 g (0.010 mol, 144 parts by mass) of 2-chloro-4,6-dimethoxy-1,3,5-triazine were added to a 50 mL three-neck flask equipped with a 50 mL dropping funnel, a magnetic stirrer, and a thermometer. The mixture was dissolved at a temperature of 25°C and then cooled to 0°C to obtain a first solution. 1.05 g (0.010 mol, 86 parts by mass) of N-methylmorpholine was added dropwise to and mixed with the first solution so that the temperature of the first solution did not exceed 5°C. 10 mL of THF (dehydrated) and 1.22 g (0.010 mol, 100 parts by mass) of benzoic acid were added to a separate beaker and dissolved to obtain a second solution. The second solution was added dropwise to the first solution and mixed, ensuring that the temperature of the first solution did not exceed 5°C, to obtain a reaction solution. The reaction solution was stirred for 1 hour while maintaining the temperature at 0°C, and then further stirred at 25°C for 1 hour. After stirring, the reaction solution was filtered to remove precipitated salts. The solvent was removed from the filtrate using an evaporator, and 20 mL of ethyl acetate was added to the residue to dissolve it. The solution was transferred to a separatory funnel and washed once with 20 mL of water, three times with 20 mL of 0.5 M aqueous sodium bicarbonate solution, and once with 20 mL of saturated saline. The washed solution was transferred to an Erlenmeyer flask. An appropriate amount of anhydrous magnesium sulfate was added to the flask to dehydrate it, and then filtered. The solvent was removed from the filtrate using an evaporator, and the mixture was dried under reduced pressure at 25°C, yielding 1.68 g of a white powder (Compound A) in a yield of 64.3%.

[0112] (Identification) The white powder was subjected to the following measurements to identify its structure.

[0113] ( １ H NMR measurement, １３C NMR measurement) １ H NMR measurements were performed using an NMR measurement device (JNM-ECZ600R / S1 manufactured by JEOL). More specifically, 20 mg of the white powder and 0.5 mL of deuterated chloroform were added to a vial to prepare a sample for measurement, and measurements were performed under the conditions of a magnetic field strength of 600 MHz and an accumulation count of 8. The results were normalized so that the resonance peak of tetramethylsilane in a deuterated solvent was 0.00 ppm. １３ C NMR measurement １ Samples were prepared in the same manner as in the H NMR measurements, and measurements were performed using the same instrument under the conditions of magnetic field strength: 600 MHz, and number of accumulations: 128. The results were normalized so that the chloroform resonance peak was at 77.0 ppm. In each measurement, the chemical shift delta δ was expressed in ppm. The coupling constant J was expressed in hertz (Hz). The notations d and t represent d (doublet) and t (triplet), respectively.

[0114] (FT-IR Measurement) Fourier transform infrared spectroscopy (FT-IR) measurement was carried out by the KBr method using an FT-IR device (FT / IR-4100 manufactured by JASCO). More specifically, 1.0 mg of the white powder and 100 mg of KBr powder were homogeneously mixed, then placed in a tablet press and tableted to prepare a measurement sample. Thereafter, 25 integration times and a resolution of 2 cm were used. －１ The spectrum was measured under the following conditions.

[0115] (MS Measurement) Mass spectrometry (MS: Mass Spectrometry) was performed using atmospheric pressure chemical ionization (APCI: Atmospheric Pressure Chemical Ionization) and field desorption mass spectrometry (FD-MS: Field Desorption-Mass Spectroscopy). For APCI, the white powder was dissolved in a solvent (acetone) and the sample solution was adjusted to a sample concentration of 10 mg / mL. The sample solution was then filtered and analyzed using a mass spectrometer (Advion CMS expression) under the conditions of mobile phase: acetone, nebulizer gas: nitrogen, and "low temperature low fragmentation". For FD-MS, the white powder was dissolved in tetrahydrofuran and the sample solution was adjusted to a sample concentration of 2 mg / mL. Thereafter, the sample solution was filtered, and a mass spectrometer (GC-TOFMS JMS-T100GCV manufactured by JEOL) was used to carry out analysis under the following conditions: measurement mode: eiFI FD+, cathode (emitter applied) voltage: −10 kV, detector voltage: 2.4 kV, emitter current: 0 mA to 40 mA (increase rate of 51.2 mA / min).

