JP2018199774A - Triazine ring-containing hyperbranched polyamide and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hyperbranched polyamide having excellent heat resistance, transparency and solubility in an organic solvent and exhibiting a high refractive index, and a film-forming composition containing the same. SOLUTION: A triazine ring-containing hyperbranched polyamide containing a structural unit represented by the formula (1) and sealed with an end-sealing compound having an ethynyl group at the end. [R1 to R4 are independently H, alkyl group, alkoxy group, aryl group or aralkyl group; R5 and R6 are independently H, alkyl group or aryl group, and at least one of R5 and R6 is an alkyl group or aryl group. Ar1 and Ar2 are independently C6 to 20 arylene groups] [Selection diagram] None

Description

  The present invention relates to a triazine ring-containing hyperbranched polyamide and a method for producing the same.

  Hyperbranched polyamides are widely used in the fields of fibers, molding materials, composite materials, electric / electronic parts, etc., because they are excellent in heat resistance, transparency, mechanical properties and the like. However, in general, hyperbranched polyamides have problems such as intermolecular hydrogen bonding and stacking between aromatic groups resulting in large intermolecular cohesion and extremely low solubility in organic solvents, and insolubilization during the reaction. There is.

In the case of linear polyamide, as a method for improving the solubility, a method using a monomer in which a flexible structural unit such as oxygen, SO ₂ and a methylene group is introduced (Patent Document 1), or a fluorene group is used. A method using a diamine compound having a group having a large molecular size is known (Patent Document 2).

  Unlike general linear polymers, hyperbranched polymers have a highly branched structure, resulting in less entanglement between molecules, low viscosity regardless of the molecular structure of the main chain, and solubility in organic solvents. It has properties such as high properties. In addition, the number of terminals is large, and by functionalizing them, it becomes possible to design a multifunctional polymer, and application in various fields is expected.

As a method for producing a hyperbranched polymer, two kinds of methods, AB ₂ method and A ₂ + B ₃ method, are known, and A and B correspond to functional groups in the monomer. For example, in the AB ₂ method, a trifunctional monomer having one functional group A and two functional groups B reacts to give a hyperbranched polymer. On the other hand, in the A ₂ + B ₃ method, a monomer having two functional groups A reacts with a monomer having three functional groups B to give a hyperbranched polymer. In the A ₂ + B ₃ method, in the ideal case, a 1: 1 reactant having only one functional group A and two functional groups B is produced from two monomers, and this reactant is further reacted. To give a hyperbranched polymer.

With regard to such a hyperbranched polyamide, AB ₂ type polycondensation having a carboxylic acid and an amino group in the molecule (Non-patent Document 1), and A ₂ + B ₃ type polycondensation by benzenetricarboxylic acid and a diamine compound It has been reported (Non-Patent Document 2). However, these methods have problems that it is difficult to control insolubilization and that the reaction takes a long time. Further, at least the hyperbranched aromatic polyamide obtained by the technique as described in Non-Patent Document 2 also has insufficient solubility in organic solvents. Furthermore, these hyperbranched polyamides were inferior in film forming property.

JP 2005-23106 A JP 2006-77185 A

J. Polym. Sci. Part A: Polym. Chem., 2004, 42, pp.1293-1309. Macromolecules, 1999, 32, pp.2061-2064.

  The present invention has been made in view of such circumstances, and is excellent in heat resistance, transparency, solubility in organic solvents, and after thermal crosslinking, film-forming properties, solvent resistance, high transparency, and high refraction. It is an object of the present invention to provide a hyperbranched polyamide that exhibits a rate and a method for producing the same.

  As a result of intensive studies to achieve the above object, the present inventors are a triazine ring-containing hyperbranched polyamide obtained by reacting benzenetricarboxylic acid with a predetermined diamine compound containing a triazine ring, Those whose ends are sealed with an end-capping compound having an ethynyl group are excellent in heat resistance, transparency, solubility in organic solvents, exhibit a high refractive index, and further improve heat resistance after thermal crosslinking, In addition, the present inventors have found that the solvent resistance and film-forming property are improved and can be suitably used as a base polymer of a film-forming composition when an electronic device is produced, and the present invention has been completed.

