TW202208476A - Method for producing benzoxazine compound-containing mixture - Google Patents

Abstract

To provide a method for producing a mixture containing a benzoxazine compound. The mixture has compatibility with other resins (and preferably epoxy compounds) and, when incorporated in a curable composition, can give a cured product having high heat resistance. Provided is a method for producing a mixture containing a benzoxazine compound represented by formula (1), the method including a step for subjecting p-aminophenol, an aromatic primary monoamine compound, a bisphenol compound and a formaldehyde compound to a condensation reaction. In the condensation reaction step, the ratio (OH/NH2) of phenolic hydroxyl groups derived from the p-aminophenol and the bisphenol compound and amino groups derived from the p-aminophenol and the aromatic primary monoamine compound is 1.05/1-1.15/1.

Description

Method for producing mixtures containing benzos

The present invention relates to a method for producing a mixture containing a benzodiazepine compound.

Hardening resins are used in various applications such as semiconductor sealing materials and fiber-reinforced plastics, and benzoxyl compounds are used as one of the raw materials. The benzodiazepine compound refers to a compound containing a benzodiazepine ring having a benzene skeleton and a skeleton skeleton, and its cured product (polymer) has excellent physical properties such as heat resistance, and is used as a high-performance material in various applications.

As a benzodiazepine compound, for example, Patent Document 1 discloses a benzodiazepine compound having a specific structure as a raw material for producing a cured benzodiazepine resin having high thermal conductivity, and a method for producing the same.

In addition, Patent Document 2 discloses a thermosetting resin in which reactive ends of a polybenzodiazepine resin having a benzodiazepine ring structure having a specific structure in the main chain are blocked.

Furthermore, as a method for obtaining a benzodiazepine compound, a method using p-aminophenol as a raw material is known. For example, Non-Patent Document 1 discloses a benzodiazepine compound synthesized using p-aminophenol. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2013-060407 [Patent Document 2] Japanese Patent Laid-Open No. 2012-036318 [Non-patent literature]

[Non-Patent Document 1] TAREK AGAG, TSUTOMU TAKEICHI, Journal of Polymer Science: Part A: Polymer Chemistry, 2007, vol.45, p.1878-1888

[Problems to be Solved by Invention]

According to the research of the present inventors, it can be known that when a benzodiazepine compound is obtained by using p-aminophenol as a raw material, it is difficult to control its molecular weight distribution, the high molecular weight will reduce the compatibility with other resins, and the low molecular weight will reduce the compatibility with other resins. Reduce heat resistance. Furthermore, according to the study by the present inventors, it was found that although the formation of high molecular weight compounds can be suppressed by adding aromatic primary monoamines or monophenols as end-capping agents, there are also reasons for the presence of aromatic primary monoamines and The problem of reduced heat resistance after curing of the benzophenone monomers produced by monophenols.

Therefore, an object of the present invention is to provide a benzodiazepine-containing compound which is compatible with other resins (preferably epoxy compounds), and which, when contained in a curable composition, can have a hardened product with high heat resistance A method for producing the resulting mixture.

The inventors of the present invention have made intensive studies in order to solve the above-mentioned problems, and as a result, they have found that a mixture containing a benzodiazepine compound synthesized by using a specific raw material in a specific ratio can suppress the formation of high molecular weight and low molecular weight forms. The resin (preferably an epoxy compound) has excellent compatibility and can reduce the viscosity when mixed with other resins (preferably an epoxy compound), and when the mixture is included in the curable composition, the cured product The high heat resistance is excellent, and the present invention has been completed. [Technical means to solve problems]

式(1) [式(1)中，L為碳數1～10之伸烷基、碳數7～21之伸芳烷基、氧、硫或磺醯基，Ar分別獨立為可經取代之芳基，m、n分別獨立為0以上之整數] [2]如[1]所記載之方法，其中式(1)之芳基可由1～3個取代基R₁ 取代，該取代基R₁ 分別獨立地選自由烷基、烷氧基、酯基、醯胺基、氰基及鹵素原子所組成之群。 [3]如[1]或[2]所記載之方法，其中於上述縮合反應步驟中，上述對胺基苯酚及上述芳香族一級單胺類之胺基中之上述對胺基苯酚之胺基的含有率為25～75莫耳%。 [4]如[1]至[3]中任一項所記載之方法，其中於上述縮合反應步驟中，源自上述對胺基苯酚及上述雙酚類之酚性羥基中之上述對胺基苯酚之酚性羥基的含有率為25～75莫耳%以下。 [5]如[1]至[4]中任一項所記載之方法，其中上述混合物之數量平均分子量為600～1500， 相對於上述混合物總量，式(1)中之m及n為0之苯并㗁𠯤化合物之比率為20面積%以下。 [6]如[1]至[5]中任一項所記載之方法，其中上述混合物係包含式(1)中之m及n之合計值不同之苯并㗁𠯤化合物而成。 [7]如[1]至[6]中任一項所記載之方法，其中上述混合物係包含式(1)中之m及n之合計值為1以上之苯并㗁𠯤化合物而成。 [8]如[1]至[7]中任一項所記載之方法，其中相對於上述混合物總量，式(1)中之m及n之合計值為5以上之苯并㗁𠯤化合物之比率為20面積%以上70面積%以下。 [9]如[1]至[8]中任一項所記載之方法，其中相對於上述混合物總量，式(1)中之m及n之合計值為1～4之苯并㗁𠯤化合物之比率為25面積%以上。 [10]如[1]至[9]中任一項所記載之方法，其中上述混合物之分子量分散度為1.05～2.50。 [11]一種混合物，其係藉由如[1]至[10]中任一項所記載之方法而獲得。 [12]一種硬化性組合物，其係包含如[11]所記載之混合物而成。 [13]如[12]所記載之硬化性組合物，其係進而包含硬化劑及所需之硬化促進劑而成。 [14]如[12]或[13]所記載之硬化性組合物，其進而包含環氧化合物。 [15]一種硬化物，其係使如[12]至[14]中任一項所記載之硬化性組合物硬化而成。 [發明之效果]That is, the present invention includes the following inventions. [1] A method for producing a mixture comprising the step of subjecting p-aminophenol, aromatic primary monoamines, bisphenols and formaldehyde to a condensation reaction, the mixture comprising the following formula (1) The benzodiazepine compound represented by the above-mentioned condensation reaction step is composed of the phenolic hydroxyl group derived from the above-mentioned p-aminophenol and the above-mentioned bisphenols, and the above-mentioned p-aminophenol and the above-mentioned aromatic group. The ratio of the amine groups of the primary monoamines (OH/NH ₂ ) is 1.05/1 to 1.15/1. [hua 1]

Formula (1) [In formula (1), L is an alkylene group having 1 to 10 carbon atoms, an aralkylene group having 7 to 21 carbon atoms, oxygen, sulfur or sulfonyl group, and Ar is independently substituted. Aryl group, m and n are each independently an integer of 0 or more] [2] The method according to [1], wherein the aryl group of the formula (1) may be substituted by 1 to 3 substituents R ₁ , and the substituent R ₁ They are independently selected from the group consisting of alkyl group, alkoxy group, ester group, amide group, cyano group and halogen atom. [3] The method according to [1] or [2], wherein in the condensation reaction step, the amine group of the p-aminophenol among the amine groups of the p-aminophenol and the aromatic primary monoamines The content of 25 to 75 mol%. [4] The method according to any one of [1] to [3], wherein in the condensation reaction step, the p-amino group derived from the p-aminophenol and the phenolic hydroxyl group of the bisphenols The content rate of the phenolic hydroxyl group of phenol is 25 to 75 mol % or less. [5] The method according to any one of [1] to [4], wherein the number average molecular weight of the mixture is 600 to 1500, and m and n in the formula (1) are 0 with respect to the total amount of the mixture The ratio of the benzoic compound is 20 area % or less. [6] The method according to any one of [1] to [5], wherein the mixture comprises a benzodiazepine compound having different total values of m and n in formula (1). [7] The method according to any one of [1] to [6], wherein the mixture contains a benzodiazepine compound whose total value of m and n in formula (1) is 1 or more. [8] The method according to any one of [1] to [7], wherein the sum of m and n in the formula (1) is 5 or more of the benzodiazepine compound with respect to the total amount of the mixture. The ratio is 20 area % or more and 70 area % or less. [9] The method according to any one of [1] to [8], wherein the total value of m and n in the formula (1) is 1 to 4 with respect to the total amount of the mixture. The ratio is 25% by area or more. [10] The method according to any one of [1] to [9], wherein the molecular weight dispersion of the mixture is 1.05 to 2.50. [11] A mixture obtained by the method as described in any one of [1] to [10]. [12] A curable composition comprising the mixture according to [11]. [13] The curable composition according to [12], further comprising a curing agent and a desired curing accelerator. [14] The curable composition according to [12] or [13], further comprising an epoxy compound. [15] A cured product obtained by curing the curable composition according to any one of [12] to [14]. [Effect of invention]

According to the present invention, it is possible to provide a product comprising the benzodiazepine compound represented by the formula (1), which is compatible with other resins (preferably epoxy compounds) and can produce a cured product with high heat resistance. A mixture (hereinafter also referred to as a mixture containing a benzodiazepine compound of formula (1)). The mixture containing the benzodiazepine compound of the present invention is advantageous in that it can reduce the viscosity of the preparation (ie, the curable composition) of the mixture and other resins (preferably epoxy compounds). Further, according to the present invention, a curable composition for obtaining a cured product having high heat resistance can be provided.

