Compound, reagent for epoxy group-containing compound, curable composition and chemical reaction method

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 technology]

[0002] Epoxy resins are thermosetting resins that are cured by a polyaddition reaction between an epoxy group-containing compound and a curing agent, and are used in paints, adhesives, solder resists for circuit boards, etc. These epoxy resins are widely used because the cured products thereof exhibit excellent properties in terms of heat resistance, adhesiveness, chemical resistance, etc.

[0003] In the process of curing, the amino group or the like contained in the curing agent is added to the epoxy group contained in the monomer, which opens the ring, and a crosslinked body having a mesh-like molecular structure is generated, and the epoxy resin is cured. With the ring-opening of the epoxy group, the oxygen atom contained in the epoxy ring is converted to a hydroxyl group, so that the crosslinked body contains a hydroxyl group in its structure. Therefore, the obtained cured product has disadvantages such as a large dielectric constant and hygroscopicity due to the presence of the hydroxyl group in the structure.

[0004] In light of this background, Non-Patent Document 1 proposes an addition reaction between an epoxy group-containing compound and an active ester of a carboxylic acid. This reaction does not produce a hydroxyl group after the epoxy group is opened, so the above problem can be solved. However, since this reaction requires a quaternary ammonium salt or the like as a catalyst, when an epoxy resin is formed using this reaction system, the presence of a hygroscopic quaternary ammonium salt or the like causes a side reaction with water during curing, and the quaternary ammonium salt or the like or its decomposition product remains in the cured product, which is a disadvantage. [Prior art documents] [Non-patent literature]

[0005] [Non-Patent Document 1] T. Nishikubo, A. Kameyama, Prog. Polym. Sci. 1993, 18, 963-995. Summary of the Invention [Problem to be solved by the invention]

[0006] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a compound or reactant that undergoes an addition reaction with the epoxy group of an epoxy group-containing compound without the use of a catalyst and does not generate a hydroxyl group after the reaction, and a curable composition using the same. [Means for solving the problem]

[0007] The present inventors 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 the molecule undergoes an autocatalytic addition reaction with an epoxy group-containing compound, and the epoxy group is opened and added without generating a hydroxyl group. The present invention is an invention in which an active ester compound is reacted with an epoxy group-containing compound, as in the invention described in Non-Patent Document 1. However, while the invention described in Non-Patent Document 1 requires a nitrogen-containing compound, a quaternary ammonium compound, as a catalyst, in the present invention, since the active ester compound has a nitrogen-containing heterocycle in the molecule, the compound itself is considered to have an autocatalytic effect. The present invention has been completed based on such findings, and provides the following. The chemical reactions shown in the following chemical formulas (A) to (C) are examples of the present invention shown for explanatory 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 relates to a compound represented by the following general formula (1). [ka] (In the above general formula (1), the ring represented by A (ring A) is a nitrogen-containing heterocycle, and when one nitrogen atom contained in the ring is called a specific nitrogen atom, the three bonds originating from ring A shown in the above general formula (1) are bonds from elements constituting ring A that are not the specific nitrogen atom, and R 1 and R 2 are each independently a hydrogen atom, a halogen atom, a nitro group, or a monovalent organic group, or are linked together to form a ring structure; R 3 is a monovalent organic group.

[0010] (2) The present invention also relates to a compound according to item (1) which is represented by any one of the following general formulas (2) to (4). [ka] (In the above general formula (2), R 1 and R 2 are each independently a hydrogen atom, a halogen atom, a nitro group, or a monovalent organic group, or are linked together to form a ring structure; R 3 In the above general formula (3), R 1 and R 2 are each independently a hydrogen atom, a halogen atom, a nitro group, or a monovalent organic group, or are linked together to form a ring structure; R 3 In the above general formula (4), R 1 and R 2 are each independently a hydrogen atom, a halogen atom, a nitro group, or a monovalent organic group, or are linked together to form a ring structure; R 3 is a monovalent organic group.

[0011] (3) The present invention also relates to compounds according to item (1) or (2), which are represented by the following general formulas (2a) to (4a): [ka] (R in the above general formula (2a) 3 In the above general formula (3a), R is a monovalent organic group, and Ar is an aromatic ring. 3In the above general formula (4a), R is a monovalent organic group, and Ar is an aromatic ring. 3 is a monovalent organic group, and Ar is an aromatic ring.