[0116] (Results) White powder １ H NMR measurement results, １３ The C NMR measurement results, FT-IR measurement results, and MS measurement results are as follows. １ H NMR (600 MHz, CDCl ３ , TMS): δ = 8.15 (d, J = 7.5 Hz, 2H), 7.81 (t, J = 7.5 Hz, 1H), 7.68 (t, J = 7.5 Hz, 2H), 4.06 (s, 6H) １３ C NMR (100 MHz, CDCl ３ ): δ = 174.3 (triazine), 172.7 (triazine), 171.0 (triazine), 162.6 (C=O), 134.6 (phenyl group), 130.7 (phenyl group), 128.9 (phenyl group), 128.8 (phenyl group), 56.1 (CH ３ ) FT-IR (KBr, cm －１ ): 3083 (Ar-H stretching vibration), 2952 (CH３ stretching vibration), 1750 (C═O stretching vibration), 1574 (benzene ring skeletal vibration), 1558 (triazine ring skeletal vibration), 1449 (phenyl group skeletal vibration), 1228 (phenyl group skeletal vibration) MS (APCI): m / z 262.08 [M+H ＋ ] ＋ From these analytical results, it was confirmed that the white powder (compound A) was 2,4-dimethoxy-6-benzoyloxy-1,3,5-triazine.

[0117] (Synthesis of Compounds B to E) Compounds B to E were synthesized in the same manner as for Compound A, except that the types of raw materials were changed.

[0118] (Nitrophenyl acetate)

[0119] 2. Evaluation of Monofunctional Active Ester Compounds 2-1. Reactivity (Example 1) Compound A was added to epoxy compound I (jER828 manufactured by Mitsubishi Chemical Corporation, bisphenol A-type epoxy resin, see the formula below) so that the molar equivalent of the ester group in compound A was the same as the epoxy group in epoxy compound I. Furthermore, 2 parts by mass of dimethylaminopyridine (DMAP) relative to the epoxy compound was added as an auxiliary agent, and the mixture was mixed in a mortar until uniform, to obtain a composition. The reaction temperature with the epoxy compound was determined by DSC (differential scanning calorimetry). Specifically, 10 mg of the obtained composition was placed in an aluminum pan, and the temperature was raised from 0°C to 200°C at a rate of 10°C / min under a nitrogen stream using a differential scanning calorimeter (DSC 3+, manufactured by METTLER TOLEDO). The peak top temperature of the first exothermic peak observed was read and used as the reaction temperature. The reaction temperature was 131°C.

[0120] Examples 2 to 5 The reaction temperature was measured in the same manner as in Example 1, except that the compounds shown in Table 1 were used instead of Compound A.

[0121] Comparative Example 1 The reaction temperature was measured in the same manner as in Example 1, except that nitrophenyl acetate, a general active ester compound, was used instead of Compound A, and the reaction temperature was found to be 184°C.

[0122] (Evaluation Results) The evaluation results are shown in Table 1.

[0123] (Discussion) As shown in Table 1, compounds A to E (Examples 1 to 5) have lower peak temperatures than nitrophenyl acetate (Comparative Example 1), and are found to react with epoxy compounds at lower temperatures.

[0124] Figure 1 is a graph showing the results of DSC measurement of a monofunctional active ester compound. As shown in Figure 1, it can be seen that compound A (Example 1) reacts with an epoxy compound at a lower temperature than nitrophenyl acetate (Comparative Example 1).