式(1) [式(1)中，L為碳數1～10之伸烷基、碳數7～21之伸芳烷基、氧、硫或磺醯基，Ar分別獨立為可經取代之芳基，m、n分別獨立為0以上之整數]。 A mixture containing a benzodiazepine compound According to one embodiment of the present invention, a mixture containing a benzodiazepine compound produced by the method for producing a mixture containing a benzodiazepine compound of the present invention comprises the following formula (1 ) represented by the benzo 㗁𠯤 compound. In addition, the above-mentioned mixture containing a benzodiazepine compound may be contained in the curable composition. [hua 2]

Formula (1) [In formula (1), L is an alkylene group having 1 to 10 carbon atoms, an aralkylene group having 7 to 21 carbon atoms, oxygen, sulfur or sulfonyl group, and Ar is independently substituted. In the aryl group, m and n are each independently an integer of 0 or more].

In the above formula (1), L is, for example, an alkylene group having 1 to 10 carbon atoms, an aralkylene group having 7 to 21 carbon atoms, oxygen, sulfur or sulfonyl group, preferably an alkylene group having 1 to 3 carbon atoms. Alkyl, oxygen, sulfur or sulfonyl.

The alkylene group having 1 to 10 carbon atoms represented by L in the above formula (1) is preferably an alkylene group having 1 to 6 carbon atoms, more preferably an alkylene group having 1 to 3 carbon atoms. Specific examples of the above alkylene group include methylene group, ethylidene group, propylidene group, isopropylidene group, tetramethylene group, hexamethylene group and the like, and methylene group and isopropylidene group are preferred. base.

The aralkylene group having 7 to 21 carbon atoms represented by L in the above formula (1) is preferably an arylene group having 7 to 15 carbon atoms, more preferably an arylene group having 7 to 10 carbon atoms. Specific examples of the above-mentioned arylene group include phenylmethylene, diphenylmethylene, 1-phenylethylidene, naphthylmethylene, and the like, preferably phenylmethylene, diphenylmethylene, and the like. Phenylmethylene.

The number of carbon atoms of the aryl group represented by Ar in the above formula (1) is not particularly limited, and examples thereof include 6 to 14, preferably 6 to 10 (except when substituted). Specific examples of the aryl group include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a phenanthryl group, a biphenyl group, and the like, and a phenyl group, a 1-naphthyl group, and a 2-naphthyl group are preferred. Furthermore, the aryl groups represented by Ar in the above formula (1) may be the same or different. In addition, when m and n are 0, Ar is directly bonded to the nitrogen atom of the benzodiazepine ring to which L is bonded.

The aryl group represented by Ar in the above formula (1) may be substituted. Specifically, the above-mentioned aryl group may be substituted by 1 to 3 substituents R ₁ . The substituent R ₁ may, for example, be a group independently selected from the group consisting of an alkyl group, an alkoxy group, an ester group, an amide group, a cyano group and a halogen atom, preferably an alkyl group and an alkoxy group.

The number of carbon atoms in the above-mentioned alkyl group is not particularly limited, but 1-10 may be mentioned, preferably 1-8, and more preferably 1-6. Specific examples of the above-mentioned alkyl group include methyl, ethyl, n-propyl, n-butyl, octyl, dodecyl, isopropyl, isobutyl, sec-butyl, and tert-butyl. , n-pentyl, n-hexyl, etc., preferably methyl, ethyl, n-propyl, n-hexyl.

Although the carbon number of the alkyl chain of the said alkoxy group is not specifically limited, 1-10 are mentioned, Preferably it is 1-6, More preferably, it is 1-3. As a specific example of the said alkoxy group, a methoxy group, an ethoxy group, a propoxy group, etc. are mentioned, Preferably they are a methoxy group and an ethoxy group.

As a specific example of the said ester group, an acyloxy group, an orthoester group, an alkoxycarbonyl group, etc. are mentioned. Here, as a preferable acyloxy group, an acetoxy group, a propionyloxy group, and a pivaloyloxy group can be exemplified, a preferable orthoester group can be exemplified by a trimethoxymethyl group, and a preferable alkane group can be exemplified The oxycarbonyl group may, for example, be a methoxycarbonyl group. As an ester group, an acetoxy group and a propionyloxy group are preferable.

As a specific example of the above-mentioned amide group, an acetamide group, a propionamide group, a dimethyl amide group, a diethyl amide group, etc. may be mentioned, and an acetamide group and a dimethyl amide group are preferred. base.

As a specific example of the said halogen atom, a chlorine atom, a fluorine atom, a bromine atom, an iodine atom etc. are mentioned, Preferably it is a chlorine atom, a fluorine atom, and a bromine atom.

Specific examples of the substituted aryl group include o-tolyl, m-tolyl, p-tolyl, ethylphenyl, xylyl (dimethylphenyl), trimethylphenyl, o-chlorobenzene Base, m-chlorophenyl, p-chlorophenyl, chlorotolyl, dichlorophenyl, trichlorophenyl, o-fluorophenyl, m-fluorophenyl, p-fluorophenyl, o-bromophenyl, m-bromophenyl , p-bromophenyl, fluorochlorophenyl, methoxyphenyl, ethoxyphenyl, cyanophenyl, methoxymethylphenyl, trifluoromethylphenyl, acetamidophenyl, acetoxyphenyl phenyl, methyl naphthyl, ethyl naphthyl, dimethyl naphthyl, etc., preferably o-tolyl, m-tolyl, p-tolyl, methoxyphenyl, and xylyl.

According to a preferred embodiment of the present invention, in the benzodiazepine compound represented by the formula (1), as L in the above formula (1), an alkylene group having 1 to 10 carbon atoms, oxygen, etc. can be exemplified. Preferred are methylene, isopropylidene, and oxygen, and Ar in the above formula (1) is phenyl.

According to a preferred embodiment of the present invention, specific examples of the benzodiazepine compound represented by the formula (1) include the following benzodiazepine compounds. [hua 3]

In the above formula (1), m and n are not particularly limited as long as they are independently 0 or more, but the integers 1 to 10 are preferred, and the integers 1 to 8 are more preferred.

According to a preferred embodiment of the present invention, the mixture containing the benzodiazepine compound of the formula (1) contains the benzodiazepine compound in which the total value of m and n in the formula (1) is different.

According to a preferred embodiment of the present invention, the mixture containing the benzodiazepine compound of the formula (1) contains the benzodiazepine compound whose total value of m and n in the formula (1) is 1 or more. As the mixture containing the above-mentioned benzodiazepine compound, it is preferable to contain each benzodiazepine compound whose total value of m and n in formula (1) is 0, 1, 2, 3, 4, and 5, respectively.

In addition, based on the number of benzodiazepine rings present in the compound, the above-mentioned benzodiazepine compound is also referred to as an x-polymer (here, x is an integer of 1 or more). For example, in the formula (1), the compound of m+n=0 is also called a dimer, and the compound of m+n=1 is also called a trimer. In addition, a monomer means the compound which has one benzodiazepine ring.

According to a preferred embodiment of the present invention, in the mixture containing the benzodiazepine compound of the formula (1), with respect to the total amount of the mixture, m and n in the formula (1) are 0. The ratio of polymer) is 20 area % or less, preferably 10 area % or less, more preferably 3 area % or less. By setting the ratio of the benzodiazepine compound in which m and n are 0 in the formula (1) to 20 area % or less, the heat resistance of the cured product can be further improved.

The content ratio of the x-polymer to the total amount of the mixture (ie, the content ratio of each of the monomers, dimers, trimers, etc.) (area %) can be measured by gel permeation chromatography (GPC). It was calculated from the GPC calibration curve obtained using the benzodiazepine compound described in the examples as a molecular weight conversion standard material. Such measurement and conversion can be easily performed by using a commercially available GPC apparatus (eg, manufactured by Tosoh Corporation) and columns (eg, TSKgel SuperHZ3000, TSKgel SuperHZ2000, and TSKgel SuperHZ1000 (manufactured by Tosoh Corporation, respectively)). conduct. The above measurement and conversion can be performed under the following conditions. Device: HLC-8420GPC (Tosoh Corporation); Column: TSKgel SuperHZ3000+TSKgel SuperHZ2000+TSKgel SuperHZ1000×2 (Tosoh Corporation, respectively); Elution solution: Tetrahydrofuran (THF); Flow rate: 0.35 ml/min; Measurement temperature : 40° C.; Injection volume: 3 μL; Detector: UV (Ultraviolet) detector; Detection wavelength: 254 nm;

According to a preferred embodiment of the present invention, in the mixture containing the benzoic compound of the formula (1), the benzoic compound in which m and n in the formula (1) are 5 or more relative to the total amount of the mixture ( 7 or more area %) is 15 area % or more and 70 area % or less, preferably 20 area % or more and 60 area % or less, more preferably 25 area % or more and 50 area % or less, and still more preferably 25 area % or more. 40 Area % or less. Compatibility with epoxy compounds can be further improved by setting the ratio of the benzodiazepine compound in which m and n are 5 or more in formula (1) to 15 area % or more and 70 area % or less.