[0012] (4) The present invention also provides R 3 is a phenyl group which may have a substituent.

[0013] (5) The present invention also relates to a compound having two or more partial structures represented by the following general formula (5). [ka] (In the above general formula (5), the ring represented by A (ring A) is a nitrogen-containing heterocycle, and when one nitrogen atom contained in the ring is referred to as a specific nitrogen atom, the three bonds derived from ring A shown in the above general formula (5) are bonds from elements constituting ring A that are not the specific nitrogen atom, and each bond marked with an * independently represents a bond to another element.)

[0014] (6) The present invention also relates to a compound according to item (5), which has two or more partial structures represented by any one of the following general formulae (6) to (8). [ka] (In the above general formulas (6) to (8), each bond marked with an * independently represents a bond to another element.)

[0015] (7) The present invention also relates to a compound according to item (5) or (6), which has two or more partial structures represented by any one of the following general formulae (6a) to (8a): [ka] (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 absence or a bond to another element.)

[0016] (8) The present invention also relates to a reactant for an epoxy group-containing compound, which comprises the compound according to any one of the above items (1) to (7).

[0017] (9) The present invention also relates to a curable composition containing an epoxy resin and the compound according to any one of the above items (5) to (7).

[0018] (10) The present invention also relates to the curable composition according to (9), which does not contain a curing reaction catalyst.

[0019] (11) The present invention also relates to the curable composition according to item (9) or (10), which is cured by heating.

[0020] (12) The present invention also relates to a chemical reaction method, which comprises reacting the compound according to any one of the above items (1) to (7) with an epoxy group-containing compound. Effect of the Invention

[0021] According to the present invention, there are provided a compound or reactant which undergoes an addition reaction with the epoxy group of an epoxy group-containing compound without the use of a catalyst and does not generate a hydroxyl group after the reaction, and a curable composition using the same. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0022] Hereinafter, the first and second embodiments of the compound of the present invention, one embodiment of the reactant 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 will be described. Note that the present invention is not limited to the following embodiments and aspects, and can be practiced by making 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 a compound represented by the following general formula (1), which is characterized in that it can be added to the epoxy group of an epoxy group-containing compound by ring-opening without using a catalyst, and does not generate a hydroxyl group in the adduct after the reaction.

[0024] [ka]

[0025] In the above general formula (1), the ring represented by A (called Ring A) is a nitrogen-containing heterocycle. When one nitrogen atom contained in Ring A is called a specific nitrogen atom, the three bonds arising from Ring A shown in the above general formula (1) are bonds from elements constituting Ring A that are not specific nitrogen atoms. In other words, in order to cause the above reaction to occur, Ring A must contain either a free nitrogen atom having no bonds other than those for constituting the ring, or N-CH 3 As shown above, one nitrogen atom bonded to an alkyl group is required, and the above explanation represents this. Such a specific nitrogen atom is necessary to cause an autocatalytic reaction. When only one nitrogen atom is included as an element constituting the A ring, the three bonds arising from the A ring are generated from an atom other than the nitrogen atom. When two or more nitrogen atoms are included as an element constituting the A ring, any or all of the three bonds arising from the A ring are allowed to be generated from a nitrogen atom, provided that one free nitrogen atom or a nitrogen atom bonded to an alkyl group remains. As described above, an alkyl group may be bonded to the specific nitrogen atom, and in this case, the number of carbon atoms in the alkyl group is preferably 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 is a double bond. The size of the A ring can be about 5-membered to 8-membered rings, and among these, a 5-membered ring is preferably included. In addition, the A ring, which is a nitrogen-containing heterocycle, may contain other heteroatoms such as oxygen atoms and sulfur atoms in addition to nitrogen atoms.

[0026] In the above general formula (1), R 1 and R 2 are each independently a hydrogen atom, a halogen atom, a nitro group, or a monovalent organic group. Examples of such an organic group include an alkyl group and an alkyloxy group having 12 or less carbon atoms. 1 and R 2 may be linked to each other to form a ring structure. Examples of such a ring structure include an aliphatic ring or an aromatic ring which may have a heteroatom or may be a condensed ring. Among these, an aromatic ring is preferred, and a benzene ring is more preferred.