[0125] 2-2. Confirmation of Reaction (Experimental Method) Compound A was added to glycidyl phenyl ether (GPE) as an epoxy compound so that the molar equivalents of the ester groups in Compound A and the epoxy groups in GPE were the same. Furthermore, DMAP was added in an amount equivalent to 1% by mass of the total composition, and the mixture was mixed in a mortar until uniform, yielding a composition. The composition was then added to a flask, and heated to 130°C using an oil bath while stirring. The heated product was collected at 0.5, 1, 2, 3, and 4 hours after heating.

[0126] ( １ 1H NMR measurement) In order to confirm the reaction progress of the epoxy compound and compound A, the fractions of each heated product were １ H NMR measurement was carried out. １H NMR measurements were performed using an NMR measurement device (JEOL JMM-ECZ600R / S1). More specifically, 20 mg of the resulting heated product and 0.5 mL of a heavy solvent (chloroform-d) were added to a vial to prepare a sample for measurement, and measurements were performed under the following conditions: magnetic field strength: 600 MHz, and 8 accumulations. The results were normalized so that the resonance peak of tetramethylsilane was 0 ppm. As a result, the peak at 2.7 to 2.9 ppm derived from the epoxy group decreased with heating time, and the peak at 5.6 ppm derived from the reaction product increased. Furthermore, the peak at 2.7 to 2.9 ppm derived from the epoxy group was not observed in the heated product separated 3 hours after heating. These results indicate that the reaction between the ester group of compound A and the epoxy group of the epoxy compound began immediately at 130°C, progressed over time, and was nearly complete at 3 hours.

[0127] (MS Measurement) Mass spectrometry was performed on each of the separated heated products using atmospheric pressure chemical ionization (APCI). Specifically, the obtained heated products were dissolved in a solvent (acetone) and a sample solution was prepared so that the sample concentration was 10 mg / mL. Thereafter, the sample solution was filtered and analyzed using a mass spectrometer (CMS expression manufactured by Advion) ​​under the conditions of mobile phase: acetone, nebulizer gas: nitrogen, and "low temperature, low fragmentation". As a result, a peak at m / z = 412 was observed from the heated products for all heating times. This is the [M+1] of the adduct of compound A and the epoxy compound. ＋ From the results of NMR measurement and MS measurement, it was confirmed that an addition reaction had occurred between the epoxy group of the epoxy compound and compound A.

[0128] 3. Preparation of Polyfunctional Active Ester Compound (Synthesis of Compound F) 200 mL of THF (dehydrated) and 12.6 g (0.072 mol, 249 parts by mass) of 2-chloro-4,6-dimethoxy-1,3,5-triazine were added to a 500 mL three-neck flask equipped with a 200 mL dropping funnel, a calcium chloride tube, a magnetic stirrer, and a thermometer, and the mixture was dissolved at a temperature of 25°C. The mixture was then cooled to 0°C to obtain a first solution. In a separate beaker, 50 mL of THF (dehydrated) and 8.69 g (0.086 mol, 172 parts by mass) of N-methylmorpholine were added and dissolved to obtain a second solution. The second solution was added dropwise to and mixed with the first solution, ensuring that the temperature of the first solution did not exceed 5°C, to obtain a mixed solution. Next, 70 mL of THF (dehydrated) and 5.06 g (0.024 mol, 100 parts by mass) of 1,3,5-benzenetricarboxylic acid were added to another beaker and dissolved to obtain a third solution. The third solution was added dropwise to the mixed solution so that the temperature of the mixed solution did not exceed 5°C, and a reaction solution was obtained. The reaction solution was stirred for 1 hour while maintaining the temperature at 0°C. After stirring, the reaction solution was filtered to remove precipitated salts. The filtrate was transferred to a separatory funnel and washed three times with 120 mL of 10% saline solution adjusted to pH 2 with hydrochloric acid. The filtrate was further washed once with 100 mL of saturated saline, and the washed filtrate was separated into an Erlenmeyer flask. An appropriate amount of magnesium sulfate was added to the mixture to dehydrate it, and then filtered. The solvent was removed from the filtrate using an evaporator, and the residue was dried under reduced pressure in a desiccator at 25° C. for 21 hours to obtain 8.12 g of a white powder (compound F) in a yield of 54.1%.

