Hardening components

Abstract

To provide: a compound and a reagent each of which generates an addition reaction to an epoxy group of an epoxy group-containing compound without using a catalyst and does not generate a hydroxyl group after the reaction; and a curable composition using the compound.SOLUTION: A compound comprising a nitrogen-containing heterocycle and ester structure as illustrated in the following general formula (1), and a reagent comprising the compound as a partial structure are used. In the following general formula (1), a ring represented by A (A ring) is a nitrogen-containing heterocycle and, when one nitrogen atom included in the ring is referred to as a specific nitrogen atom, three bonding hands extending from the A ring as represented in the general formula (1) are those from constituent elements of the A ring, which are not the specific nitrogen atom; R1 and R2 are each independently a hydrogen atom, a halogen atom, a nitro group, or a monovalent organic group, or they may be linked with each other to form a ring structure; and R3 is a monovalent organic group.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a compound, a reactant for an epoxy group-containing compound, a curable composition, and a chemical reaction method.

Background Art

[0002] An epoxy resin is a thermosetting resin that cures by undergoing a polyaddition reaction between an epoxy group-containing compound and a curing agent, and is used in paints, adhesives, solder resists for substrates, and the like. These epoxy resins are widely used because their cured products exhibit excellent properties in terms of heat resistance, adhesiveness, chemical resistance, and the like.

[0003] In the process of curing an epoxy resin, amino groups and the like contained in the curing agent are added to the epoxy groups contained in the monomer to open the ring, and the epoxy resin cures by forming a crosslinked product having a network molecular structure. Along with the opening of the epoxy group, the oxygen atom contained in the epoxy ring is converted into a hydroxyl group, so the above crosslinked product contains a hydroxyl group in its structure. Therefore, the obtained cured product has demerits such as an increased dielectric constant and hygroscopicity due to the presence of the hydroxyl group contained in its structure.

[0004] From such a background, in Non-Patent Document 1, an addition reaction between an epoxy group-containing compound and an active ester of carboxylic acid has been proposed. According to this reaction, since no hydroxyl group is generated after the epoxy group is opened, the above problems can be solved. However, in this reaction, a quaternary ammonium salt or the like is required as a catalyst. Therefore, when an epoxy resin is formed using this reaction system, demerits such as side reactions caused by water during curing or the residue of a quaternary ammonium salt or the like and its decomposition products in the cured product occur due to the presence of a hygroscopic quaternary ammonium salt or the like.

Prior Art Documents

Non-Patent Documents

[0005]

Non-Patent Document 1

[0006] The present invention has been made in view of the above circumstances, and aims to provide compounds, reagents, and curable compositions using the same that undergo an addition reaction with respect to the epoxy group of an epoxy group-containing compound without the use of a catalyst, and that do not generate a hydroxyl group after the reaction. [Means for solving the problem]

[0007] The inventors of this invention have conducted extensive research to solve the above problems and have found that, as shown in the following chemical formulas (A) to (C), a carboxylic acid ester compound having a basic nitrogen in its molecule undergoes an autocatalytic addition reaction with an epoxy group-containing compound, opening the epoxy group and adding it without generating a hydroxyl group. The present invention, like the invention described in Non-Patent Document 1, involves the action of an active ester compound on an epoxy group-containing compound. However, while the invention described in Non-Patent Document 1 requires a quaternary ammonium compound, which is a nitrogen-containing compound, as a catalyst, the present invention has a nitrogen-containing heterocycle in the molecule of the active ester compound, so the compound itself is considered to possess autocatalytic activity. The present invention has been completed based on these findings and provides the following. Note that the chemical reactions shown in the following chemical formulas (A) to (C) are examples of the present invention shown for illustrative purposes, and the present invention is not limited to the examples of the following chemical formulas (A) to (C).