[0027] In the above general formula (1), R 3 is a monovalent organic group. In this specification, the term "organic group" refers to a group that contains at least one carbon atom, and may also contain various atoms other than carbon atoms. 3 Examples of the substituent include an alkyl group, haloalkyl group or cycloalkyl group having 1 to 10 carbon atoms which may have a heteroatom or a substituent, and an aryl group which may have a heteroatom or a substituent. Examples of the substituent in the expression "may have a substituent" include a halogen atom, a nitro group, and an alkyloxy group. Examples of the aryl group include a phenyl group, a naphthyl group, a pyridyl group, and a thienyl group, and as mentioned above, a substituent may be bonded to these aryl groups. In addition, the monovalent organic group R 3 In the structure, "R 3 Among these, R 3 A preferred example of the alkyl group is a phenyl group which may have a substituent, but is not particularly limited thereto.

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

[0029] [ka]

[0030] The compounds represented by the above general formulas (2) to (4) are all those in which the A ring moiety in the above general formula (1) is specified as a triazole ring, an oxazole ring, or a thiazole ring. 1 and R 2 are each independently a hydrogen atom, a halogen atom, a nitro group, or a monovalent organic group, or are linked together to form a ring structure; R 3 In the above general formula (3), R 1 and R 2 are each independently a hydrogen atom, a halogen atom, a nitro group, or a monovalent organic group, or are linked together to form a ring structure; R 3 In the above general formula (4), R 1 and R 2 are each independently a hydrogen atom, a halogen atom, a nitro group, or a monovalent organic group, or are linked together to form a ring structure; R 3 R in the general formulas (2) to (4) is a monovalent organic group. 1 , R 2 and R 3 is the same as in the above general formula (1), so the explanation will be omitted here.

[0031] Preferred examples of the 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) are all the same as R 1 and R 2 In the above general formula (2a), R 3 In the above general formula (3a), R is a monovalent organic group, and Ar is an aromatic ring. 3In the above general formula (4a), R is a monovalent organic group, and Ar is an aromatic ring. 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 a substituent, may be a condensed ring, or may be a heteroaromatic ring containing a heteroatom. Examples of such aromatic rings include a benzene ring, a naphthalene ring, and an anthracene ring. Among these, a benzene ring is preferred, but is not particularly limited. R in these general formulas (2a) to (4a) 3 is the same as in the above general formula (1), so the explanation will be omitted here.

[0035] As already explained, the compound represented by the general formula (1) autocatalytically opens the epoxy group of the epoxy group-containing compound and adds to it. Although the mechanism of this reaction is not necessarily clear, the following chemical reaction formula shows two possible reaction mechanisms when benzotriazolyl benzoate (BAB) is added to the epoxy group-containing compound to form a β-adduct. When an α-adduct is formed instead of a β-adduct, the unshared electron pair of the nitrogen atom in intermediate 1 attacks the carbon atom to which R is bonded. In addition, in the following reaction mechanism, a compound represented by the general formula (1) having a triazole ring is exemplified, but in this chemical reaction, the presence of the nitrogen atom in the nitrogen-containing heterocycle is important, and the same chemical reaction occurs not only with the triazole ring but also with other nitrogen-containing heterocycle-containing compounds.

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

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

[0038] As shown in the above chemical reaction formula, when the compound of the present invention represented by the above general formula (1) is added by opening the epoxy group of the epoxy group-containing compound, the oxygen atom contained in the epoxy group forms an ester, so unlike the reaction with amines, no hydroxyl group is generated. Therefore, the compound of the present invention can be said to be a novel and useful reactant 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, a nitrogen-containing heterocyclic portion and an ester structure portion bonded thereto can be mentioned as a structure necessary for ring-opening and adding the epoxy group of the epoxy group-containing compound to the ring. The compound of this embodiment has two or more of these necessary structures. This compound has two or more sites (i.e., partial structures represented by the following general formula (5)) that react with the epoxy group to form a bond, so that it can crosslink epoxy compounds and can be used as a crosslinking agent for epoxy resins, for example. Such a compound may be, for example, a relatively low molecular weight compound having two or more partial structures represented by the following general formula (5), or a polymer compound having a plurality of partial structures represented by the following general formula (5) by a method such as providing a partial structure represented by the following general formula (5) on the side chain of a polymer.