According to a preferred embodiment of the present invention, in the mixture containing the benzodiazepine compound of the formula (1), the total value of m and n in the formula (1) is 1 to 4 benzos with respect to the total amount of the mixture. The ratio of the compound (tri- to hexamer) is 25 area % or more, preferably 30 area % or more, more preferably 40 area % or more, and still more preferably 50 area % or more. The upper limit of the ratio of the benzodiazepine compound in which the sum of m and n in formula (1) is 1 to 4 is, for example, 95 area % or less, preferably 80 area % or less, and more preferably 70 area % or less. . By setting the ratio of the benzodiazepine compound in which m and n in the formula (1) are 1 to 4 to 25 area % or more, the heat resistance of the cured product can be further improved.

式(2) [式(2)中，Ar如式(1)中所定義]。 [化5]

式(3)According to a preferred embodiment of the present invention, in the mixture containing the benzodiazepine compound of the formula (1), the ratio of the compound (monomer) having one benzodiazepine ring with respect to the total amount of the mixture is 5 areas % or less, preferably 3 area % or less, more preferably 1 area % or less, still more preferably 0.1 area % or less. The lower limit is not particularly limited, but is preferably 0 area % or more. By setting the ratio of the compound having one benzodiazepine ring to the total amount of the mixture to 5 area % or less, the heat resistance of the cured product can be further improved. As the molecular weight of the compound having one benzodiazepine ring, 210 to 250 may, for example, be mentioned. The compound is preferably at least one selected from the group consisting of the compound of the following formula (2) and the compound of the formula (3), more preferably the compound of the formula (2) or the compound of the formula (3) in which Ar is a phenyl group . [hua 4]

Formula (2) [In Formula (2), Ar is as defined in Formula (1)]. [hua 5]

Formula (3)

According to an embodiment of the present invention, the number-average molecular weight (Mn) of the mixture containing the benzodiazepine compound of formula (1) is not particularly limited, and may be 600-1500, preferably 650-1200, more preferably 600-1500. 700-1000, more preferably 700-800. The number-average molecular weight of the mixture containing the benzodiazepine compound of formula (1) can be determined by gel permeation chromatography (GPC) as described above.

According to an embodiment of the present invention, the molecular weight dispersion of the mixture containing the benzodiazepine compound of the formula (1) is not particularly limited, and may be 1.05-2.50, preferably 1.08-2.00, more preferably 1.10-1.50 , and more preferably 1.13 to 1.20. The molecular weight dispersion is the weight average molecular weight (Mw)/number average molecular weight (Mn). Here, the weight average molecular weight (Mw) of the mixture containing the benzodiazepine compound of the formula (1) can be measured by the above-mentioned gel permeation chromatography (GPC).

According to one embodiment of the present invention, the mixture containing the benzodiazepine compound represented by the above formula (1) is obtained by condensing p-aminophenol, aromatic primary monoamines, bisphenols, and formaldehydes mixture of compounds. Therefore, the above-mentioned mixture may be a reaction product obtained by a condensation reaction.

According to another embodiment of the present invention, the mixture containing the benzodiazepine compound represented by the above formula (1) can be prepared by using p-aminophenol, aromatic primary monoamines, bisphenols and formaldehydes. A mixture of compounds obtained by condensation (for example, reaction products) is obtained by performing separation washing, recrystallization, column purification, and the like.

(Characteristics of Mixtures Containing the Benzopic Compounds of Formula (1)) According to one embodiment of the present invention, the mixture containing the benzodiazepine compound of formula (1) exhibits high compatibility with other resins (preferably epoxy compounds). Compatibility can be confirmed by mixing the mixture containing the benzodiazepine compound of formula (1) and other resins under heating of the same mass, respectively. The mixture containing the benzodiazepine compound of formula (1) is preferably compatible with epoxy compounds at temperatures below 80°C.

According to one embodiment of the present invention, other resins are not particularly limited, and examples thereof include epoxy compounds, bismaleimide resins, cyanate resins, isocyanate resins, and the like, and epoxy compounds, bismaleimide resins, and the like are preferred. Lysimide resin.

The method for producing a mixture containing a benzodiazepine compound The mixture comprising the benzodiazepine compound represented by the formula (1) can be prepared by including p-aminophenol, aromatic primary monoamines, bisphenols and formaldehyde It is manufactured by a method of performing a condensation reaction step.

According to an embodiment of the present invention, in the condensation reaction step, the phenolic hydroxyl group derived from the above-mentioned p-aminophenol and the above-mentioned bisphenols, and the amine group derived from the above-mentioned p-aminophenol and the above-mentioned aromatic primary monoamines The ratio (OH/NH ₂ ) is not particularly limited, but is, for example, 1.05/1 to 1.15/1, preferably 1.07/1 to 1.13/1, and more preferably 1.09/1 to 1.11/1. From the viewpoint of the generation of side reactants or the difficulty of molecular weight control, the molar ratio of the starting material usually needs to match the stoichiometric ratio. Specifically, in the synthesis of benzodiazepines, since phenols, amines, and formaldehyde react in a molar ratio of 1:1:2 to form a benzodiazepine ring, the phenols and amines are The compounding ratio is carried out with the molar ratio of hydroxyl group and amine group being 1:1. Therefore, it is an unexpected fact that by changing the molar ratio of the raw materials in the above-mentioned manner, it is possible to obtain a mixture containing benzodiazepine, which is excellent in compatibility with other resins and can reduce the viscosity when mixed with other resins. A mixture; further, when the mixture is contained in a curable composition, the cured product is excellent in high heat resistance. In addition, in the above-mentioned mixture containing a benzodiazepine compound, the fact that the formation of a low molecular weight body or a high molecular weight body is suppressed is also an unexpected fact.

According to an embodiment of the present invention, in the condensation reaction step, the content of the phenolic hydroxyl group of the p-aminophenol in the phenolic hydroxyl group derived from the p-aminophenol and the bisphenol is not particularly limited, and is, for example, 25-75 mol %, preferably 30-65 mol %, more preferably 35-55 mol %, and still more preferably 40-50 mol %.

According to an embodiment of the present invention, in the condensation reaction step, the content of the amine group derived from the p-aminophenol in the amine group derived from the p-aminophenol and the above-mentioned aromatic primary monoamine is not particularly limited, For example, it is 25-75 mol %, preferably 30-70 mol %, more preferably 35-60 mol %, and still more preferably 40-55 mol %.

(Aromatic Primary Monoamines) The aromatic primary monoamines are not particularly limited as long as they are aromatic compounds having one primary amine group in one molecule, and Ar-NH ₂ (wherein , Ar is an aryl group substituted by a substituent R ₁ independently selected from the group consisting of alkyl, alkoxy, ester, amido, cyano and halogen atoms. Specifically, the above-mentioned aromatic primary monoamines can be exemplified by aniline, o, m, p-toluidine, o, m, p-ethylaniline, xylidine, 2,4,6-tritoluidine, o, m, p Chloroaniline, chlorotoluidine, dichloroaniline, trichloroaniline, o, m, p-fluoroaniline, o, m, p-bromoaniline, fluorochloroaniline, methoxyaniline, ethoxyaniline, aminobenzonitrile, 2 -Methoxy-5-methylaniline, trifluoromethylaniline, p-aminoacetaniline, naphthylamine, etc., preferably aniline, o-, m-, p-toluidine, and methoxyaniline. These aromatic primary monoamines may be used alone, or two or more of them may be used. In addition, o-aminophenol, m-aminophenol, and p-aminophenol are not included in the aromatic primary monoamines.

The usage-amount of aromatic primary monoamines is not particularly limited, but is preferably 0.1-2 mol, more preferably 0.2-1.5 mol, relative to 1 mol of p-aminophenol.

(Bisphenols) The bisphenols are not particularly limited as long as they are compounds having two phenolic hydroxyl groups, and examples thereof include bisphenol A, bisphenol F, 4,4'-bisphenol F, bisphenol S, 4,4 '-dihydroxydiphenyl ether, bis(4-hydroxyphenyl) sulfide, bis(4-hydroxyphenyl) sulfide, etc., preferably bisphenol F, 4,4'-bisphenol F, bisphenol A, 4,4'-Dihydroxydiphenyl ether. These bisphenols may be used alone, or two or more of them may be used.

The amount of bisphenol used is not particularly limited, but is preferably 0.05 to 2 mol, more preferably 0.1 to 0.75 mol, relative to 1 mol of p-aminophenol.

(Formaldehyde) Although it does not specifically limit as formaldehyde, For example, formaldehyde, paraformaldehyde, 1,3,5- triacetane, tetraformaldehyde, formalin etc. are mentioned, Preferably they are formaldehyde, paraformaldehyde, and formalin. When these formaldehydes are used, they may be used alone, or two or more of them may be used.

The amount of formaldehyde used is not particularly limited, but is preferably 1 to 3 mol, more preferably 1.5 to 2.5 mol, relative to 1 mol of the total of p-aminophenol and aromatic primary monoamines. Here, the molar amount in the case of using paraformaldehyde as formaldehyde is the molar amount converted to formaldehyde.