[0008] [ka]

[0009] (1) The present invention is A curable composition characterized by containing a compound having two or more substructures represented by the following general formula (7) or (8) and an epoxy resin, and not containing a curing reaction catalyst. That is the case. [ka] ( In the general formulas (7) and (8) above, each bond marked with an asterisk (*) independently represents a bond to another element. )

[0010] (2) Furthermore, the present invention is The curable composition according to item (1), wherein the above compound comprises two or more substructures represented by the following general formula (7a) or (8a). That is the case. [ka] ( In the above general formulas (7a) and (8a), each bond marked with * independently represents a bond to another element, and each bond marked with ** independently represents either no bond or a bond to another element. )

[0011] (3) Furthermore, the present invention is A curable composition according to item (1) or (2), characterized by being thermally latent and curing upon heating. That is the case. [Effects of the Invention]

[0021] According to the present invention, compounds and reagents that undergo an addition reaction with the epoxy group of an epoxy group-containing compound without the use of a catalyst, and that do not produce hydroxyl groups after the reaction, as well as curable compositions using the same, are provided. [Modes for carrying out the invention]

[0022] The following describes the first and second embodiments of the compound of the present invention, one embodiment of the reagent for the epoxy group-containing compound of the present invention, one embodiment of the curable composition of the present invention, and one embodiment of the chemical reaction method of the present invention. It should be noted that the present invention is not limited to the following embodiments and examples, and can be implemented with appropriate modifications within the scope of the present invention.

[0023] [First embodiment of the compound] First, a first embodiment of the compound of the present invention will be described. The compound of this embodiment is represented by the following general formula (1), and is characterized by being able to open the ring and add to the epoxy group of an epoxy group-containing compound without the use of a catalyst, and by not producing a hydroxyl group in the adduct after the reaction.

[0024] [ka]

[0025] In the general formula (1) above, the ring represented by A (referred to as the A ring) is a nitrogen-containing heterocycle. When one nitrogen atom contained in the A ring is called a specific nitrogen atom, the three bonds that arise from the A ring, as shown in the general formula (1) above, are bonds from elements of the A ring that are not the specific nitrogen atom. In other words, in order for the above reaction to occur, the A ring needs either a free nitrogen atom that has no bonds other than those that form the ring, or one nitrogen atom that has an alkyl group bonded to it, such as N-CH3, in addition to the bonds that form the ring. The above explanation represents this. Such a specific nitrogen atom is necessary for autocatalysis to occur. If the A ring contains only one nitrogen atom, the three bonds that arise from the A ring will come from atoms other than that nitrogen atom. If the A ring contains two or more nitrogen atoms, it is permissible for any or all of the three bonds that arise from the A ring to come from nitrogen atoms, provided that one free nitrogen atom or one nitrogen atom with an alkyl group bonded to it remains. As mentioned above, an alkyl group may be bonded to the specific nitrogen atom, and in this case, it is preferable that the alkyl group has 6 or fewer carbon atoms. When the specific nitrogen atom is free, one of the two bonds generated from the specific nitrogen atom to form the ring becomes a double bond. The size of ring A can range from a 5-membered ring to an 8-membered ring, but among these, a 5-membered ring is preferred. Furthermore, ring A, which is a nitrogen-containing heterocycle, may contain other heteroatoms such as oxygen atoms or sulfur atoms in addition to nitrogen atoms.

[0026] In the above general formula (1), R 1 and R 2 Each of these is independently a hydrogen atom, a halogen atom, a nitro group, or a monovalent organic group. Examples of such organic groups include alkyl groups and alkyloxy groups having 12 or fewer carbon atoms. Also, R 1 and R 2may be connected to each other to form a ring structure. Examples of such a ring structure include an alicyclic or aromatic ring that may have a heteroatom and may be a condensed ring. Among these, an aromatic ring is preferably mentioned, and a benzene ring is more preferably mentioned.

[0027] In the general formula (1) above, R 3 is a monovalent organic group. In this specification, the "organic group" contains at least one carbon atom and may additionally contain various atoms other than carbon atoms. Although not particularly limited, examples of R 3 include an alkyl group having 1 to 10 carbon atoms, a haloalkyl group or a cycloalkyl group which may have a heteroatom or a substituent, an aryl group which may have a heteroatom or a substituent, and the like. As an example of the substituent in the expression "may have a substituent", a halogen atom, a nitro group, an alkyloxy group, etc. can be mentioned. Examples of the aryl group mentioned above include a phenyl group, a naphthyl group, a pyridyl group, a thienyl group, etc. As already described, a substituent may be bonded to these aryl groups. Also, R 3 which is a monovalent organic group may contain one or more of the "portion excluding R 3 " in the general formula (1) in its structure. Among these, a phenyl group which may have a substituent can be preferably mentioned as R 3 , but it is not particularly limited.