[0040] Furthermore, like the compound of the present invention represented by the above general formula (1), the compound of the present embodiment has a nitrogen-containing heterocyclic moiety and an ester structural moiety bonded thereto as a site for ring-opening and adding to the epoxy group of an epoxy group-containing compound, and therefore can be ring-opened and added to the epoxy group of an epoxy group-containing compound without using a catalyst, and has the characteristic of not generating a hydroxyl group in the adduct after the reaction.

[0041] [ka]

[0042] In the above general formula (5), the ring represented by A (referred to as ring A) is a nitrogen-containing heterocycle. When one nitrogen atom contained in ring A is referred to as a specific nitrogen atom, the three bonds arising from ring A shown in general formula (5) are bonds from elements constituting ring A that are not specific nitrogen atoms. This is as described in the above general formula (1), and therefore the description here is omitted. As in the case of general formula (1), an alkyl group may be bonded to the specific nitrogen atom, and in this case, the number of carbon atoms in the alkyl group is preferably 6 or less. When the specific nitrogen atom is free, one of the two bonds arising from the specific nitrogen atom to form a ring is a double bond. The size of ring A may be about 5-membered to 8-membered, and among these, a 5-membered ring is preferred. In addition, ring A, which is a nitrogen-containing heterocycle, 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 * independently represents a bond to another element. As already mentioned, in the reactant of the present invention, it is the A ring, which is a nitrogen-containing heterocycle, and the ester structure bonded thereto that imparts reactivity to epoxy groups, so the other parts, i.e., the partial structures to which each bond marked with * is bonded, may be any structure. The compound of this embodiment has two or more structures represented by the above general formula (5), so it functions as a crosslinking agent (i.e., a curing agent) in epoxy resin. As already mentioned, the compound of the present invention does not generate hydroxyl groups after opening the epoxy group and adding it to it. Therefore, if the compound of this embodiment is used as a curing agent for epoxy resin, a cured product containing no hydroxyl groups can be obtained, which is different from a cured product containing hydroxyl groups and has reduced dielectric properties and hygroscopicity. The compound of this embodiment may be a low molecular weight compound having a molecular weight equivalent to that of a normal amine-based curing agent, or a polymeric compound having a plurality of side chains having the structure represented by the above general formula (5).

[0044] The reaction mode when a compound having general formula (5) as a partial structure reacts with an epoxy group is similar to that of the compound represented by general formula (1) above, and therefore will not be described here.

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

[0046] [ka]

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

[0048] Preferred examples of the compound having any of the above general formulae (6) to (8) as a partial structure include compounds having any of the following general formulae (6a) to (8a) as a partial structure.

[0049] [ka]

[0050] The partial structures represented by the above general formulae (6a) to (8a) each specify that the two bonds bonded to the nitrogen-containing heterocycle in the above general formulae (6) to (8) are bonded to atoms constituting an aromatic ring. In the above general formulae (6a) to (8a), each bond marked with * independently represents a bond to another element, and each bond marked with ** independently represents nonexistence or a bond to another element.

[0051] [Reactants for epoxy group-containing compounds] The reactants for epoxy group-containing compounds, which are composed of the compounds of the first embodiment and the second embodiment, are also one aspect of the present invention. These compounds have 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 the epoxy group-containing compound, so that they can be ring-opened and added to the epoxy group of the epoxy group-containing compound without using a catalyst, and have the characteristic of not producing a hydroxyl group in the adduct after the reaction. Therefore, these compounds are good reactants for epoxy group-containing compounds. The reactants for epoxy group-containing compounds of the present invention utilize the characteristics of the compounds of the present invention. These points have already been explained, so the explanation here will be omitted.

[0052] The reactant for the epoxy group-containing compound of the present invention has a property that it hardly reacts at around room temperature, but exhibits an addition reaction with the epoxy group when heated. Therefore, the reactant for the epoxy group-containing compound of the present invention is preferably used for a heat-latent curable composition using an epoxy resin.