(Reaction conditions) The condensation reaction can usually be carried out in the presence of a solvent. The solvent can be refluxed in the reaction. Examples of the solvent include alcohol-based solvents such as methanol, ethanol, isopropanol, n-butanol, n-hexanol, and cyclohexanol; ether-based solvents such as tetrahydrofuran, diethane, and dimethoxyethane; toluene, dimethoxyethane, and the like. Aliphatic hydrocarbon solvents such as toluene and benzene; aprotic polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone and dimethylsulfoxide ; nitrile solvents such as acetonitrile and benzonitrile; halogenated hydrocarbon solvents such as dichloromethane, chloroform, 1,2-dichloroethane, carbon tetrachloride and chlorobenzene; water; etc.; preferably diethane, chloroform , Toluene. As the solvent, a plurality of solvents can be mixed and used.

The reaction can be carried out under normal pressure conditions, under pressure conditions, or under reduced pressure conditions. Moreover, you may carry out in inert gas atmosphere, such as nitrogen and argon.

The reaction temperature is usually 30°C to 120°C, preferably 60°C to 110°C.

The reaction time is not particularly limited, but is, for example, 3 hours to 100 hours.

According to an embodiment of the present invention, when the mixture containing the benzodiazepine compound represented by the formula (1) is produced, when the purity of the mixture obtained by the above production method is low, it is preferably Purification is carried out by concentration, separation washing, filtration, distillation, recrystallization, reprecipitation, column purification, or a combination thereof.

The structure of the benzodiazepine compound represented by the formula (1) can be identified by ¹ H-NMR, infrared absorption spectrum, or the like.

According to a preferred embodiment of the present invention, aniline is used as the aromatic primary monoamine, bisphenol F or 4,4'-bisphenol F is used as the bisphenol, and formaldehyde, paraformaldehyde or formalin is used as the aldehyde In this case, a compound in which L is a methylene group and Ar is a phenyl group in the formula (1) can be obtained as the benzodiazepine compound represented by the formula (1).

According to one embodiment of the present invention, a curable composition is characterized in that it is a curable composition containing a mixture containing the benzodiazepine compound represented by the above formula (1). become.

In the above curable composition, from the viewpoint of effectively imparting heat resistance by the cured product, other necessary components may be contained in combination with a mixture containing the benzodiazepine compound represented by the above formula (1). Ingredients (eg hardeners, epoxy compounds, hardening accelerators, etc.).

Hereinafter, each component which can be contained in a curable composition is demonstrated in detail.

(Mixture containing the benzodiazepine compound represented by the formula (1)) The mixture containing the benzodiazepine compound represented by the formula (1) is as described above.

According to an embodiment of the present invention, the content of the mixture containing the benzodiazepine compound of formula (1) in the curable composition is preferably 5 parts by mass relative to the total amount of 100 parts by mass of the curable composition. The range of to 99 parts by mass is more preferably the range of 10 to 80 parts by mass, still more preferably the range of 30 to 60 parts by mass. By including the mixture containing the benzodiazepine compound of the formula (1) within this range, a cured product with more excellent heat resistance can be obtained.

(hardener) According to an embodiment of the present invention, as the curing agent that can be included in the curable composition, acid anhydride-based compounds, anionic compounds (for example, amine-based compounds, phenol-based compounds, and latent curing agents), etc., are exemplified, and preferably Phenolic compounds.

Examples of the acid anhydride-based compound contained in the curable composition of the present invention include hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, and methyltetrahydrophthalic anhydride. Phthalic anhydride, endomethylene tetrahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, methylbutenyl tetrahydrophthalic anhydride, hydrogenated methyl tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride Phthalic anhydride, cyclohexanetricarboxylic anhydride, methylcyclohexene dicarboxylic anhydride, methylcyclohexanetetracarboxylic dianhydride, maleic anhydride, phthalic anhydride, succinic anhydride, dodecene succinic anhydride, octenyl succinic anhydride, pyromellitic dianhydride, trimellitic anhydride, alkyl styrene-maleic anhydride copolymer, chloroplastic anhydride, polyazelaic anhydride, benzophenone tetracarboxyl Acid dianhydride, ethylene glycol bis-anhydro trimellitate, tritrimellitic acid glyceride, glycerol bis (anhydro trimellitate) monoacetate, benzophenone tetracarboxylic acid, polyadipic anhydride , polysebacic anhydride, poly(ethyl octadecanedioic acid) anhydride, poly(phenylhexadecanedioic acid) anhydride, chloro bridge acid anhydride, nor alkane-2,3-dicarboxylic acid anhydride, etc.

As the amine compound, imidazoles (2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 1-benzyl-2-phenylimidazole, 2-methylimidazole, 2- -Phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, 2,4-diamino-6-[2-methylimidazolyl-(1)]ethyl Symmetrical tris, 2-phenylimidazoline, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole and other imidazoles), polyoxyethylene diamine, polyoxypropylene diamine, polyoxyethylene diamine Oxybutene diamine, polyoxypentene diamine, polyoxyethylene triamine, polyoxypropylene triamine, polyoxybutene triamine, polyoxypentene triamine, diethylenetriamine, triethylenetriamine Tetraamine, Tetrakenylpentamine, m-xylylenediamine, trimethylhexamethylenediamine, 2-methylpentanediamine, diethylaminopropylamine, isophoronediamine, 1,3 -Bisaminomethylcyclohexane, bis(4-aminocyclohexyl)methane, noralkanediamine, 1,2-diaminocyclohexane, diaminodiphenylmethane, m-phenylenediamine, Diaminodiphenyl, N-aminoethylpiperazine, etc.

The phenolic compound may, for example, be phenol, pyrogallol, or resorcinol. As the bisphenol, any compound having two phenolic hydroxyl groups is not particularly limited. For example, bisphenol A, Bisphenol F, Bisphenol C, Bisphenol S, Bisphenol Z, 4,4'-dihydroxydiphenyl ether, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfoxide, as phenolic The varnishes include xylylene skeleton-containing phenolic novolak resins, dicyclopentadiene skeleton-containing phenolic novolak resins, biphenyl skeleton-containing phenolic novolak resins, and phenolic skeleton-containing phenolic novolak resins Novolak resin, phenolic novolak resin containing terpene skeleton, bisphenol A novolak, bisphenol F novolak, bisphenol S novolak, bisphenol AP novolak, bisphenol C novolak, bisphenol E novolak , bisphenol Z novolak, biphenol novolak, tetramethyl bisphenol A novolak, dimethyl bisphenol A novolak, tetramethyl bisphenol F novolak, dimethyl bisphenol F novolak, tetramethyl bisphenol F novolak base bisphenol S novolac, dimethyl bisphenol S novolac, tetramethyl-4,4'-biphenol novolac, trihydroxyphenylmethane novolac, resorcinol novolac, hydroquinone novolac Novolac, pyrogallol novolac, diisopropylidene novolac, 1,1-di-4-hydroxyphenyl novolac, phenolic polybutadiene novolac, phenolic novolac, cresol novolac Varnish, ethylphenol novolak, butylphenol novolak, octylphenol novolak, naphthol novolak, etc.

As a latent hardener, a thermal cation initiator, dicyandiamide, dihydrazine adipic acid, dihydrazine sebacate, dihydrazine dodecanedioate, dihydrazine isophthalate, , Ketimine, imidazole compound, dihydrazide compound, amine adduct system hardener, etc.

The curable composition of this invention may contain 1 type or 2 or more types of the above-mentioned hardeners.

From the viewpoint of the heat resistance of the cured product, the content of the curing agent in the curable composition is preferably in the range of 1 to 50 parts by mass with respect to 100 parts by mass of the total amount of the curable composition, and more The range of 3-30 mass parts is preferable.

(hardening accelerator) According to one embodiment of the present invention, as the curing accelerator contained in the curable composition, for example, triphenylphosphine, triphenylbenzylphosphonium tetraphenyl borate, tetrabutylphosphonium diethyl Dithiophosphate, tetraphenylphosphonium bromide, tetrabutylphosphonium acetate, tetra-n-butylphosphonium bromide, tetra-n-butylphosphonium benzotriazole, tetra-n-butylphosphonium tetrafluoroborate, tetra-n-butylphosphonium Butylphosphonium tetraphenyl borate, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, ethyltriphenylphosphonium iodide, ethyltriphenylphosphonium acetate, methyltributylphosphonium Diethylphosphonate, n-butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium tetraphenylborate and other phosphines and their quaternary salts; 2-ethyl-4 -methylimidazole, 1,2-dimethylimidazole, 1-benzyl-2-phenylimidazole, 2-methylimidazole, 2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl yl-4-methylimidazole, 2,4-diamino-6-[2-methylimidazolyl-(1)]ethyl symmetric tris𠯤, 2-phenylimidazoline, 2,3-dihydro- Imidazoles such as 1H-pyrrolo[1,2-a]benzimidazole; tertiary amines such as tris(dimethylaminomethyl)phenol, dimethylbenzylamine, tetrabutylammonium bromide and their quaternary salts ; 1,8-diazabicyclo(5,4,0)undecene-7, 1,5-diazabicyclo(4,3,0)nonene-5 and other super basic organic compounds ;Organic carboxylic acid metal salts such as zinc octoate, zinc laurate, zinc stearate, tin octoate, etc.; Metal-organic chelate compounds such as compounds; tetra-n-butyl perionium O, O-diethyldithiophosphate, etc. Here, as a hardening accelerator, as long as it has the acceleration|stimulation effect of hardening reaction, the same compound as a hardening agent may be sufficient as it, and a different compound may be sufficient as it.

The curable composition of this invention may contain 1 type or 2 or more types of the above-mentioned hardening accelerator.