[0028] Preferred examples of the compound represented by the general formula (1) above include compounds represented by any of the following general formulas (2) to (4).

[0029] [Chemical formula]

[0030] The compounds represented by the general formulas (2) to (4) above are all those in which the A ring portion in the general formula (1) is specified by a triazole ring, an oxazole ring or a thiazole ring. In the general formula (2) above, R 1 and R2 Each is either an independent hydrogen atom, a halogen atom, a nitro group, or a monovalent organic group, or they are linked together to form a ring structure, R 3 R is a monovalent organic group. In the above general formula (3), 1 and R 2 Each is either an independent hydrogen atom, a halogen atom, a nitro group, or a monovalent organic group, or they are linked together to form a ring structure, R 3 R is a monovalent organic group. In the above general formula (4), 1 and R 2 Each is either an independent hydrogen atom, a halogen atom, a nitro group, or a monovalent organic group, or they are linked together to form a ring structure, R 3 R is a monovalent organic group. These are R in general formulas (2) to (4). 1 , R 2 and R 3 Since this is the same as in the general formula (1) above, we will omit the explanation here.

[0031] Preferred examples of compounds represented by the above general formulas (2) to (4) include compounds represented by any of the following general formulas (2a) to (4a).

[0032] [ka]

[0033] The compounds represented by the above general formulas (2a) to (4a) all have R in the above general formulas (2) to (4). 1 and R 2 This specifies that they are linked to each other to form an aromatic ring. In the above general formula (2a), R 3 R is a monovalent organic group, and Ar is an aromatic ring. In the above general formula (3a), 3 R is a monovalent organic group, and Ar is an aromatic ring. In the above general formula (4a), 3 is a monovalent organic group, and Ar is an aromatic ring.

[0034] In the above general formulas (2a) to (4a), the aromatic ring represented by Ar may have substituents, may be a fused ring, or may be a heteroaromatic ring containing a heteroatom. Examples of such aromatic rings include benzene rings, naphthalene rings, and anthracene rings. Among these, benzene rings are preferred, but are not particularly limited. 3 Since this is the same as in the general formula (1) above, we will omit the explanation here.

[0035] As already explained, the compound represented by general formula (1) autocatalytically opens the epoxy group of an epoxy group-containing compound and adds to it. The mechanism of this reaction is not entirely clear, but the following chemical reaction equation shows two possible reaction mechanisms when benzotriazolylbenzoate (BAB) is used as the compound represented by general formula (1) and adds to an epoxy group-containing compound to form a β-adduct. Note that if an α-adduct is formed instead of a β-adduct, the lone pair of electrons on the nitrogen atom in intermediate 1 will attack the carbon atom to which R is bonded. Furthermore, in the reaction mechanism below, a compound with a triazole ring is used as an example of the compound represented by general formula (1), but the presence of a nitrogen atom in the nitrogen-containing heterocycle is important in this chemical reaction, and similar chemical reactions will occur with other nitrogen-containing heterocycle-containing compounds, not just triazole rings.

[0036] (Estimated reaction mechanism 1) [ka]

[0037] (Estimated reaction mechanism 2) [ka]

[0038] As shown in the chemical reaction equation above, when the compound of the present invention represented by the general formula (1) is added by ring-opening the epoxy group of an epoxy group-containing compound, the oxygen atoms contained in the epoxy group form an ester, and thus, unlike when amines are reacted, no hydroxyl group is generated. For this reason, the compound of the present invention can be said to be a novel and useful reagent for epoxy group-containing compounds.

[0039] [Second embodiment of the compound] Next, a second embodiment of the compound of the present invention will be described. In the compound of the first embodiment already described, the structures necessary for ring-opening and adding to the epoxy group of an epoxy group-containing compound include a nitrogen-containing heterocyclic portion and an ester structure portion bonded thereto. The compound of this embodiment has two or more of these necessary structures. Since this compound has two or more sites that react with the epoxy group to form a bond (i.e., the substructure represented by the general formula (5) below), it can crosslink epoxy compounds and can be used, for example, as a crosslinking agent for epoxy resins. Such a compound may be, for example, a relatively low molecular weight compound having two or more substructures represented by the general formula (5) below, or it may be a polymer compound having multiple substructures represented by the general formula (5) below, for example, by providing the substructure in the side chain of the polymer.