[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 partial structure serves as a reactant for an epoxy group-containing compound. This reactant ring-opens the epoxy group in the epoxy group-containing compound without a catalyst and adds to it. Therefore, a compound having two or more partial structures represented by the above general formula (5) is useful as a curing agent for an epoxy resin. 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 partial structures represented by the above general formula (5) (i.e., the compound of the second embodiment).

[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 partial structures represented by the above general formula (5). The compound having two or more partial structures represented by the above general formula (5) has already been described, so description thereof will be omitted here. Since the curable composition of the present invention does not require a curing reaction catalyst, it is preferable that the curing composition does not contain a curing reaction catalyst that becomes an impurity in the cured product and increases the hygroscopicity of the cured product. The curable composition of the present invention is thermosetting, and the curing temperature can be, for example, about 80 to 150°C, but is not particularly limited.

[0055] The epoxy resin may be any epoxy resin that has been used in the field of curable compositions without any particular limitation. Examples of 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, triphenol methane type epoxy resins, alkyl modified triphenol methane 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, etc. These may be used alone or in combination of multiple types.

[0056] The curable composition of the present invention can suppress the generation of hydroxyl groups accompanying the ring opening of epoxy groups during curing, and therefore can provide a cured product with excellent properties such as low dielectric constant and low hygroscopicity. Therefore, the curable composition of the present invention can be preferably used in the fields of adhesives, electronic circuit boards, solder resists, etc. In addition, as already mentioned, the reactant for the epoxy group-containing compound used in this curable composition has the property of hardly reacting at room temperature and showing an addition reaction to the epoxy group when heated. Therefore, the curable composition of the present invention can be stored without curing at around room temperature, and has the thermal latency to be cured by heating.

[0057] [Chemical reaction method] The present invention also includes a chemical reaction method characterized by reacting the compound of the present invention with an epoxy group-containing compound. Since this has already been described, the description thereof will be omitted here. EXAMPLES

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

[0059] Synthesis of compound 1 [ka]

[0060] To a 300 mL three-necked flask, 4.63 g (34.3 mmol) of 1-hydroxybenzotriazole (HOBt) was added, 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 added salt, and a dry-THF solution (30 mL) of 4.84 g (34.5 mmol) of benzoyl chloride (BC) was added dropwise thereto, and the system was stirred for 5 hours while maintaining the temperature below -15 °C. The reaction solution was poured into 700 mL of ice water and stirred for 10 minutes, then the solid was recovered by suction filtration and dried under reduced pressure. This was dissolved in 750 mL of hexane at 50 °C, and then allowed to stand at room temperature for recrystallization. The precipitated solid was recovered by suction filtration to obtain 7.11 g of white plate-like crystals of Compound 1 (yield 87%).

[0061] The physical property data of the product are as follows. Melting point 78.1 - 78.3 °C 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,CDCl 3 ) 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]

Chemical Structure

[0063] Synthesis of compound 2 [ka]

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

[0065] The physical property data of the product is as follows: Melting point: 138.2-139.0℃ 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, CDCl 3 ) 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] 5.01g (33.1mmol) of 3H-benzothiazol-2-one (BT) was added to a 300mL three-neck flask, and 100mL of dry-THF and 5.45g (35.8mmol) of DBU were added under an argon stream. The system was cooled to -7°C in an ice bath containing salt, and 4.80g (34.1mmol) of benzoyl chloride (BC) in dry-THF (30mL) was added dropwise to the system, and the system was stirred for 4.5 hours while keeping the temperature below -7°C. The reaction solution was poured into 700mL of ice water and stirred for 10 minutes, after which the solid was collected by suction filtration and dried under reduced pressure. This was dissolved in 430mL of hexane, and then left to stand at room temperature for recrystallization. The precipitated solid was collected by suction filtration to obtain compound 3 as a white plate crystal (yield 3.70g, 44%).