From the viewpoint of the heat resistance of the cured product, the content of the curing accelerator in the curable composition of the present invention is preferably 0.01 to 10 parts by mass relative to 100 parts by mass of the total amount of the curable composition. The range of 0.1-6 mass parts is more preferable.

(epoxy compound) According to one embodiment of the present invention, the curable composition may contain an epoxy compound according to the application. Examples of the epoxy compound include glycidyl ether type epoxides, glycidyl ester type epoxides, glycidyl amine type epoxides, alicyclic epoxides, and the like, and alicyclic epoxides are preferred. matter.

Examples of glycidyl ether-type epoxides include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, tetramethyl biphenol diglycidyl ether, and hydrogenated bisphenol. A diglycidyl ether, brominated bisphenol A diglycidyl ether and other glycidyl ethers of diphenols; dihydroxynaphthyl cresol triglycidyl ether, tris(hydroxyphenyl)methane triglycidyl ether, tetrakis(hydroxybenzene) base) ethane tetraglycidyl ether, binaphthol triglycidyl ether, phenolic novolac glycidyl ether, cresol novolac glycidyl ether, phenolic novolac glycidyl ether containing xylylene skeleton, containing Dicyclopentadiene skeleton phenolic novolak glycidyl ether, phenolic novolak glycidyl ether containing biphenyl skeleton, phenolic novolak glycidyl ether containing terpene skeleton, bisphenol A novolac glycidyl ether, Bisphenol F novolac glycidyl ether, bisphenol S novolac glycidyl ether, bisphenol AP novolac glycidyl ether, bisphenol C novolac glycidyl ether, bisphenol E novolac glycidyl ether, bisphenol Z novolac glycidyl ether Glycidyl ether, biphenol novolac glycidyl ether, tetramethyl bisphenol A novolac glycidyl ether, dimethyl bisphenol A novolac glycidyl ether, tetramethyl bisphenol F novolac glycidyl ether, dimethyl base bisphenol F novolac glycidyl ether, tetramethylbisphenol S novolac glycidyl ether, dimethylbisphenol S novolac glycidyl ether, tetramethyl-4,4'-biphenol novolac glycidyl ether , trihydroxyphenylmethane novolac glycidyl ether, resorcinol novolac glycidyl ether, hydroquinone novolac glycidyl ether, pyrogallol novolac glycidyl ether, diisopropylidene novolac glycidyl ether Glyceryl ether, 1,1-di-4-hydroxyphenyl novolac glycidyl ether, phenolated polybutadiene novolac glycidyl ether, ethylphenol novolac glycidyl ether, butylphenol novolac glycidyl ether , glycidyl ether of polyphenols such as octylphenol novolac glycidyl ether, naphthol novolac glycidyl ether, hydrogenated phenol novolak glycidyl ether, etc.; ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1, 4-Butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, cyclohexane dimethylol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, etc. Glycidyl ethers of dihydric alcohols; glycidyl ethers of polyhydric alcohols such as trimethylolpropane triglycidyl ether, glycerol triglycidyl ether, pentaerythritol tetraglycidyl ether, sorbitol hexaglycidyl ether, polyglycerol polyglycidyl ether, etc. ether; triglycidyl isocyanurate, etc.

As glycidyl ester type epoxide, glycidyl methacrylate, diglycidyl phthalate, diglycidyl isophthalate, diglycidyl terephthalate, cyclohexane may, for example, be mentioned. Glycidyl esters of carboxylic acids such as diglycidyl dicarboxylate and triglycidyl 1,2,4-benzenetricarboxylic acid, or glycidyl ester type polyepoxides, and the like.

As the glycidylamine type epoxide, N,N-diglycidylaniline, N,N-diglycidyltoluidine, N,N,N',N'-tetraglycidyldiamine may, for example, be mentioned. Diphenylmethane, N,N,N',N'-tetraglycidyldiaminodiphenylmethane, N,N,N',N'-tetraglycidyldiethyldiphenylmethane, etc. Glyceryl aromatic amines; bis(N,N-diglycidylaminocyclohexyl)methane (N,N,N',N'-tetraglycidyldiaminodiphenylmethane hydride), N, N,N',N'-tetraglycidyl-1,3-(bisaminomethyl)cyclohexane (N,N,N',N'-tetraglycidylxylylenediamine hydride) , triglycidyl melamine, triglycidyl-p-aminophenol, N-glycidyl-4-glycidyloxypyrrolidone and other glycidyl heterocyclic amines, etc.

Examples of the alicyclic epoxide include vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, tricyclopentadiene dioxide, bis(2,3-epoxycyclopentadiene) ) ether, ethylene glycol diepoxydicyclopentyl ether, 3',4'-epoxy-6'-methylcyclohexanecarboxylic acid 3,4-epoxy-6-methylcyclohexylmethyl ester, 3,4-Epoxycyclohexanecarboxylic acid 3,4-epoxycyclohexylmethyl ester, 3,4-epoxy-1-methylhexanecarboxylic acid 3,4-epoxy-1-methylcyclohexyl Esters, 3,4-epoxy-3-methylhexanecarboxylic acid 3,4-epoxy-3-methylcyclohexylmethyl ester, 3,4-epoxy-5-methylcyclohexanecarboxylic acid 3 , 4-epoxy-5-methylcyclohexyl methyl ester, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-m-dioxane, Methylenebis(3,4-epoxycyclohexane), (3,3',4,4'-diepoxy)bicyclohexane, 2,2-bis(hydroxymethyl)-1- 1,2-epoxy-(2-oxiranyl)cyclohexane adduct of butanol, tetrahydroindene diepoxide, etc., preferably 3,4-epoxycyclohexanecarboxylic acid 3 ',4'-Epoxycyclohexylmethyl ester.

The curable composition of the present invention may contain one or two or more of the above-mentioned epoxy compounds.

The content of the epoxy compound is preferably in the range of 10 to 90 parts by mass, more preferably 30 to 70 parts by mass with respect to 100 parts by mass of the total amount of the curable composition from the viewpoint of the heat resistance of the cured product range.

(Solvent/Other) According to one embodiment of the present invention, the curable composition may further contain a solvent. Examples of the solvent include halogen-based solvents such as acetone, methyl ethyl ketone, ethyl acetate, toluene, ethanol, chloroform, and dichloromethane; amide-based solvents.

According to an embodiment of the present invention, the curable composition may contain various additives within a range not impairing its characteristics. Examples of additives include fillers (fillers), silane coupling agents, mold release agents, colorants, flame retardants, antioxidants, light stabilizers and plasticizers, defoaming agents, light stabilizers, pigments or Colorants such as dyes, plasticizers, pH adjusters, coloration inhibitors, matting agents, deodorants, weathering agents, antistatic agents, line friction reducers, luster agents, ion exchangers, etc.

(Characteristics of curable composition) The viscosity of the curable composition of the present invention can be evaluated based on the viscosity of the curable composition before curing.

The viscosity of the curable composition at 30° C. is not particularly limited, but may, for example, be 100 Pa·s or less, preferably 50 Pa·s or less, and more preferably 30 Pa·s or less. The lower limit is not particularly limited, but is preferably 0.1 Pa·s or more. Viscosity can be measured by a rheometer. Such measurement can be performed by the parallel plate method using a commercially available rheometer (for example, manufactured by TA Instruments).

According to an embodiment of the present invention, a curable composition comprising a mixture containing the benzodiazepine compound of formula (1) and other resins (preferably epoxy compounds) exhibits a very low Viscosity is therefore advantageous in terms of excellent formability and fluidity. In particular, if the viscosity of the mixture containing the benzodiazepine compound of the formula (1) is low when mixed with other resins (preferably epoxy compounds), the curable composition can contain more fillers, etc. It is advantageous in that the obtained curable composition and its cured product can be easily modified or highly functionalized.

Manufacturing method of curable composition According to an embodiment of the present invention, in the manufacture of curable composition, the components and curable composition further included in the curable composition can be appropriately selected according to the technical knowledge widely known by the trade. the preparation method.

According to a preferred embodiment of the present invention, as a method for producing a curable composition, for example, by adding the above-mentioned components and other components to the above-mentioned mixture of the present invention containing the benzodiazepine compound of the formula (1), as necessary The components are kneaded or mixed to produce a curable composition.

The kneading or mixing method is not particularly limited, and for example, it can be carried out using mixing devices such as planetary mixers, PD mixers, butterfly mixers, twin-screw extruders, hot rolls, kneaders, Plastomills, and dispersing mixers, kneaders, and the like. mix.

Cured product According to one embodiment of the present invention, the cured product obtained by curing the above-mentioned curable composition has the characteristics of high glass transition temperature and excellent heat resistance.

(Characteristics of hardened objects) According to one embodiment of the present invention, the heat resistance of the cured product can be evaluated by measuring the glass transition temperature. From the viewpoint of imparting heat resistance, the glass transition temperature is preferably high.

The glass transition temperature can be determined by dynamic viscoelasticity measurement (DMA). The measurement of the glass transition temperature by DMA can be easily performed by using a commercially available viscoelasticity measuring apparatus (for example, manufactured by Hitachi High-Tech Science Co., Ltd., product name: DMA-7100).

The glass transition temperature of the cured product of the present invention obtained by DMA is 240°C or higher, preferably 245°C or higher, preferably 250°C or higher. The upper limit is not particularly limited, but is preferably 300°C or lower.