[0040] Furthermore, the compound of this embodiment, like the compound of the present invention represented by the general formula (1) above, has a nitrogen-containing heterocyclic portion and an ester structure portion bonded thereto as a site for ring-opening and adding to the epoxy group of an epoxy group-containing compound. Therefore, it can be ring-opened and added to the epoxy group of an epoxy group-containing compound without the use of a catalyst, and the adduct after the reaction does not produce a hydroxyl group.

[0041] [ka]

[0042] In the general formula (5) above, the ring represented by A (referred to as the A ring) is a nitrogen-containing heterocycle. When one nitrogen atom contained in the A ring is called the specific nitrogen atom, the three bonds arising from the A ring in the general formula (5) above are bonds from A ring constituent elements other than the specific nitrogen atom. This is as explained in the explanation for general formula (1) above, so the explanation is omitted here. Also, as in the case of general formula (1) above, an alkyl group may be bonded to the specific nitrogen atom, in which case it is preferable that the number of carbon atoms in the alkyl group is 6 or less. When the specific nitrogen atom is free, one of the two bonds arising from the specific nitrogen atom to form the ring becomes a double bond. The size of the A ring can range from a 5-membered ring to an 8-membered ring, but among these, a 5-membered ring is preferred. In addition, the nitrogen-containing heterocycle A ring may contain other heteroatoms such as oxygen atoms and sulfur atoms in addition to nitrogen atoms.

[0043] In the above general formula (5), each bond marked with an asterisk (*) independently represents a bond to another element. As already stated, in the reactant of the present invention, the nitrogen-containing heterocycle A ring and the ester structure bonded to it are what impart reactivity to the epoxy group; therefore, the other parts, i.e., the substructures to which each bond marked with an asterisk (*) is bonded, can be any structure. The compound of this embodiment has two or more structures represented by the above general formula (5), and therefore functions as a crosslinking agent (i.e., curing agent) in epoxy resins. As already stated, the compound of the present invention does not produce hydroxyl groups after ring-opening the epoxy group and adding to it. Therefore, if the compound of this embodiment is used as a curing agent in epoxy resins, a cured product without hydroxyl groups is obtained, and unlike cured products containing hydroxyl groups, it has suppressed dielectric properties and hygroscopicity. The compound of this embodiment may be a low molecular weight compound with a molecular weight similar to that of a typical amine-based curing agent, or it may be a high molecular weight compound having the structure represented by the above general formula (5) in multiple side chains.

[0044] The reaction mechanism when a compound having general formula (5) as a substructure reacts with an epoxy group is the same as that of the compound represented by general formula (1), so the explanation is omitted here.

[0045] Preferred examples of compounds having the above general formula (5) as a substructure include ester compounds having any of the following general formulas (6) to (8) as a substructure.

[0046] [ka]

[0047] The substructures represented by the above general formulas (6) to (8) are all obtained by specifying the A ring portion of the above general formula (5) as a triazole ring, oxazole ring, or thiazole ring. In the above general formulas (6) to (8), each bond marked with an asterisk (*) independently represents a bond to another element. This is the same as in the above general formula (5), so the explanation is omitted here.

[0048] Preferred examples of compounds having any of the above general formulas (6) to (8) as a substructure include compounds having any of the following general formulas (6a) to (8a) as a substructure.

[0049] [ka]

[0050] The substructures represented by the above general formulas (6a) to (8a) all specify that the two bonders attached to the nitrogen-containing heterocycle in the above general formulas (6) to (8) are attached to the atoms constituting the aromatic ring. In the above general formulas (6a) to (8a), each bond marked with * independently represents a bond to another element, and each bond marked with ** independently represents either no bond or a bond to another element.

[0051] [Reagents for epoxy group-containing compounds] A reactant for epoxy group-containing compounds, comprising the compounds of the first embodiment and the compounds of the second embodiment described above, is also part of the present invention. These compounds have a nitrogen-containing heterocyclic portion and an ester structure portion bonded to it as a site for ring-opening and adding to the epoxy group of the epoxy group-containing compound. Therefore, they can ring-open and add to the epoxy group of the epoxy group-containing compound without the use of a catalyst, and they have the characteristic of not producing hydroxyl groups in the adduct after the reaction. Accordingly, these compounds are good reactants for epoxy group-containing compounds. The reactant for epoxy group-containing compounds of the present invention utilizes these characteristics of the compounds of the present invention. As these have already been explained, further explanation is omitted here.