[0129] (Identification) The obtained white powder was measured in the same manner as above to identify its structure.

[0130] (Results) White powder １ H NMR measurement results, １３ The C NMR measurement results, FT-IR measurement results and MS measurement results are as follows. １ H NMR (600MHz, DMSO-d6, TMS): δ = 8.67 (s, 3H), 3.91 (s, 6H) １３C NMR (150 MHz, DMSO-d): δ = 173.5 (triazine), 168.5 (triazine), 166.4 (triazine), 157.5 (C=O), 133.8 (phenyl group), 132.4 (phenyl group), 130.9 (phenyl group), 55.7 (CH ３ ) FT-IR (KBr, cm －１ ): 3069 (Ar-H stretching vibration), 2954 (CH ３ stretching vibration), 1722 (C═O stretching vibration), 1600 (benzene ring skeletal vibration), 1540 (triazine ring skeletal vibration), 1241 (phenyl group skeletal vibration), 1099 (phenyl group skeletal vibration) MS (FD-MS): m / z 628.14 [M + H ＋ ] ＋ From these analytical results, it was confirmed that the white powder (compound F) was a triazine compound represented by the following formula:

[0131] (Synthesis of Compound H) Into a 50 mL three-neck flask equipped with a 50 mL dropping funnel, a magnetic stirrer, and a thermometer, 20 mL of THF (dehydrated), 1.93 g (0.010 mol, 150 parts by mass) of 2-chloro-4,6-di(p-methoxybenzenethio)-1,3,5-triazine, and 1.29 g of 4,4'-dicarboxydiphenyl ether (0.005 mol, 100 parts by mass) were added and dissolved at a temperature of 25°C, followed by cooling to 0°C to obtain a first solution. Into a separate beaker, 50 mL of THF (dehydrated) and 1.52 g (0.015 mol, 118 parts by mass) of N-methylmorpholine were added and dissolved to obtain a second solution. The second solution was added dropwise to the first solution and mixed, taking care not to allow the temperature of the first solution to exceed 5°C, to obtain a mixed solution. The reaction solution was stirred for 1 hour while maintaining the temperature at 0°C, and then stirred for 1 hour at 25°C. After stirring, the reaction solution was filtered to remove precipitated salts. The solvent was removed from the filtrate using an evaporator, and 20 mL of chloroform was added to the residue to dissolve it. The solution was transferred to a separatory funnel and washed twice with 20 mL of water. The resulting organic layer was dried over anhydrous magnesium sulfate, and the solid was filtered off and the solvent was removed using an evaporator to obtain a yellow-white powder (Compound H) in a yield of 84.1%.

[0132] (Synthesis of Compounds G to U) Compounds R to U were synthesized in the same manner as compound F, except that the types and amounts of raw materials were changed. Compounds G to Q were synthesized in the same manner as compound H, except that the types and amounts of raw materials were changed.

[0133] (TAB: triacetoxybenzene)

[0134] 4. Evaluation of Polyfunctional Active Ester Compounds 4-1. Reactivity (Example 6) The reaction temperature was measured in the same manner as in Example 1, except that Compound F was used instead of Compound A.

[0135] Example 7 The reaction temperature was measured in the same manner as in Example 6, except that DMAP was not added.

[0136] Example 8 The reaction temperature was measured in the same manner as in Example 6, except that epoxy compound II (Celloxide 2021P manufactured by Daicel Corporation, an epoxy compound represented by the following formula) was used instead of epoxy compound I (jER828 manufactured by Mitsubishi Chemical Corporation).