（式中、Ｒ¹〜Ｒ⁴は、それぞれ独立に、水素原子、アルキル基、アルコキシ基、アリール基又はアラルキル基であり、Ｒ⁵及びＲ⁶は、それぞれ独立に、水素原子、アルキル基又はアリール基であるが、Ｒ⁵及びＲ⁶の少なくとも一方は、アルキル基又はアリール基であり、Ａｒ¹及びＡｒ²は、それぞれ独立に、炭素数６〜２０のアリーレン基である。）
２．末端封止化合物が、エチニルアニリンである１のトリアジン環含有ハイパーブランチポリアミド。
３．Ａｒ¹及びＡｒ²が、フェニレン基である１又は２のトリアジン環含有ハイパーブランチポリアミド。
４．Ｒ¹〜Ｒ⁴が、水素原子である１〜３のいずれかのトリアジン環含有ハイパーブランチポリアミド。
５．Ｒ⁵が水素原子であり、Ｒ⁶がフェニル基である１〜４のいずれかのトリアジン環含有ハイパーブランチポリアミド。
６．Ｒ⁵及びＲ⁶が、ともにフェニル基である１〜４のいずれかのトリアジン環含有ハイパーブランチポリアミド。
７．１〜６のいずれかのトリアジン環含有ハイパーブランチポリアミドを含む膜形成用組成物。
８．１〜６のいずれかのトリアジン環含有ハイパーブランチポリアミドを含む膜。
９．基材と、この基材上に形成された８の膜とを備える電子デバイス。
１０．基材と、この基材上に形成された８の膜とを備える光学部材。
１１．下記式（３）で表されるベンゼントリカルボン酸と下記式（４）で表されるジアミン化合物とエチニル基を有する末端封止化合物とを、縮合剤を用いて有機溶媒中で重縮合させる工程により、下記式（１）で表される構造単位を含み、ベンゼントリカルボン酸末端又はアミン末端がエチニル基を有する末端封止化合物によって封止されたトリアジン環含有ハイパーブランチポリアミドの製造方法。

（式中、Ｒ¹〜Ｒ⁶、Ａｒ¹及びＡｒ²は、前記と同じ。）
１２．下記式（３'）で表されるベンゼントリカルボン酸トリハライドと下記式（４）で表されるジアミン化合物とエチニル基を有する末端封止化合物とを、有機溶媒中で重縮合させる工程により、下記式（１）で表される構造単位を含み、ベンゼントリカルボン酸末端又はアミン末端がエチニル基を有する末端封止化合物によって封止されたトリアジン環含有ハイパーブランチポリアミドの製造方法。

（式中、Ｒ¹〜Ｒ⁶、Ａｒ¹及びＡｒ²は、前記と同じ。Ｘは、それぞれ独立に、ハロゲン原子を表す。） That is, this invention provides the following triazine ring containing hyperbranched polyamide and its manufacturing method.
1. A triazine ring-containing hyperbranched polyamide containing a structural unit represented by the following formula (1) and having a benzenetricarboxylic acid terminal or amine terminal sealed with an end-capping compound having an ethynyl group.

Wherein R ^{1 to} R ⁴ are each independently a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or an aralkyl group, and R ⁵ and R ⁶ are each independently a hydrogen atom, an alkyl group or an aryl group. In this case, at least one of R ⁵ and R ⁶ is an alkyl group or an aryl group, and Ar ¹ and Ar ² are each independently an arylene group having 6 to 20 carbon atoms.)
2. 1 Triazine ring-containing hyperbranched polyamide, wherein the end-capping compound is ethynylaniline.
3. 1 or 2 triazine ring-containing hyperbranched polyamide, wherein Ar ¹ and Ar ² are phenylene groups.
4). ^One of the triazine ring containing hyperbranched polyamide of any one of 1-3 whose R < ¹ > -R < ⁴ > is a hydrogen atom.
5. One of the triazine ring containing hyperbranched polyamide of any one of 1-4 whose R < ⁵ > is a hydrogen atom and R < ⁶ > is a phenyl group.
6). One of the triazine ring containing hyperbranched polyamide of any one of 1-4 whose R < ⁵ > and R < ⁶ > are both phenyl groups.
A film forming composition comprising the triazine ring-containing hyperbranched polyamide according to any one of 7.1 to 6.
The film | membrane containing the triazine ring containing hyperbranched polyamide in any one of 8.1-6.
9. An electronic device comprising a base material and eight films formed on the base material.
10. An optical member comprising a base material and eight films formed on the base material.
11. By the step of polycondensing a benzenetricarboxylic acid represented by the following formula (3), a diamine compound represented by the following formula (4) and an end-capping compound having an ethynyl group in an organic solvent using a condensing agent. A method for producing a triazine ring-containing hyperbranched polyamide comprising a structural unit represented by the following formula (1) and having a benzenetricarboxylic acid terminal or amine terminal sealed with an end-capping compound having an ethynyl group.

(In the formula, R ^{1 to} R ⁶ , Ar ¹ and Ar ² are the same as described above.)
12 By the step of polycondensing a benzene tricarboxylic acid trihalide represented by the following formula (3 ′), a diamine compound represented by the following formula (4) and an end-capping compound having an ethynyl group in an organic solvent, the following formula: A method for producing a triazine ring-containing hyperbranched polyamide comprising the structural unit represented by (1) and having a benzenetricarboxylic acid terminal or amine terminal sealed with an end-capping compound having an ethynyl group.

(In the formula, R ^{1 to} R ⁶ , Ar ^1, and Ar ² are the same as described above. X independently represents a halogen atom.)