[0052] Furthermore, the reagent for epoxy group-containing compounds of the present invention hardly reacts at room temperature and exhibits an addition reaction to the epoxy group upon heating. For this reason, the reagent for epoxy group-containing compounds of the present invention is preferably used in applications of thermally latent curable compositions using epoxy resins.

[0053] [Curable composition] Next, the curable composition of the present invention will be described. As already explained, a compound having the above general formula (5) as a substructure acts as a reactant for epoxy group-containing compounds. This reactant opens the ring of the epoxy group in the epoxy group-containing compound without a catalyst and adds to it. For this reason, a compound having two or more substructures represented by the above general formula (5) is useful as a curing agent for epoxy resins. The curable composition of the present invention focuses on this point and is characterized by containing an epoxy resin and a compound having two or more substructures represented by the above general formula (5) (i.e., the compound of the second embodiment described above).

[0054] The curable composition of the present invention comprises an epoxy resin which is an epoxy group-containing compound and a compound having two or more substructures represented by the general formula (5) above. The compound having two or more substructures represented by the general formula (5) above has already been described, so its description here will be omitted. Furthermore, since the curable composition of the present invention does not require a curing reaction catalyst, it is preferable that it does not contain a curing reaction catalyst, which would become an impurity in the cured product and increase the hygroscopicity of the cured product. Furthermore, the curable composition of the present invention is thermosetting, and its curing temperature can be exemplified as being around 80 to 150°C, but is not particularly limited.

[0055] Examples of epoxy resins include those that have been used in the field of curable compositions, without any particular limitations. Such epoxy resins include phenol novolac type epoxy resins, cresol novolac type epoxy resins, hydroquinone type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, biphenyl type epoxy resins, stilbene type epoxy resins, triphenolmethane type epoxy resins, alkyl-modified triphenolmethane type epoxy resins, triazine nucleus-containing epoxy resins, dicyclopentadiene-modified phenol type epoxy resins, phenol aralkyl type epoxy resins having a phenylene and / or biphenylene skeleton, naphthol type epoxy resins, naphthalene type epoxy resins, naphthol aralkyl type epoxy resins having a phenylene and / or biphenylene skeleton, and the like. These may be used individually or in combination of multiple types.

[0056] The curable composition of the present invention suppresses the formation of hydroxyl groups associated with ring-opening of epoxy groups during curing, thereby yielding a cured product with excellent properties such as low dielectric constant and low hygroscopicity. For this reason, the curable composition of the present invention can be preferably used in fields such as adhesives, electronic circuit boards, and solder resists. Furthermore, as already mentioned, the reactant for the epoxy group-containing compound used in this curable composition hardly reacts at room temperature and exhibits an addition reaction to the epoxy group upon heating. For this reason, the curable composition of the present invention can be stored without curing at around room temperature and possesses thermal latent properties that allow it to cure upon heating.

[0057] [Chemical reaction method] A chemical reaction method characterized by reacting the compound of the present invention described above with an epoxy group-containing compound is also one of the present inventions. As this has already been explained, a further explanation will be omitted here. [Examples]

[0058] The present invention will be described in more detail below with reference to examples, but the present invention is not limited in any way to the following examples.

[0059] • Synthesis of Compound 1 [ka]

[0060] 4.63 g (34.3 mmol) of 1-hydroxybenzotriazole (HOBt) was added to a 300 mL three-necked flask, and 100 mL of dry tetrahydrofuran (THF) and 4.92 mL (33.0 mmol) of 1,8-diazabicyclo[5.4.0]-7-undecene (DBU) were added under an argon stream. The system was cooled to -15°C in an ice bath with sodium chloride, and 30 mL of a dry THF solution of 4.84 g (34.5 mmol) of benzoyl chloride (BC) was added dropwise. The system was stirred for 5 hours while maintaining the temperature below -15°C. The reaction mixture was poured into 700 mL of ice water and stirred for 10 minutes. The solid was collected by suction filtration and dried under reduced pressure. This was dissolved in 750 mL of hexane at 50°C, and then recrystallized at room temperature. The precipitated solid was recovered by suction filtration to obtain compound 1 as a white, plate-like crystalline material (yield 7.11 g, yield 87%).