[0137] Examples 9, 11, 15 to 25, and 27 The reaction temperature was measured in the same manner as in Example 6, except that the compounds shown in Table 2 were used instead of Compound F.

[0138] Examples 10 and 12 The reaction temperature was measured in the same manner as in Example 7, except that the compounds shown in Table 2 were used instead of Compound F.

[0139] Example 13 The reaction temperature was measured in the same manner as in Example 8, except that the compound shown in Table 2 was used instead of compound F.

[0140] Example 14 The reaction temperature was measured in the same manner as in Example 13, except that DMAP was not added.

[0141] Example 26 The reaction temperature was measured in the same manner as in Example 6, except that epoxy compound III (EPICLON 830 (Bis-F) manufactured by DIC Corporation) was used instead of epoxy compound I (jER828 manufactured by Mitsubishi Chemical Corporation) and compound T was used instead of compound F.

[0142] Comparative Example 2 The reaction temperature was measured in the same manner as in Example 6, except that TAB (triacetoxybenzene) was used instead of Compound F.

[0143] Comparative Example 3 The reaction temperature was measured in the same manner as in Example 13, except that TAB (triacetoxybenzene) was used instead of Compound H.

[0144] (Evaluation Results) The evaluation results of Examples 6 to 27 and Comparative Examples 2 and 3 are shown in Table 2.

[0145] (Discussion) (1) Differences depending on the type of active ester compound As shown in Table 2, compounds F to U (Examples 6 to 27) have lower peak temperatures than TAB (Comparative Examples 2 and 3), indicating that they react with epoxy compounds at lower temperatures.

[0146] 2 is a graph showing the DSC measurement results of a polyfunctional active ester compound. For comparison, the DSC measurement results of compound A are also shown. As shown in FIG. 2, compound F (Example 6) reacts with an epoxy compound at an even lower reaction temperature than compound A (Example 1). This indicates that compound F exhibits even higher reactivity than compound A. It is also clear that compound F exhibits good reactivity even without the use of the co-catalyst DMAP (Example 7).

[0147] Figure 3A is a graph showing the DSC measurement results for compound F, Figure 3B is a graph showing the DSC measurement results for compound H, and Figure 4 is a graph showing the DSC measurement results for TAB. Each figure shows the results for 1) the compound alone, 2) the case where the compound was reacted with a bisphenol A epoxy compound, and 3) the case where the compound was reacted with a bisphenol A epoxy compound in the presence of DMAP. Comparing the case of 3), TAB has a reaction peak around 170°C (see Figure 4), whereas compound H has a reaction peak around 130°C and compound F has a reaction peak around 110°C (see Figures 3A and 3B), indicating that the reaction temperatures are low in both cases.

[0148] (2) Differences Depending on the Type of Epoxy Compound Figure 5 is a graph showing the results of DSC measurement of compound H (Examples 11 and 13) with different types of epoxy compounds. As shown in Figure 5, the reaction temperature when reacted with epoxy compound II (alicyclic epoxy compound) is almost the same as the reaction temperature when reacted with epoxy compound I (glycidyl-based epoxy compound). It is also clear that the peak end position when reacted with epoxy compound II (alicyclic epoxy compound) is shifted to a lower temperature than the peak end position when reacted with epoxy compound I (glycidyl-based epoxy compound). These findings indicate that the reaction time can be further shortened by combining an alicyclic epoxy compound with an active ester compound.

[0149] 5. Compatibility Study 5-1. Preparation of Curable Composition 100 parts by mass of dimethylacetamide (DMAc) was placed in a vial, and 10 parts by mass of compound F (reaction temperature Tp = 110°C), 8.1 parts by mass of epoxy compound I, and 0.2 parts by mass of DMAP were added. The mixture was ultrasonically dispersed at a temperature of just under 50°C for 1 hour, but none of the components dissolved. The resulting composition was then heated under the temperatures and times specified in conditions 1 to 5 to form a homogeneous solution. Condition 1: 100°C, 30 minutes; Condition 2: 100°C, 60 minutes; Condition 3: 100°C, 120 minutes; Condition 4: 100°C, 180 minutes; Condition 5: 80°C, 120 minutes. The solution was then dried under reduced pressure at 40°C for 16 hours, and the state after drying for 2 hours was photographed and visually observed.