  The triazine ring-containing hyperbranched polyamide of the present invention is excellent in solubility and can be easily dissolved in various organic solvents, making it easy to mold, taking advantage of its excellent physical properties, fiber, molding material, composite material, electric / electronic Applications in various fields such as parts can be expected. Further, since the triazine ring-containing hyperbranched polyamide of the present invention is excellent in solubility in an organic solvent, it can be easily formed into a thin film using a coating method, and the thin film has high heat resistance and high transparency. And high refractive index. Furthermore, after the thermal crosslinking of the terminal ethynyl group, the heat resistance is further improved, and the solvent resistance and film forming property are improved.

  The film produced using the triazine ring-containing hyperbranched polyamide of the present invention having such characteristics is a liquid crystal display, an organic electroluminescence (EL) display, an optical semiconductor (LED) element, a solid-state imaging element, an organic thin film solar cell, It can be suitably used as a member for producing electronic devices such as dye-sensitized solar cells and organic thin film transistors (TFTs).

[Triazine ring-containing hyperbranched polyamide]
The triazine ring-containing hyperbranched polyamide of the present invention includes a structural unit represented by the following formula (1), and a benzenetricarboxylic acid terminal or an amine terminal is sealed with an end-capping compound having an ethynyl group. .

In formula (1), R < ¹ > -R < ⁴ > is a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group each independently.

  Although carbon number of the said alkyl group is not specifically limited, 1-20 are preferable, 1-10 are more preferable when considering improving the heat resistance of polyamide more, and 1-3 are still more preferable. The structure may be linear, branched or cyclic.

  Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclobutyl group, 1-methylcyclopropyl. Group, 2-methylcyclopropyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group Group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, cyclopentyl group, 1-methylcyclobutyl group, 2-methylcyclobutyl group, 3-methylcyclobutyl group, 1,2-dimethylcyclopropyl group, 2,3-dimethylcyclopropyl group, 1-ethylcyclopropyl group, 2-ethylcyclopropyl group N-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n- Butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3 -Dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl Group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, cyclohexyl group, 1-methylcyclopentyl group, 2-methylcyclopentyl group, 3-methylcyclopentyl group, 1 -Ethylcyclobutyl group, 2-ethylcyclo Til group, 3-ethylcyclobutyl group, 1,2-dimethylcyclobutyl group, 1,3-dimethylcyclobutyl group, 2,2-dimethylcyclobutyl group, 2,3-dimethylcyclobutyl group, 2,4- Dimethylcyclobutyl group, 3,3-dimethylcyclobutyl group, 1-n-propylcyclopropyl group, 2-n-propylcyclopropyl group, 1-isopropylcyclopropyl group, 2-isopropylcyclopropyl group, 1,2, 2-trimethylcyclopropyl group, 1,2,3-trimethylcyclopropyl group, 2,2,3-trimethylcyclopropyl group, 1-ethyl-2-methylcyclopropyl group, 2-ethyl-1-methylcyclopropyl group , 2-ethyl-2-methylcyclopropyl group, 2-ethyl-3-methylcyclopropyl group, and the like.

  Although carbon number of the said alkoxy group is not specifically limited, 1-20 are preferable, and when considering improving the heat resistance of polyamide more, C1-C10 is more preferable and 1-3 are still more preferable. In addition, the structure of the alkyl moiety may be any of linear, branched or cyclic.

  Examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxy group, 1-methyl-n. -Butoxy group, 2-methyl-n-butoxy group, 3-methyl-n-butoxy group, 1,1-dimethyl-n-propoxy group, 1,2-dimethyl-n-propoxy group, 2,2-dimethyl- n-propoxy group, 1-ethyl-n-propoxy group, n-hexyloxy group, 1-methyl-n-pentyloxy group, 2-methyl-n-pentyloxy group, 3-methyl-n-pentyloxy group, 4-methyl-n-pentyloxy group, 1,1-dimethyl-n-butoxy group, 1,2-dimethyl-n-butoxy group, 1,3-dimethyl-n-butoxy group, 2,2-dimethyl Til-n-butoxy group, 2,3-dimethyl-n-butoxy group, 3,3-dimethyl-n-butoxy group, 1-ethyl-n-butoxy group, 2-ethyl-n-butoxy group, 1,1 1,2-trimethyl-n-propoxy group, 1,2,2-trimethyl-n-propoxy group, 1-ethyl-1-methyl-n-propoxy group, 1-ethyl-2-methyl-n-propoxy group, etc. Can be mentioned.

  The number of carbon atoms of the aryl group is not particularly limited, but is preferably 6 to 40, more preferably 6 to 16 and even more preferably 6 to 13 in view of further improving the heat resistance of the polyamide.

  Examples of the aryl group include a phenyl group, o-chlorophenyl group, m-chlorophenyl group, p-chlorophenyl group, o-fluorophenyl group, p-fluorophenyl group, o-methoxyphenyl group, p-methoxyphenyl group, p- Nitrophenyl group, p-cyanophenyl group, 1-naphthyl group, 2-naphthyl group, o-biphenylyl group, m-biphenylyl group, p-biphenylyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group and the like can be mentioned.