[0061] The physical properties of the product are as follows: Melting point: 78.1-78.3℃ FT-IR(KBr,cm -1 ):3066(ν C-H,芳香族 ),1777(νC=O),1597(ν C-C,芳香族 ),1490(ν N=N ),1230(ν C-O ),1085(ν C-N ),984(ν N-O ),705(δ C-H,芳香族 ). 1 H-NMR(500MHz, CDCl3) δ(ppm):8.30(d,J=7.5Hz,2.00H,Hc),8.12(d,J=8.0Hz,0.98H,Hd),7.79(t,J=7.5Hz,1.02H, Ha),7.63(t,J=8.0Hz,2.05H,Hb),7.57(t,J=7.5Hz,1.04H,He),7.49-7.44(m,2.04H,Hf,Hg).

[0062] [ka]

[0063] • Synthesis of Compound 2 [ka]

[0064] 4.46 g (33.0 mmol) of 2-benzoxazolinone (BO) was added to a 300 mL three-necked flask, and 110 mL of dry THF and 4.93 g (32.4 mmol) of DBU were added under an argon stream. The system was cooled to -10°C in an ice bath with sodium chloride, and 20 mL of a dry THF solution of 4.47 g (31.8 mmol) of benzoyl chloride (BC) was added dropwise. The system was stirred for 4.5 hours while maintaining the temperature below -10°C. The reaction mixture was poured into 700 mL of ice water and stirred for 10 minutes. The solid was collected by suction filtration and dried under reduced pressure. This was dissolved in 153 mL of chloroform, and then 58 mL of hexane was added. Recrystallization was performed at room temperature. The precipitated solid was collected by suction filtration to obtain compound 2 as white plate-like crystals (yield 5.48 g, yield 75%).

[0065] The physical properties of the product are as follows: Melting point: 138.2–139.0°C FT-IR(KBr,cm -1 ):3053(ν C-H,芳香族 ),1699(ν C=O ),1600(ν C-C,芳香族 ),1312(ν C-O ),1480(ν C-C ),1141(ν C-O,複素環 ),756(δ C-H,芳香族 ). 1 H-NMR(500MHz, CDCl3) δ(ppm):7.86(t,J=5.0Hz,0.97H,Hb),7.81(d,J=7.5Hz,1.92H,Hc),7.65(t,J=7 .5Hz,0.99H,Ha),7.51(t,J=8.0Hz,2.00H,He,Hf),7.30-7.26(m,3.32H,Hd,Hg).

[0066] [ka]

[0067] • Synthesis of compound 3 [ka]

[0068] 5.01 g (33.1 mmol) of 3H-benzothiazole-2-one (BT) was added to a 300 mL three-necked flask, and 100 mL of dry THF and 5.45 g (35.8 mmol) of DBU were added under an argon stream. The system was cooled to -7°C in an ice bath with sodium chloride, and 30 mL of a dry THF solution of 4.80 g (34.1 mmol) of benzoyl chloride (BC) was added dropwise. The system was stirred for 4.5 hours while maintaining the temperature below -7°C. The reaction mixture was poured into 700 mL of ice water and stirred for 10 minutes. The solid was collected by suction filtration and dried under reduced pressure. This was dissolved in 430 mL of hexane and allowed to stand at room temperature for recrystallization. The precipitated solid was collected by suction filtration to obtain compound 3 as white plate-like crystals (yield 3.70 g, yield 44%).

[0069] The physical properties of the product are as follows: Melting point: 91.2-92.0°C FT-IR(KBr,cm -1 ):3062(ν C-H,芳香族 ),1685(ν C=O ),1464(ν C-C,環伸縮振動 ),1154(ν C-O-C,逆対称伸縮振動 ),751(δ C-H,芳香族面外変角振動 ). 1 H-NMR(500MHz, CDCl3) δ(ppm):7.88(d,J=7.5Hz,1.96H,Hc),7.65(t,J=7.5Hz,1.00H,Ha),7.58(d,J=8.0Hz,1.35H,Hd),7.51(d,J= 8.0Hz,1.96H,Hb),7.46(d,J=8.0Hz,0.95H,Hg),7.33(t,J=7.5Hz,1.00H,Hf),7.27(t,J=7.5Hz,1.57H,He).