Manufacturing method of cured product According to one embodiment of the present invention, a cured product can be obtained by curing the above-mentioned curable composition of the present invention. The curing method of the curable composition is not particularly limited, and can be appropriately performed by heating or the like.

When the curable composition is cured by heating, it is preferable to heat the curable composition in multiple stages. Thereby, the hardening reaction can be sufficiently advanced. For example, a hardening reaction can be performed by the primary heating at 160-200 degreeC for 60-240 minutes, and the secondary heating at 220-270 degreeC for 60-300 minutes. The temperature increase rate to the primary heating temperature and the temperature increase rate from the primary heating temperature to the secondary heating temperature are not particularly limited, but are preferably 1 to 4°C/min. However, the conditions of the curing reaction are not limited to the above, and are preferably carried out by appropriately changing the content of the mixture containing the benzodiazepine compound of the formula (1), the properties of other compounds contained in the curable composition, and the like. .

Use of hardened product According to one embodiment of the present invention, the use of hardened product may specifically include: adhesive, adhesive, coating on metal, resin film, glass, paper, wood and other substrates. Surface protection film, hard coating agent, antifouling film and antireflection film for coatings, semiconductor elements or organic thin film elements (such as organic electroluminescent elements or organic thin film solar cell elements), lenses, filters, filters Various optical components such as devices, image display materials, lens arrays, sealing materials or reflective materials for optical semiconductor elements, sealing materials for semiconductor elements, optical waveguides, light guide plates, light diffusing plates, diffractive elements, and optical adhesives, casting Materials, interlayer insulators, protective insulating films for printed and aligned substrates, fiber-reinforced composite materials, and other materials, anti-corrosion materials, etc. [Example]

Hereinafter, the present invention will be described in further detail by way of examples, but the present invention is not limited to these examples.

The substances used in the following Examples and Comparative Examples are shown below. ・P-aminophenol: manufactured by Tokyo Chemical Industry Co., Ltd. ・Phenol: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. ・Bisphenol F: manufactured by Tokyo Chemical Industry Co., Ltd. ・4,4'-Bisphenol F: manufactured by Tokyo Chemical Industry Co., Ltd. ・Bisphenol A: manufactured by Tokyo Chemical Industry Co., Ltd. ・Paraformaldehyde: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. ・4,4'-Diaminodiphenylmethane: manufactured by Aldrich Corporation ・Aniline: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. ・Chloroform: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. ・1,4-Dioxane: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. ・Epoxy compound: Celloxide 2021P (made by Daicel Co., Ltd.)

The evaluation of the mixture containing the benzodiazepine compound in the following Examples and Comparative Examples was carried out by the following method. ( Measurement of the number-average molecular weight and weight-average molecular weight of the mixture containing the benzodiazepine compound, and the measurement of the content of the x - polymer in the mixture containing the benzodiazepine compound ) The following examples and comparative examples obtained The determination of the number average molecular weight (Mn) and the weight average molecular weight (Mw) of the mixture is carried out by GPC (gel permeation chromatography). In addition, the content rate (area %) of the x-polymer with respect to the total amount of the mixture was also calculated from the GPC calibration curve obtained by using the following molecular weight conversion standard substance based on the measurement result of GPC. Specifically, the content ratio (area %) of the x-polymer is the ratio of the peak area of the x-polymer to the sum of the peak areas derived from the mixture. Here, as the peak area, when the peaks are separated, it is the area value obtained by connecting the peak start point and the end point, and when the peaks overlap, it is the area value obtained by vertically dividing the minimum value between the peaks.

Specifically, GPC was performed under the following conditions. [GPC conditions] Measuring device: HLC-8420GPC (Tosoh Corporation) Column: TSKgel SuperHZ3000+TSKgel SuperHZ2000+TSKgel SuperHZ1000×2 (Tosoh Corporation, respectively) (Columns are based on two of TSKgel SuperHZ3000, TSKgel SuperHZ2000, and TSKgel SuperHZ1000 Serial connection) Eluent: THF Flow rate: 0.35 ml/min Measurement temperature: 40°C Injection volume: 3 μL (sample is diluted or dissolved with THF to prepare a solution of about 0.5 wt%) Detector: UV detector detection Wavelength: 254 nm Molecular weight conversion standard material: Four kinds of benzos with the following structures were used. [hua 6]

In the above-mentioned GPC measurement, the peak area of the x-polymer was determined as follows. The peak area of the compound having the molecular weight of the peak top in the range of 210 to 250 was taken as the peak area of the monomer. The peak area of the compound having the molecular weight of the peak top in the range of 320 to 420 was taken as the peak area of the dimer. The peak area of the compound having the molecular weight of the peak top in the range of 430 to 550 was taken as the peak area of the trimer. The peak area of the compound having the molecular weight of the peak top in the range of 570 to 650 was taken as the peak area of the tetramer. The peak area of the compound having the molecular weight of the peak top in the range of 670 to 760 was taken as the peak area of the pentamer. The peak area of the compound having the molecular weight of the peak top in the range of 780 to 850 was taken as the peak area of the hexamer. The peak area of the compound having the molecular weight of the peak top in the range of 880 to 1100 was defined as the peak area of the compound having a 7-mer or more.

( Measurement of ¹ H-NMR spectrum of mixture containing benzodiazepine compound ) The mixture obtained in the following Examples and Comparative Examples was measured by ¹ H-NMR spectrum. Specifically, it was performed under the following conditions. [Measurement conditions of ¹ H-NMR] Measuring device: DD2 (Agilent Technologies) Solvent: CDCl ₃ Measuring frequency: 600 MHz Sample concentration: 0.3 to 0.8 mass % Accumulation times: 16 times

( Measurement of Infrared Absorption Spectrum of Mixtures Containing Benzoic Compounds ) By ATR method (attenuated total reflectance method, attenuated total reflection method), infrared absorption of the mixtures obtained in the following Examples and Comparative Examples under the following conditions Spectra (IR) were measured. [Measurement conditions of infrared absorption spectrum] Apparatus: Nicolet iS10 (Thermo Fisher Scientific) Measurement range: 4000 to 400 cm ^-1 Accumulation times: 10 times

( Measurement of Compatibility of Mixtures Containing Benzoic Compounds with Epoxy Compounds ) 50 parts by mass of the mixtures obtained in the following Examples and Comparative Examples and 50 parts by mass of an epoxy compound ( Celloxide 2021P, manufactured by Daicel Co., Ltd.) Parts by mass were heated to 80°C, 100°C, or 120°C and mixed to obtain a sample. The compatibility of the obtained samples was evaluated based on the following criteria. Regarding the obtained sample, the state in which no insoluble residue remained was evaluated as "compatible". The so-called "compatibility" refers to a state in which the entire mixture is dissolved in the epoxy compound and is a homogeneous solution. ◎: Compatible below 80°C: Compatible below 100°C △: Compatible below 120°C ×: Undissolved

( Measurement of Viscosity of Preparation ( Thermosetting Composition ) of a Mixture Containing a Benzoic Compound and an Epoxy Compound ) 50 parts by mass of the mixture obtained in the following Examples and Comparative Examples, and an epoxy compound ( Celloxide2021P , Daicel (Co., Ltd.) 50 parts by mass was heated to prepare a homogeneous solution, and then cooled to room temperature, and the obtained product was used as a sample. The viscosity of the sample was measured using a rheometer (DHR-2, manufactured by TA Instruments). Specifically, the sample was sandwiched between a parallel plate with a gap adjusted to 1 mm, the temperature was increased from 20°C to 140°C at a temperature increase rate of 2°C/min, and the measurement was performed, and the viscosity at 30°C was obtained. The measurements were carried out at a rotational speed of 10 rad/s.

( Glass transition temperature of hardened product; Tg) 50 parts by mass of the mixture obtained in the following Examples and Comparative Examples and 50 parts by mass of the epoxy compound were put into a cup, and heated to 100° C. (only Comparative Example 3 was 120 °C), it was prepared by mixing and degassing by MAZERUSTAR (KK-V350W, vacuum planetary stirring defoaming device, manufactured by Kurashiki Textile Co., Ltd.). After that, the obtained preparation was injected into a mold, heated in an oven from 100°C to 180°C at a heating rate of 2°C/min, heated at 180°C for 2 hours, and thereafter heated at 2°C/min The temperature increase rate was raised to 250°C, and the cured product was produced by heating at 250°C for 4 hours. The obtained hardened material was cut into a size of about 10 mm in length, about 50 mm in width, and about 3 mm in thickness to obtain a test piece. Using this test piece, Tg was measured from the peak top of tanδ by the following viscoelasticity measuring apparatus under the following conditions. The results are shown in Table 1. Apparatus: DMA-7100 (manufactured by Hitachi High-Tech Science Co., Ltd.) Measurement conditions: _N2 flow rate; 20 ml/min, measurement range; 30 to 350°C, heating rate; 5°C/min

Example 1 : Synthesis of a mixture containing benzodiazepines (p-AP/BisF/ aniline = 2/1.2/2) p - aminophenol (109 g, 1.00 mol), bisphenol F (120 g, 0.60 mol), aniline (93 g, 1.00 mol), and paraformaldehyde (132 g, 4.4 mol) were dissolved in chloroform (0.4 L)/1,4-dioxane (0.6 L), and heated to reflux (oil bath). temperature: 80°C) and stirred for 60 hours. After the reaction was completed, the reactant was filtered, and the filtrate was concentrated to 1/3 of the amount, followed by crystallization with hexane, filtration separation, and vacuum drying to obtain 315 g of a mixture containing the target benzodiazepine compound (the yield was 315 g). 90 mol%). Table 1 shows the above-mentioned raw materials in molar ratios and the like.