  The number of carbon atoms of the aralkyl group is not particularly limited, but is preferably 7 to 20, and the alkyl portion may be linear, branched or cyclic. Specific examples thereof include benzyl group, p-methylphenylmethyl group, m-methylphenylmethyl group, o-ethylphenylmethyl group, m-ethylphenylmethyl group, p-ethylphenylmethyl group, 2-propylphenylmethyl group. 4-isopropylphenylmethyl group, 4-isobutylphenylmethyl group, α-naphthylmethyl group and the like.

Among these, as R < ¹ > -R < ⁴ >, a hydrogen atom, a methyl group, a phenyl group, etc. are preferable, and a hydrogen atom is more preferable.

In formula (1), R ⁵ and R ⁶ are each independently a hydrogen atom, an alkyl group or an aryl group. However, at least one of R ⁵ and R ⁶ is an alkyl group or an aryl group. Examples of the alkyl group and aryl group are the same as those described above.

As R ⁵ and R ⁶ , one is preferably a hydrogen atom and the other is preferably a phenyl group. It is also preferred that both R ⁵ and R ⁶ are phenyl groups. In this case, the solubility of the polymer in the organic solvent can be improved.

In Formula (1), Ar ¹ and Ar ² are each independently an arylene group having 6 to 20 carbon atoms. Examples of the arylene group include groups obtained by further removing one hydrogen atom from the aryl group described above, specifically, a 1,2-phenylene group, a 1,3-phenylene group, a 1,4-phenylene group, 1,3-naphthylene group, 1,4-naphthylene group, 1,5-naphthylene group, 1,6-naphthylene group, 1,7-naphthylene group, 2,6-naphthylene group, 2,7-naphthylene group, etc. Can be mentioned. Among these, Ar ¹ and Ar ² are 1,3-phenylene group, 1,4-phenylene group, 1,5-naphthylene group, 1,6-naphthylene group, 1,7-naphthylene group, 2,6 -A naphthylene group etc. are preferable, a 1, 3- phenylene group or a 1, 4- phenylene group is more preferable, and a 1, 3- phenylene group is still more preferable from a viewpoint of transparency.

（式中、Ｒ¹〜Ｒ⁶、Ａｒ¹及びＡｒ²は、前記と同じ。） As the structural unit represented by the formula (1), those represented by the following formula (1 ′) are particularly preferable.

(In the formula, R ^{1 to} R ⁶ , Ar ¹ and Ar ² are the same as described above.)

  In the triazine ring-containing hyperbranched polyamide of the present invention, a carboxylic acid terminal derived from benzene tricarboxylic acid and an amine terminal derived from a diamine compound are sealed with an end-capping compound having an ethynyl group.

Examples of the end capping compound for capping the carboxylic acid end include amine compounds represented by the following formula (2).

In formula (2), Ar is an arylene group having 6 to 20 carbon atoms. Examples of the arylene group include the same groups as those described above as specific examples of Ar ¹ and Ar ² . Of these, Ar is preferably a 1,3-phenylene group or a 1,4-phenylene group.

  Examples of the amine compound represented by the formula (2) include 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 3- (3-ethynylphenoxy) aniline, 4- (4-ethynylbenzoyl) aniline and the like. It is done. Of these, 3-ethynylaniline and 4-ethynylaniline are preferable.

  Examples of the end-capping compound for capping the amine end include acid chlorides and acid anhydrides having an ethynyl group. Specific examples thereof include 2-ethynylbenzoyl chloride, 3-ethynylbenzoyl chloride, 4-ethynylbenzoyl chloride, 4-ethynylphthalic anhydride, 4- (4-ethynylphenoxy) phthalic anhydride, and the like.

  As the triazine ring-containing hyperbranched polyamide of the present invention, a carboxylic acid terminal derived from benzenetricarboxylic acid is preferably sealed with an end-capping compound having an ethynyl group.

  The number average molecular weight (Mn) of the triazine ring-containing hyperbranched polyamide of the present invention is preferably 1,000 to 100,000, more preferably 2,000 or more from the viewpoint of further improving heat resistance, 50,000 or less are preferable and 20,000 or less are more preferable from the viewpoint of further increasing the solubility and decreasing the viscosity of the obtained solution. In the present invention, Mn is an average molecular weight obtained in terms of standard polystyrene by gel permeation chromatography (GPC) analysis.

  The refractive index at 588 nm (d line) of the triazine ring-containing hyperbranched polymer of the present invention is preferably 1.65 or more, more preferably 1.68 or more, and even more preferably 1.72 or more.