[0069] The physical property data of the product is as follows: Melting point: 91.2-92.0℃ 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, CDCl 3 ) 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 glycidyl phenyl ether (GPE) in solvent Compound 1 (0.479 g, 2.00 mmol), glycidyl phenyl ether (GPE) (0.300 g, 2.00 mmol) and N-methylpyrrolidone (2.7 mL, 1.5 mol / L) were added to a two-neck flask, and the mixture was placed under an argon stream and heated to 150°C in an oil bath with stirring. The reaction was tracked by thin layer chromatography (TLC), and heating was stopped 5 hours after the GPE spot disappeared. The reaction solution was transferred to a sample bottle, 20 mL of water was added, and the mixture was stirred for 1 hour, followed by decantation. The resulting dark brown viscous liquid was dried under reduced pressure at room temperature to obtain a crude product of the reaction between compound 1 and GPE (crude yield 78.7%).

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

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

[0074] The physical property data of the obtained 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, CDCl 3 )δ(ppm):7.98(d,J=8.5Hz,1.00H,Hl),7.92(d,J=7.5Hz,1.99H,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 physical property data of the obtained AD-1(β) is 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, CDCl 3 )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] In addition, ESI-TOF-MS measurements were performed on the obtained AD-1(α) and AD-1(β). As a result, a peak at m / z=412.21 was observed for each sample. This is due to the sodium ion (Na + ) adduct, it was supported that the adducts obtained by the above procedure had the structures shown as AD-1(α) and AD-1(β).

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

[0080] Reaction of compound 1 with GPE under solvent-free conditions 1 H-NMR Tracking As described above, the reaction of compound 1 with GPE under solvent-free conditions afforded two adducts, AD-1(α) and AD-1(β), which were 1 The H-NMR signal was confirmed. Therefore, when the reaction temperature was set to 90°C, 100°C, or 110°C under solvent-free conditions, 1 The yields were calculated by H-NMR. 1.23 g (5.14 mmol) of compound 1 and 0.771 g (5.14 mmol) of GPE were added to a two-neck flask, and the flask was placed under a nitrogen stream. The flask was then heated to 90°C in an oil bath with stirring, and samples were taken every hour. 1 The reaction was monitored by H-NMR. After 9 hours, when it was confirmed that the GPE signal had disappeared, heating was stopped and the reaction mixture was heated to 100°C. 1 The yields of each compound were calculated based on the H-NMR signals. Using the same 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 H-NMR analysis revealed that the yield of the adduct was 70% or more at 90°C or higher, and 85% or more at 100°C or higher. The ratio of AD-1(α) to AD-1(β) was approximately 36:64 regardless of the reaction temperature.

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

[0084] Reaction of compound 3 with GPE Compound 3 (0.510 g, 2.00 mmol), GPE (0.300 g, 2.00 mmol) and N-methylpyrrolidone (2.7 mL, 1.5 mol / L) were added to a two-neck flask, and the flask was placed under an argon stream and heated to 150°C in an oil bath with a stirrer. The reaction was tracked by thin layer chromatography (TLC), and heating was stopped 22 hours after the GPE spot disappeared. The reaction solution was transferred to a sample bottle, water (20 mL) was added, and the mixture was stirred for 1 hour, followed by decantation. The resulting dark brown viscous liquid was dried under reduced pressure at room temperature to obtain a reaction product 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. From the above, it was demonstrated that the compounds of the present invention are good reactants for epoxy group-containing compounds.

Claims

1. A curable composition comprising an epoxy resin and a compound having two or more partial structures represented by the following general formula (5), and not containing a curing reaction catalyst: 【Chemistry 1】 (In the above general formula (5), the ring represented by A (ring A) is a nitrogen-containing heterocycle, and when one nitrogen atom contained in the ring is referred to as a specific nitrogen atom, the three bonds derived from ring A shown in the above general formula (5) are bonds from elements constituting ring A that are not the specific nitrogen atom, and each bond marked with * independently represents a bond to another element.)

2. The curable composition according to claim 1, wherein the compound has two or more partial structures represented by any one of the following general formulas (6) to (8): 【Chemistry 2】 (In the above general formulas (6) to (8), each bond marked with an * independently represents a bond to another element.)

3. The curable composition according to claim 1 or 2, wherein the compound has two or more partial structures represented by any one of the following general formulas (6a) to (8a): 【Chemistry 3】 (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 absence or a bond to another element.)

4. 4. The curable composition according to claim 1, which is heat latent and is cured by heating.

Images