[0070] [ka]

[0071] • Reaction of compound 1 with glycidylphenyl ether (GPE) in a solvent. 0.479 g (2.00 mmol) of compound 1, 0.300 g (2.00 mmol) of glycidylphenyl ether (GPE), and 2.7 mL (1.5 mol / L) of N-methylpyrrolidone were added to a two-necked flask. The mixture was then heated to 150°C using an oil bath while stirring under an argon stream. The reaction was monitored by thin-layer chromatography (TLC), and heating was stopped after 5 hours when the GPE spots disappeared. The reaction solution was transferred to a sample bottle, 20 mL of water was added, and the mixture was stirred for 1 hour before decantation. The resulting dark brown viscous liquid was dried under reduced pressure at room temperature to obtain the crude reaction product of compound 1 and GPE (crude yield 78.7%).

[0072] • Reaction of compound 1 with glycidylphenyl ether (GPE) under solvent-free conditions [ka]

[0073] As described above, a crude product, an adduct of compound 1 and GPE, was obtained by reacting compound 1 with GPE in a solvent. However, when compound 1 is added to GPE, it can add to one of the two carbon atoms contained in the epoxy group of GPE, resulting in the formation of an α-adduct (AD-1(α)) and a β-adduct (AD-1(β)). Therefore, we attempted to isolate the α-adduct and β-adduct by adding compound 1 to GPE under solvent-free conditions. 1.23 g (5.14 mmol) of compound 1 and 0.771 g (5.14 mmol) of GPE were added to a two-necked flask. The mixture was then heated to 90°C using an oil bath while stirring under a nitrogen stream. The reaction was monitored by thin-layer chromatography (TLC), and heating was stopped after 5 hours when the GPE spot disappeared to obtain the crude product of the reaction between compound 1 and GPE (crude yield 1.86 g, crude yield 93%). Silica gel chromatography (developing solvent: ethyl acetate / hexane = 1 / 9 → 1 / 4) was performed on the obtained crude product to obtain the α-adduct AD-1(α) (yield 14%) and the β-adduct AD-1(β) (yield 26%).

[0074] The obtained physical property data for AD-1(α) are as follows: FT-IR(KBr,cm -1 ):3063(ν C-H,芳香族 ),2953(ν C-H,アルキル ),1722(ν C=O ),1599(ν C-C ),1495(ν C-N ),1451(ν N=N ),1269(ν C-O ),1110(ν C-O-C ),712(δ C-H ). 1 H-NMR(500MHz,CDCl3)δ(ppm):7.98(d,J=8.5Hz,1.00H,Hl),7.92(d,J=7.5Hz,1.99 H,Hm),7.59(m,3.09H,Ho,Hi,Hj),7.42(t,J=7.5Hz,2.05H,Hn),7.37(t,J=8.0Hz,1 .09H,Hk),7.31(t,J=8.5Hz,2.01H,Hb),7.01(t,J=7.5Hz,1.01H,Ha),6.94(d,J=7. 5Hz,1.98H,Hc),5.78(m,1.01H,Hf),4.94(m,2.00H,Hg,Hh),4.28(m,2.03H,Hd,He).

[0075] [ka]

[0076] The obtained physical property data for AD-1(β) are as follows: FT-IR(KBr,cm -1 ):3063(ν C-H,芳香族 ),2953(ν C-H,アルキル ),1722(ν C=O ),1599(ν C-C ),1495(ν C-N ),1451(ν N=N ),1269(ν C-O ),1110(ν C-O-C ),712(δ C-H ). 1 H-NMR(500MHz,CDCl3)δ(ppm):7.98(d,J=8.5Hz,3.00H,Hl,Ho),7.63(t,J=7.5Hz,1.06H,Hm),7.49(m,1.06H,Hi),7.42(m,3.05H,Hn,Hj),7.35 (3.09H,Hk,Hb),7.01(t,J=8.5Hz,1.06H,Ha),6.98(d,J=7.5Hz,2.03H, Hc),5.85(m,0.95H,Hf),5.05(m,1.94H,Hg,Hh),4.50(m,2.01H,Hd,He).