[Method for producing triazine ring-containing hyperbranched polyamide]
The triazine ring-containing hyperbranched polyamide of the present invention is, for example, a benzene tricarboxylic acid represented by the formula (3) and a diamine compound represented by the formula (4) which is a triazine-based condensing agent. -Dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium chloride (DMT-MM) in a suitable organic solvent as shown in the following scheme 1 And synthesizing a polymer containing the structural unit represented by the formula (1), and then sealing the terminal with an end-capping compound having an ethynyl group.

（式中、Ｒ¹〜Ｒ⁶、Ａｒ¹及びＡｒ²は前記と同じである。）

(In the formula, R ^{1 to} R ⁶ , Ar ¹ and Ar ² are the same as described above.)

  Alternatively, a benzenetricarboxylic acid represented by formula (3), a diamine compound represented by formula (4), and an end-capping compound having an ethynyl group are combined with 4- (4,6-dimethoxy) which is a triazine-based condensing agent. It can be obtained by direct polycondensation using -1,3,5-triazin-2-yl) -4-methylmorpholinium chloride (DMT-MM) in a suitable organic solvent.

  Examples of the benzenetricarboxylic acid represented by the formula (3) include 1,3,5-benzenetricarboxylic acid and 1,2,4-benzenetricarboxylic acid, and 1,3,5-benzenetricarboxylic acid is particularly preferable. . These can use a commercial item.

As the diamine compound represented by the formula (4), those represented by the following formula are particularly preferable.

  In the production method of Scheme 1, the amount of each monomer charged is arbitrary as long as the target polymer is obtained, but the diamine compound is preferably 0.01 to 10 equivalents relative to 1 equivalent of benzenetricarboxylic acid, More preferably, it is 0.1 to 5 equivalents. The amount of DMT-MM used is preferably 0.1 to 10 equivalents and more preferably 1 to 5 equivalents with respect to 1 equivalent of benzenetricarboxylic acid.

  As the organic solvent, various solvents usually used in this kind of reaction can be used, for example, tetrahydrofuran, dioxane, N, N-dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, tetramethylurea. , Hexamethylphosphoramide, N, N-dimethylacetamide, N-methyl-2-piperidone, N, N-dimethylethyleneurea, N, N, N ′, N′-tetramethylmalonic acid amide, N-methylcaprolactam N-acetylpyrrolidine, N, N-diethylacetamide, N-ethyl-2-pyrrolidone, N, N-dimethylpropionic acid amide, N, N-dimethylisobutyramide, N-methylformamide, N, N′-dimethylpropylene Amides such as urea, 1,3-dimethyl-2-imidazolidinone, and A mixed solvent of these can be mentioned. Among these, N, N-dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, 1,3-dimethyl-2-imidazolidinone and a mixed solvent thereof are preferable, and N, N -Dimethylacetamide, N-methyl-2-pyrrolidone are preferred.

  In the polymerization reaction, the reaction temperature may be appropriately set in the range from the melting point to the boiling point of the solvent to be used. In particular, about −50 to 150 ° C. is preferable, −30 to 100 ° C. is more preferable, and −30 to 50 is preferable. ° C is even more preferred. The reaction time is preferably 0.1 to 100 hours, more preferably 0.1 to 10 hours.

  In the reaction, various commonly used bases can be used. Specific examples of this base include potassium carbonate, potassium hydroxide, sodium carbonate, sodium hydroxide, sodium hydrogen carbonate, sodium ethoxide, sodium acetate, lithium carbonate, lithium hydroxide, lithium oxide, potassium acetate, magnesium oxide, oxidized Calcium, barium hydroxide, trilithium phosphate, trisodium phosphate, tripotassium phosphate, cesium fluoride, aluminum oxide, trimethylamine, triethylamine, diisopropylamine, diisopropylethylamine, N-methylpiperidine, 2,2,6,6 -Tetramethyl-N-methylpiperidine, pyridine, 4-dimethylaminopyridine, N-methylmorpholine and the like. The amount of the base added is preferably 1 to 100 equivalents and more preferably 1 to 10 equivalents with respect to 1 equivalent of benzenetricarboxylic acid. These bases may be used as an aqueous solution.

  After completion of the reaction, the product can be easily purified according to conventional methods such as reprecipitation.

  Further, as shown in the following scheme 2, the triazine ring hyperbranched polyamide of the present invention is obtained by appropriately converting a benzene tricarboxylic acid trihalide represented by the formula (3 ′) and a diamine compound represented by the formula (4) It can also be obtained by polycondensation in an organic solvent to synthesize a polymer containing the structural unit represented by formula (1), and then sealing the end with an end-capping compound having an ethynyl group. Alternatively, the benzenetricarboxylic acid trihalide represented by the formula (3 ′), the diamine compound represented by the formula (4) and the end-capping compound having an ethynyl group are polycondensed in an appropriate organic solvent, and the formula ( A polymer containing the structural unit represented by 1) can also be obtained.