[0150] 5-2. Evaluation Figure 6 is a photograph of the state of each curable composition after drying, taken from directly above the bottom of the vial. As shown in Figure 6, after 2 hours of drying, slight solid precipitates were observed under conditions 1, 2, and 5, whereas no solid precipitates were observed under conditions 3 and 4. In particular, under condition 4, no solid precipitates were observed even after 16 hours of drying. These findings indicate that heating at a temperature equal to or higher than the reaction temperature for a predetermined period of time further enhances the compatibility between the epoxy compound and the active ester compound.

[0151] This application claims priority from Japanese Patent Application No. 2023-223593, filed December 28, 2023. The contents of the specification and drawings of that application are incorporated herein by reference in their entirety.

[0152] The reactant of the present invention can suppress the generation of hydroxyl groups and react with epoxy compounds even at low reaction temperatures, and is therefore suitable as a modifying agent or curing agent for reacting with epoxy compounds.

Claims

1. A reactant for reacting with an epoxy compound, which is an active ester compound having a structure in which an acyloxy group is directly bonded to a carbon atom constituting a 1,3,5-triazine ring. Reactant.

2. The reactant according to claim 1, which is a modifying agent for reacting with an epoxy compound and is a compound represented by the following formula (1): (In formula (1), R １ ~R ３ are each a monovalent organic group, and X and Y are each an oxygen atom, -NR- (R is a substituent), or a sulfur atom.

3. The reactant is a curing agent for an epoxy compound, and the active ester compound is a compound represented by the following formula (2). The reactant according to claim 1. (In formula (2), ２ R ３ and R ４ are each a monovalent organic group, R ４ is an m-valent organic group, m is an integer of 1 or more, when m = 1, at least two of X, Y and Z are carbonyloxy bonds, and the rest are an oxygen atom, -NR- (R is a substituent) or a sulfur atom, when m = 2 or more, at least one of X, Y and Z is a carbonyloxy bond, and the rest are an oxygen atom, -NR- (R is a substituent) or a sulfur atom.) 4. m is an integer of 2 or more, Z is a carbonyloxy bond, and X and Y are each an oxygen atom, -NR- or a sulfur atom. The reactant according to claim 3.

5. m is an integer of 2 or more, X and Y are each a carbonyloxy bond, and Z is an oxygen atom, -NR- or a sulfur atom. The reactant according to claim 3.

6. The reactant according to claim 1, wherein the reactant is a curing agent for an epoxy compound, and the active ester compound is a polymer having a structure represented by any one of the following formulas (3) to (6). (In formulas (3) and (4), R ２、 R ３ and R ６ Each of R is a monovalent organic group; ５ is a divalent organic group, R is a group constituting a repeating unit of a polymer, X and Y are each an oxygen atom, -NR- (R is a substituent) or a sulfur atom, and n is an integer of 2 or more. (In formulas (5) and (6), R ２、 R ３ and R ７ Each of R is a monovalent organic group; ８ is a divalent organic group, R is a group constituting a repeating unit of a polymer, X is an oxygen atom, -NR- (R is a substituent) or a sulfur atom, and n is an integer of 2 or more.

7. A curable composition comprising an epoxy compound and the reactant according to any one of claims 3 to 6.

8. The curable composition according to claim 7, wherein the epoxy compound is an alicyclic epoxy compound.

9. A method for reacting an epoxy compound with the reactant according to any one of claims 1 to 6. Method for reacting an epoxy compound.

10. The reaction method according to claim 9, wherein the epoxy compound is an alicyclic epoxy compound.

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