The average molecular weight of the mixture obtained in Example 1 is shown in Table 1. Furthermore, Table 1 shows the content ratio of the x-polymer in the mixture obtained in Example 1 by GPC measurement. In addition, in Table 1, "ND" means that the detection limit is not reached. Here, the detection limit is 0.1 area %.

In addition, about the mixture obtained in Example 1, the measurement of ¹ H-NMR spectrum was performed, and the measurement result is shown in FIG. 1. FIG. In the ¹ H-NMR spectrum, the peaks around 4.2 to 4.7 ppm and 5.0 to 5.4 ppm were confirmed to be peaks belonging to CH ₂ in the 㗁𠯤 ring, and the ratio of the integral values of the protons included in the two sites of the 㗁𠯤 ring. About 1:1.

( ¹ H NMR spectrum of the mixture obtained in Example 1) ¹ H NMR (600 MHz, CDCl ₃ ) δ (ppm) 7.4 - 6.6 (aromatic H), 5.4 - 5.0 (-OC H ₂ -N), 4.7 - 4.2 (NC H ₂ -C), 3.9 - 3.6 (CC H ₂ -C).

About the mixture obtained in Example 1, the infrared absorption spectrum measurement was performed, and the measurement result is shown in FIG. 2. FIG. Characteristic peaks of benzodiazepines were observed at 926 cm ^-1 , 1221 cm ^-1 , and 1492 cm ^-1 .

According to the measurement results of the above-mentioned GPC, ¹ H NMR spectrum, and infrared absorption spectrum, it was confirmed that the compound of the following formula (m+n=2 (theoretical value)) was contained in the obtained mixture. [hua 7]

Furthermore, Table 1 shows the measurement results of the compatibility with the epoxy compound, the viscosity, and the glass transition temperature of the mixture obtained in Example 1.

[Table 1] Example Comparative example 1 2 1 2 3 4 5 Morby p-aminophenol 2 2 7 Hydroxyl content 45% 45% 88% Amino group content 50% 50% 88% phenol 1 2 2 Bisphenol F 1.2 1 1 4,4'-Bisphenol F 1.2 Bisphenol A 1 4,4'-Diaminodiphenylmethane 1 1 2 1 aniline 2 2 1 OH/NH ₂ 1.10 1.10 1.00 1.00 1.00 1.00 Reaction time 60 60 42 5 5 48 - Yield (mol%) 90 90 86 100 80 83 - Average molecular weight Mn 735 718 661 1530 1000 900 - Mw/Mn 1.17 1.15 1.48 2.79 3.13 3.04 - Monomer content (area %) ND ND 4.2 ND ND ND - Dimer content (area %) 1.8 2.2 10.8 ND ND 13 - Content rate of 3-6 polymers (area %) 59.9 68.8 44.2 100 100 87 - Content rate of compounds with more than 7 polymers (area %) 38.3 29 38.2 - Compatibility with epoxy compounds ◎ ◎ × △ ◎ Viscosity (Pa・s) 20 13 155 - 4520 3880 5 (40℃) Glass transition temperature (℃) 254 254 232 - 270 230 185

Example 2 Except that the composition of the raw materials, the mixing ratio, and the reaction time were changed as shown in Table 1 above, and the paraformaldehyde (converted to formaldehyde) was set to 2.2 times the mol of the total of p-aminophenol and aniline, The mixture was synthesized in the same manner as in Example 1.

The average molecular weight of the mixture obtained in Example 2 is shown in Table 1. Furthermore, Table 1 shows the content ratio of the x-polymer in the mixture obtained in Example 2 by GPC measurement.

Moreover, about the mixture obtained in Example 2, the measurement result of ¹ H-NMR spectrum was performed, and the measurement result is shown in FIG. In the ¹ H-NMR spectrum, the peaks around 4.2 to 4.8 ppm and 5.0 to 5.6 ppm are the peaks belonging to CH ₂ of the 㗁𠯤 ring, which are included in the two parts of the 㗁𠯤 ring, and the ratio of the integral value of the protons is about 1:1.

( ¹ H NMR spectrum of the mixture obtained in Example 2) ¹ H NMR (600 MHz, CDCl ₃ ) δ (ppm) 7.4 - 6.4 (aromatic H), 5.6 - 5.0 (-O-CH ₂ -N) , 4.8 - 4.2 (N-CH ₂ -C), 3.9 - 3.6 (CC H ₂ -C).

About the mixture obtained in Example 2, the infrared absorption spectrum measurement was performed, and the measurement result is shown in FIG. 4. FIG. Characteristic peaks of benzodiazepines were observed at 931 cm ^-1 , 1222 cm ^-1 , and 1494 cm ^-1 .

Comparative Example 1 p-aminophenol (38.1 g, 0.35 mol), phenol (4.7 g, 50 mmol), aniline (4.7 g, 50 mmol), and paraformaldehyde (26 g, 0.87 mol) were dissolved in chloroform (150 ml) )/1,4-dioxane (180 ml), and stirred under reflux with heating (temperature of oil bath: 80° C.) for 42 hours. After the reaction was completed, the reactant was filtered, and the filtrate was concentrated to 1/3 of the amount, followed by crystallization with hexane, filtration separation, and vacuum drying to obtain 49 g of a mixture containing the target benzodiazepine compound (yield: 49 g). 86 mol%).

Table 1 shows the yield, average molecular weight, and x-polymer content of the mixture obtained in Comparative Example 1.

Moreover, about the mixture obtained in the comparative example 1, the measurement of ¹ H-NMR spectrum was performed, and the measurement result is shown in FIG. 5. FIG.

( ¹ H NMR spectrum of the mixture obtained in Comparative Example 1) ¹ H NMR (600 MHz, CDCl ₃ ) δ (ppm) 7.5 - 6.3 (aromatic H), 5.4 - 5.0 (-OC H ₂ -N), 4.7 - 4.0 (NCH2- _C ).

About the mixture obtained in the comparative example 1, the infrared absorption spectrum measurement was performed, and the measurement result is shown in FIG. 6. FIG. Characteristic peaks of benzodiazepines were observed at 933 cm ^-1 , 1220 cm ^-1 , and 1494 cm ^-1 .

According to the measurement results of the above-mentioned GPC, ¹ H NMR spectrum and infrared absorption spectrum, it was confirmed that the compound of the following formula (n=7 (theoretical value)) was contained in the obtained mixture. [hua 8]

Furthermore, Table 1 shows the measurement results of the compatibility with the epoxy compound, the viscosity, and the glass transition temperature of the mixture obtained in Comparative Example 1.

Comparative Example 2 Bisphenol A (70 g, 0.31 mol), 4,4'-diaminodiphenylmethane (61 g, 0.31 mol), and paraformaldehyde (40 g, 1.31 mol) were dissolved in chloroform (0.8 L) ), the mixture was stirred under heating under reflux (temperature of oil bath: 80° C.) for 5 hours. After completion of the reaction, the reactant was filtered, the filtrate was washed with a 1N aqueous NaHCO ₃ solution (1.6 L), and the filtrate was dried (NaSO ₄ ), filtered and concentrated. After drying in vacuo, 156 g of a mixture containing the target benzodiazepine compound was obtained (yield 100 mol%).

Table 1 shows the yield, average molecular weight, and x-polymer content of the mixture obtained in Comparative Example 2. In addition, in the comparative example 2, since the peak of each polymer was not isolate|separated, the sum total of the compound more than a trimer was calculated.

Moreover, about the mixture obtained in the comparative example 2, the measurement of ¹ H-NMR spectrum was performed, and the measurement result is shown in FIG. 7. FIG.

( ¹ H NMR spectrum of the mixture obtained in Comparative Example 2) ¹ H NMR (600 MHz, CDCl ₃ ) δ (ppm) 7.2 - 6.4 (aromatic H), 5.4 - 5.2 (-OC H ₂ -N), 4.6 - 4.4 (NC H ₂ -C), 3.9 - 3.7 (CC H ₂ -C), 1.7 - 1.4 (CH ₃ ).

About the mixture obtained in the comparative example 2, the measurement of the infrared absorption spectrum was performed, and the measurement result is shown in FIG. 8. FIG. Characteristic peaks of benzodiazepines were observed at 938 cm ^-1 , 1228 cm ^-1 , and 1497 and 1510 cm ^-1 .

According to the above-mentioned GPC measurement results, the measurement results of the ¹ H NMR spectrum, and the measurement results of the infrared absorption spectrum, it was confirmed that the compound having the repeating unit of the following formula was contained in the obtained mixture. [Chemical 9]

Furthermore, Table 1 shows the measurement results of the compatibility with the epoxy compound, the viscosity, and the glass transition temperature of the mixture obtained in Comparative Example 2. Furthermore, since the mixture obtained in Comparative Example 2 had poor compatibility with epoxy compounds, a uniform composition could not be obtained, so the viscosity or glass transition temperature of the mixture could not be measured.