In the formula, R ^{1 to} R ⁶ , Ar ¹ and Ar ² are the same as described above. X represents a halogen atom each independently. Examples of the halogen atom include those described above, and a chlorine atom and a bromine atom are preferable.

  As the benzenetricarboxylic acid trihalide represented by the formula (3 ′), 1,3,5-benzenetricarboxylic acid trichloride, 1,3,5-benzenetricarboxylic acid tribromide, 1,2,4-benzenetricarboxylic acid trichloride, 1 1,2,4-benzenetricarboxylic acid tribromide and the like, and 1,3,5-benzenetricarboxylic acid trichloride is particularly preferable.

  In the production method of Scheme 2, the amount of each monomer charged is arbitrary as long as the target polymer is obtained, but the diamine compound is preferably 0.01 to 10 equivalents per 1 equivalent of benzenetricarboxylic acid trihalide. More preferably, the content is 0.1 to 5 equivalents.

  The same solvent, base, reaction temperature and reaction time as those used in the reaction of Scheme 1 can be employed.

  After synthesizing the polymer containing the structural unit represented by the formula (1), the triazine ring-containing hyperbranched polyamide of the present invention can be obtained by further adding and reacting a terminal blocking compound. The amount of the end-capping compound charged is not particularly limited, but in consideration of improving the solubility of the resulting triazine ring-containing hyperbranched polyamide, with respect to 1 equivalent of benzenetricarboxylic acid or a derivative thereof used as a starting material, 0.01-10 equivalent is preferable and 0.1-5 equivalent is more preferable.

  What is necessary is just to set the reaction temperature at the time of sealing a terminal | terminus suitably in the range from melting | fusing point to boiling point of the solvent to be used, Especially about -50-150 degreeC is preferable, -30-100 degreeC is more preferable, -30 -50 ° C is even more preferable. Moreover, reaction time is 0.1 to 100 hours normally.

  The diamine compound represented by the formula (4) can be synthesized by a conventionally known method. Moreover, the compound represented by Formula (4) can be refine | purified using conventionally well-known methods, such as recrystallization.

[Composition for film formation]
Since the triazine ring-containing hyperbranched polyamide of the present invention is excellent in solubility in organic solvents, it can be suitably used as a film-forming composition (hereinafter also referred to as polymer varnish) dissolved in various solvents.

  The solvent used for dissolving the triazine ring-containing hyperbranched polyamide may be the same as or different from the solvent used during the polymerization. Considering the solubility and storage stability of the polymer, examples of the solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, Dimethyl sulfoxide, γ-butyrolactone, tetrahydrofuran, cyclopentanone, cyclohexanone and the like are preferable. These solvents may be used alone or in combination of two or more.

  At this time, the solid content concentration in the film-forming composition is not particularly limited as long as it does not affect the storage stability, and may be appropriately set according to the target film thickness. Specifically, from the viewpoint of solubility and storage stability, the solid content concentration is preferably 0.1 to 50% by mass, and more preferably 0.1 to 20% by mass.

  The composition of the present invention may contain other components other than the triazine ring-containing hyperbranched polyamide and the solvent, for example, a leveling agent, a surfactant, a crosslinking agent, etc., as long as the effects of the present invention are not impaired. Good.

  Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether; polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol ether Polyoxyethylene alkyl allyl ether such as polyoxyethylene / polyoxypropylene block copolymer; sorbitan such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate Fatty acid ester; polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as nopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, EFTOP (registered trademark) EF301, EF303, EF352 (Mitsubishi Materials Electronics Chemical Co., Ltd.), MegaFac (registered trademark) F171, F173, R-08, R-30 (DIC Corporation), FLUORAD (registered trademark) FC430, FC431 (manufactured by 3M) Asahi Guard (registered trademark) AG710 (manufactured by Asahi Glass Co., Ltd.), Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Seimi Chemical Co., Ltd.) Activator , Organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), BYK-302, BYK-307, BYK-322, BYK-323, BYK-330, BYK-333, BYK-370, BYK-375, BYK-378 (Made by Big Chemie Japan Co., Ltd.).

  These surfactants may be used alone or in combination of two or more. The amount of the surfactant used is preferably 0.0001 to 5 parts by mass, more preferably 0.001 to 1 part by mass, and 0.01 to 0.5 parts by mass with respect to 100 parts by mass of the triazine ring-containing hyperbranched polyamide. Is even more preferable.

  The crosslinking agent is not particularly limited as long as it is a compound having a substituent capable of reacting with the triazine ring-containing hyperbranched polyamide of the present invention. Such compounds include melamine compounds having a crosslinkable substituent such as a methylol group, methoxymethyl group, substituted urea compounds, compounds containing a crosslinkable substituent such as an epoxy group or an oxetane group, and blocked isocyanates. The compound containing an acid anhydride, the compound which has an acid anhydride, etc. are mentioned, The compound containing an epoxy group or an oxetane group is preferable from a heat resistant and storage stability viewpoint. These compounds need only have at least one cross-linking substituent when used for terminal treatment of triazine ring-containing hyperbranched polyamide, and when used for cross-linking treatment of triazine ring-containing hyperbranched polyamides. It must have at least two cross-linking substituents.