[0077] [ka]

[0078] Furthermore, ESI-TOF-MS measurements were performed on both the obtained AD-1(α) and AD-1(β). As a result, a peak at m / z = 412.21 was observed in both samples. This is due to the presence of sodium ions (Na) in AD-1(α) and AD-1(β). + Since the peak corresponds to the adduct, it is supported that the adduct obtained by the above procedure has the structures shown by AD-1(α) and AD-1(β).

[0079] From the above physical property data, it was found that compound 1, which has a nitrogen-containing heterocycle and an ester moiety, reacts with GPE, an epoxy group-containing compound, under catalyst-free conditions, and that the reactant does not contain a hydroxyl group.

[0080] • Reaction of compound 1 and GPE under solvent-free conditions 1 Tracking by H-NMR As described above, the reaction of compound 1 with GPE under solvent-free conditions yields two adducts, AD-1(α) and AD-1(β), and these 1 The signal was confirmed in 1H-NMR. Therefore, when the reaction temperature under solvent-free conditions was set to 90°C, 100°C, or 110°C... 1 The yields were determined by calculating them using 1H-NMR. Add 1.23 g (5.14 mmol) of compound 1 and 0.771 g (5.14 mmol) of GPE to a two-necked flask, and heat to 90°C using an oil bath while stirring under a nitrogen stream, taking samples every hour. 1 The reaction was tracked by 1H-NMR. Heating was stopped after confirming that the GPE signal had disappeared after 9 hours, and the results for AD-1(α) and AD-1(β) were obtained. 1 The yields were calculated based on the 1H-NMR signals. Using a similar procedure, the yields of AD-1(α) and AD-1(β) were calculated when the reaction temperature was changed to 100°C or 110°C. The results are shown in Table 1.

[0081] [Table 1]

[0082] 1 Analysis using 1H-NMR revealed that the yield of the adduct was over 70% at temperatures above 90°C, and over 85% at temperatures above 100°C. Furthermore, the ratio of AD-1(α) to AD-1(β) remained approximately 36:64 regardless of the reaction temperature.

[0083] • Reaction of compound 2 with GPE 0.456 g (2.00 mmol) of compound 2, 0.300 g (2.00 mmol) of GPE, and 2.7 mL (1.5 mol / L) of N-methylpyrrolidone were added to a two-necked flask. The mixture was heated to 150°C using an oil bath while stirring under an argon stream. The reaction was monitored by thin-layer chromatography (TLC), and heating was stopped after 5 hours when the GPE spots disappeared. The reaction solution was transferred to a sample bottle, 20 mL of water was added, and the mixture was stirred for 1 hour before decantation. The resulting dark brown viscous liquid was dried under reduced pressure at room temperature to obtain the reaction composition of compound 2 and GPE (crude yield 69.8%).

[0084] • Reaction of compound 3 with GPE 0.510 g (2.00 mmol) of compound 3, 0.300 g (2.00 mmol) of GPE, and 2.7 mL (1.5 mol / L) of N-methylpyrrolidone were added to a two-necked flask. The mixture was heated to 150°C using an oil bath while stirring under an argon stream. The reaction was monitored by thin-layer chromatography (TLC), and heating was stopped after 22 hours when the GPE spots disappeared. The reaction solution was transferred to a sample bottle, 20 mL of water was added, and the mixture was stirred for 1 hour before decantation. The resulting dark brown viscous liquid was dried under reduced pressure at room temperature to obtain the reaction composition of compound 3 and GPE (crude yield 77.8%).

[0085] Similar to compound 1, reaction products with GPE were also obtained for compounds 2 and 3. These results demonstrate that the compounds of the present invention are good reactants for epoxy group-containing compounds.

Claims

1. A curable composition characterized by containing a compound having two or more substructures represented by the following general formula (7) or (8) and an epoxy resin, and not containing a curing reaction catalyst. 【Chemistry 1】 (In the general formulas (7) and (8) above, each bond marked with an asterisk (*) independently represents a bond to another element.)

2. The curable composition according to claim 1, wherein the compound comprises two or more substructures represented by the following general formula (7a) or (8a). 【Chemistry 2】 (In the above general formulas (7a) and (8a), each bond marked with * independently represents a bond to another element, and each bond marked with ** independently represents a bond that does not exist or a bond to another element.)

3. A curable composition according to either claim 1 or 2, characterized by being thermally latent and curing upon heating.

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