Comparative Example 3 Bisphenol F (61 g, 0.31 mol), 4,4'-diaminodiphenylmethane (61 g, 0.31 mol), and paraformaldehyde (40 g, 1.32 mol) were dissolved in chloroform (0.8 L) ), the mixture was stirred under heating under reflux (temperature of oil bath: 80° C.) for 5 hours. After completion of the reaction, the reactant was filtered, the filtrate was washed with a 1N aqueous NaHCO ₃ solution (1.6 L), and the filtrate was dried (NaSO ₄ ), filtered and concentrated. After drying in vacuo, 112 g of a mixture containing the target benzodiazepine compound was obtained (yield: 80 mol%).

Table 1 shows the yield, average molecular weight, and x-polymer content of the mixture obtained in Comparative Example 3. In addition, in the comparative example 3, since the peak of each polymer was not isolate|separated, the sum total of the compound of a trimer or more was calculated.

Moreover, about the mixture obtained in the comparative example 3, the measurement of ¹ H-NMR spectrum was performed, and the measurement result is shown in FIG. 9. FIG.

( ¹ H NMR spectrum of the mixture obtained in Comparative Example 3) ¹ H NMR (600 MHz, CDCl ₃ ) δ (ppm) 7.2 - 6.5 (aromatic H), 5.4 - 5.1 (-OC H ₂ -N), 4.6 - 4.3 (NC H ₂ -C), 3.9 - 3.6 (CC H ₂ -C).

About the mixture obtained in the comparative example 3, the infrared absorption spectrum measurement was performed, and the measurement result is shown in FIG. 10. FIG. Characteristic peaks of benzodiazepines were observed at 928 cm ^-1 , 1223 cm ^-1 , and 1499 and 1511 cm ^-1 .

According to the measurement results of the above-mentioned GPC, ¹ H NMR spectrum and infrared absorption spectrum, it was confirmed that the compound having the repeating unit of the following formula was contained in the obtained mixture. [Chemical 10]

Furthermore, Table 1 shows the measurement results of the compatibility with the epoxy compound, the viscosity, and the glass transition temperature of the mixture obtained in Comparative Example 3. In addition, as the viscosity of the mixture obtained by the comparative example 3, the viscosity at 40 degreeC is shown.

Comparative Example 4 bisphenol F (100 g, 0.50 mol), 4,4'-diaminodiphenylmethane (198 g, 1.00 mol), phenol (94 g, 1.00 mol), paraformaldehyde (132 g, 1.00 mol) 4.4 mol) was dissolved in chloroform (1.0 L), and stirred under heating under reflux (temperature of oil bath: 80° C.) for 48 hours. After completion of the reaction, the reactant was filtered, the filtrate was washed with water (1 L, 3 times), dried (MgSO ₄ ), crystallized with hexane, separated by filtration, and dried in vacuo to obtain the target benzodiazepine. Compound mixture 352 g (yield 83 mol%).

Table 1 shows the yield, average molecular weight, and x-polymer content of the mixture obtained in Comparative Example 4. In addition, in the comparative example 4, since the peak of the compound of a trimer or more was not isolate|separated, the sum total of the compound of a trimer or more was calculated.

Moreover, about the mixture obtained in the comparative example 4, the measurement of ¹ H-NMR spectrum was performed, and the measurement result is shown in FIG. 11. FIG.

( ¹ H NMR spectrum of the mixture obtained in Comparative Example 4) ¹ H NMR (600 MHz, CDCl ₃ ) δ (ppm) 7.3 - 6.5 (aromatic H), 5.4 - 5.0 (-OC H ₂ -N), 5.0 - 4.4 (NC H ₂ -C), 3.9 - 3.6 (CC H ₂ -C).

About the mixture obtained in the comparative example 4, the measurement of the infrared absorption spectrum was performed, and the measurement result is shown in FIG. 12. FIG. Characteristic peaks of benzodiazepines were observed at 926 cm ^-1 , 1223 cm ^-1 , and 1497 and 1510 cm ^-1 .

According to the measurement results of the above-mentioned GPC, ¹ H NMR spectrum and infrared absorption spectrum, it was confirmed that the compound of the following formula (n=1 (theoretical value)) was contained in the obtained mixture. [Chemical 11]

Furthermore, Table 1 shows the measurement results of the compatibility with the epoxy compound, the viscosity, and the glass transition temperature of the mixture obtained in Comparative Example 4.

Comparative Example 5 As Comparative Example 5, commercially available phenol-diaminodiphenylmethane (Pd) type benzodiazepines (manufactured by Shikoku Chemical Co., Ltd.) shown below were used. [Chemical 12]

Table 1 shows the measurement results of the compatibility with the epoxy compound, the viscosity, and the glass transition temperature of the (P-d) type benzodiazepine of Comparative Example 5.

From the results shown in the above Table 1, it can be seen that the mixture containing the benzodiazepine compound of the formula (1) exhibits excellent compatibility with epoxy compounds and can reduce the viscosity of the curable composition. Furthermore, it turned out that the hardened|cured material of the curable composition containing the mixture containing the benzodiazepine compound of Formula (1) shows excellent heat resistance. [Reference to related applications]

This patent application is accompanied by a claim of priority based on Japanese Patent Application No. 2020-115952 filed on July 3, 2020, the entire disclosure of which is incorporated herein by reference. part.

FIG. 1 shows the ¹ H NMR (Nuclear Magnetic Resonance, nuclear magnetic resonance) peak diagram of the mixture containing the benzodiazepine compound obtained in Example 1. FIG. FIG. 2 shows the infrared absorption spectrum (IR) of the mixture containing the benzodiazepine compound obtained in Example 1. FIG. FIG. 3 shows the ¹ H NMR peak diagram of the mixture containing the benzodiazepine compound obtained in Example 2. FIG. FIG. 4 shows the infrared absorption spectrum (IR) of the mixture containing the benzodiazepine compound obtained in Example 2. FIG. FIG. 5 shows a ¹ H NMR peak diagram of the mixture containing the benzodiazepine compound obtained in Comparative Example 1. FIG. FIG. 6 shows the infrared absorption spectrum (IR) of the mixture containing the benzodiazepine compound obtained in Comparative Example 1. FIG. FIG. 7 shows a ¹ H NMR peak chart of the mixture containing the benzodiazepine compound obtained in Comparative Example 2. FIG. FIG. 8 shows the infrared absorption spectrum (IR) of the mixture containing the benzodiazepine compound obtained in Comparative Example 2. FIG. 9 shows a ¹ H NMR peak diagram of the mixture containing the benzodiazepine compound obtained in Comparative Example 3. FIG. 10 shows the infrared absorption spectrum (IR) of the mixture containing the benzodiazepine compound obtained in Comparative Example 3. FIG. FIG. 11 shows a ¹ H NMR peak diagram of the mixture containing the benzodiazepine compound obtained in Comparative Example 4. FIG. FIG. 12 shows the infrared absorption spectrum (IR) of the mixture containing the benzodiazepine compound obtained in Comparative Example 4. FIG.

Claims (10)

A method for producing a mixture comprising the steps of condensing p-aminophenol, aromatic primary monoamines, bisphenols and formaldehyde, the mixture comprising the following formula (1) The represented benzodiazepine compound, and the phenolic hydroxyl group derived from the above-mentioned p-aminophenol and the above-mentioned bisphenols in the above-mentioned condensation reaction step, and the above-mentioned p-aminophenol and the above-mentioned aromatic primary monoamine. The ratio of such amine groups (OH/NH ₂ ) is 1.05/1 to 1.15/1, [Chem. 1]

Formula (1) [In formula (1), L is an alkylene group having 1 to 10 carbon atoms, an aralkylene group having 7 to 21 carbon atoms, oxygen, sulfur or sulfonyl group, and Ar is independently substituted. In the aryl group, m and n are each independently an integer of 0 or more]. The method of claim 1, wherein the aryl group of formula (1) can be substituted by 1 to 3 substituents R ₁ , and the substituents R ₁ are independently selected from alkyl, alkoxy, ester, amido, A group consisting of cyano and halogen atoms. The method according to claim 1 or 2, wherein in the condensation reaction step, the content of the amine group of the p-aminophenol in the amine groups of the p-aminophenol and the aromatic primary monoamines is 25-75% Mol%. The method according to any one of claims 1 to 3, wherein in the condensation reaction step, the content of the phenolic hydroxyl group derived from the p-aminophenol and the phenolic hydroxyl group of the above-mentioned bisphenols The rate is 25 to 75 mol% or less. The method according to any one of claims 1 to 4, wherein the number-average molecular weight of the mixture is 600-1500, The ratio of the benzodiazepine compound in which m and n in the formula (1) are 0 is 20 area % or less with respect to the total amount of the mixture. The method according to any one of claims 1 to 5, wherein the mixture is formed by including benzodiazepine compounds having different total values of m and n in formula (1). The method according to any one of claims 1 to 6, wherein the mixture comprises a benzodiazepine compound whose total value of m and n in formula (1) is 1 or more. The method according to any one of claims 1 to 7, wherein the ratio of the benzodiazepine compound having a total value of m and n in the formula (1) of 5 or more is 15 area % or more and 70% relative to the total amount of the mixture. Area % or less. The method according to any one of claims 1 to 8, wherein the ratio of the benzodiazepine compound having a total value of m and n in formula (1) of 1 to 4 is 25 area % or more relative to the total amount of the mixture . The method according to any one of claims 1 to 9, wherein the molecular weight dispersion of the mixture is 1.05-2.50.

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