  Specific examples of the crosslinking agent include tris (2,3-epoxypropyl) isocyanurate, 1,4-butanediol diglycidyl ether, 1,2-epoxy-4- (epoxyethyl) cyclohexane, glycerol triglycidyl ether, diethylene glycol Diglycidyl ether, 2,6-diglycidylphenyl glycidyl ether, 1,1,3-tris [p- (2,3-epoxypropoxy) phenyl] propane, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, 4,4 '-Methylenebis (N, N-diglycidylaniline), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, trimethylolethane triglycidyl ether, bisphenol-A-diglycidyl ether, pentaerythritol polyglycidyl ether Tel and the like.

  In addition, as commercially available products, epoxy resins having at least two epoxy groups, YH-434, YH-434L (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), and Epolede GT-401, which is an epoxy resin having a cyclohexene oxide structure. , GT-403, GT-301, GT-302, Celoxide 2021, 3000 (manufactured by Daicel Corporation), bisphenol A type epoxy resin, jER (registered trademark) 1001, 1002, 1003, 1004, 1007, 1009, 1010, 828 (manufactured by Mitsubishi Chemical Corporation), bisphenol F type epoxy resin, jER (registered trademark) 807 (manufactured by Mitsubishi Chemical Corporation), phenol novolac type epoxy resin, jER (registered trademark) 152, 154 (Mitsubishi Chemical Corporation), EPPN 201, 202 (above, Nippon Kayaku Co., Ltd.) ), A cresol novolac type epoxy resin, EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, EOCN-1027 (manufactured by Nippon Kayaku Co., Ltd.), jER (registered trademark) 180S75 ( Mitsubishi Chemical Corporation), alicyclic epoxy resin, Denacol EX-252 (manufactured by Nagase ChemteX Corporation), Araldite (registered trademark) CY175, CY177, CY179, CY-182, CY-192, CY -184 (manufactured by Huntsman Advanced Materials), Epicron 200, 400 (manufactured by DIC Corporation), jER (registered trademark) 871, 872 (manufactured by Mitsubishi Chemical Corporation), ED-5661, ED-5661 (manufactured by Mitsubishi Chemical Corporation) Denacor EX-, an aliphatic polyglycidyl ether) 11, EX-612, EX-614, EX-622, EX-411, EX-512, EX-522, EX-421, EX-313, EX-314, EX-321 (manufactured by Nagase ChemteX Corporation) Etc. can also be used.

  Specific examples of the acid anhydride compound include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, maleic anhydride. Acid, succinic anhydride, octyl succinic anhydride, dodecenyl succinic anhydride, etc. having one acid anhydride group in the molecule; 1,2,3,4-cyclobutanetetracarboxylic dianhydride, pyromellitic acid Anhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic acid Dianhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 1,2,3,4-butanthate Carboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, etc. having two acid anhydride groups in the molecule, etc. Is mentioned.

  These crosslinking agents may be used alone or in combination of two or more. The amount of the crosslinking agent used is preferably 0.0001 to 20 parts by mass, more preferably 0.001 to 10 parts by mass with respect to 100 parts by mass of the triazine ring-containing hyperbranched polyamide. By using a crosslinking agent, the crosslinking agent reacts with the reactive terminal substituent of the triazine ring-containing hyperbranched polyamide, and effects such as improvement in film density, improvement in heat resistance, and improvement in thermal relaxation ability can be exhibited. There is a case. The other components may be added simultaneously with the mixing of the triazine ring-containing hyperbranched polyamide and the solvent, or may be added thereafter, and are not particularly limited.

  The film-forming composition of the present invention can be applied to a substrate and then heated as necessary to form a desired film. The coating method of the composition is arbitrary, for example, spin coating method, dip method, flow coating method, ink jet method, spray method, bar coating method, gravure coating method, slit coating method, roll coating method, transfer printing method, brush Methods such as coating, blade coating, and air knife coating can be employed.

  As the base material, silicon, glass with indium tin oxide (ITO) formed, glass with indium zinc oxide (IZO) formed, polyethylene terephthalate (PET), plastic, glass, quartz, ceramics A flexible substrate having flexibility can also be used.

  Although a calcination temperature is not specifically limited for the purpose of evaporating a solvent, For example, it can carry out at 40-400 degreeC. In these cases, the temperature may be changed in two or more steps for the purpose of expressing a higher uniform film forming property or allowing the reaction to proceed on the substrate.

  The firing method is not particularly limited, and may be evaporated using a hot plate or an oven in an appropriate atmosphere such as air, an inert gas such as nitrogen, or in a vacuum.

  The firing temperature and firing time may be selected in accordance with the process steps of the target electronic device, and the firing conditions may be selected so that the physical properties of the obtained film meet the required characteristics of the electronic device.

  The film made of the triazine ring-containing hyperbranched polyamide of the present invention thus obtained can achieve high heat resistance, high transparency, high refractive index, etc. by itself, so that it can be used for liquid crystal displays, organic electroluminescence (EL ) It can be suitably used as a member for producing electronic devices such as displays, optical semiconductor (LED) elements, solid-state imaging elements, organic thin film solar cells, dye-sensitized solar cells, and organic thin film transistors (TFTs).

EXAMPLES Hereinafter, although a synthesis example and an Example are given and this invention is demonstrated in more detail, this invention is not limited to these Examples. In addition, the used apparatus is as follows.
(1) ¹ H-NMR, ¹³ C-NMR: DRX400 manufactured by BRUKER
(2) FT-IR: FT / IR-4200 type A manufactured by JASCO Corporation
(3) Elemental analysis: MT-6 CHN CORDER manufactured by Yanaco Technical Science Co., Ltd.
(4) GPC: Tosoh Corporation high speed GPC system HLC-8220GPC (column: Tosoh TSK-GEL (α-M), column temperature: 45 ° C., detector: UV-8020, wavelength 254 nm, eluent: N- Methyl-2-pyrrolidone (NMP) (containing 0.01 mol / L lithium bromide), calibration curve: standard polystyrene, column flow rate: 0.2 mL / min)
(5) Differential scanning calorimetry (DSC): X-DSC 7000 manufactured by Hitachi High-Tech Science Corporation
(6) Thermogravimetric analysis (TG / DTA): TG / DTA 7300 manufactured by Hitachi High-Tech Science Corporation
(7) Ultraviolet-visible spectrophotometer: UV-1800 manufactured by Shimadzu Corporation
(8) Refractive index measurement: Metricon MODEL 2010 / M PRISM COUPLER (TM mode: In-plane refractive index)

[1] Synthesis of raw materials [Synthesis Example 1] Synthesis of 6-anilino-1,3,5-triazine-2,4-dichloride (AnTDC)

In a 1,000 mL three-necked flask equipped with a dropping funnel with a side tube, a thermometer, a nitrogen introducing tube and a stirrer, 56.16 g (0.305 mol) of cyanuric chloride and 200 mL of tetrahydrofuran (THF) were placed, and the mixture was placed on an ice bath. The solution was completely dissolved by stirring while cooling to ° C. To this solution, 200 mL of THF in which 28.16 g (0.302 mol) of aniline was dissolved was slowly added dropwise while paying attention to the temperature rise. After completion of the addition, the mixture was stirred at 0 ° C. for 2 hours to be reacted. Thereafter, an aqueous solution prepared by dissolving 19.36 g (0.183 mol) of sodium carbonate in 100 mL of distilled water was slowly added dropwise to this solution while paying attention to the temperature rise. After completion of the addition, the mixture was stirred at 0 ° C. for 2 hours to be reacted. It was.
After completion of the reaction, the reaction mixture was transferred to a separatory funnel and washed three times with 500 mL of saturated brine. The organic phase was transferred to a 1,000 mL Erlenmeyer flask and anhydrous sodium sulfate was added and dehydrated overnight. Sodium sulfate was removed by natural filtration, and the filtrate (THF) was distilled off with an evaporator. It dried under reduced pressure at 80 degreeC for 12 hours, and obtained the crude product as pale yellow solid.
The crude product was recrystallized using a toluene / hexane mixed solvent (toluene / hexane = 2/1), and the obtained crystal was dried under reduced pressure at 80 ° C. for 12 hours to obtain a light yellow solid AnTDC. (Yield: 56.1 g, Yield: 77%). The melting point was 134 ° C. The measurement results of ¹ H-NMR, ¹³ C-NMR and FT-IR are shown below.
¹ H-NMR (400 MHz, DMSO-d6, ppm): δ 7.19 (t, 1H, Ar-H), 7.40 (t, 2H, Ar-H), 7.60 (d, 2H, Ar-H), 11.13 (s, 1H, NH).
¹³ C-NMR (101 MHz, DMSO-d6, ppm): δ 121.0, 125.8, 129.2, 135.6, 164.0, 170.1, 171.3.
FT-IR (KBr, cm ^-1 ): 3371 (NH), 1604 (C = C), 1556 (C = N), 1221 (CN).

[Synthesis Example 2] Synthesis of 6-diphenylamino-1,3,5-triazine-2,4-dichloride (PTDC)

In a 500 mL three-necked flask equipped with a thermometer, a stirrer, a dropping funnel with a side tube, and a nitrogen introducing tube, 250 mL of THF and 55.32 g (0.30 mol) of cyanuric chloride were added and completely dissolved. The solution was cooled to 0 ° C. in an ice bath, and under a nitrogen stream, a solution of 50.76 g (0.30 mol) of diphenylamine dissolved in 100 mL of THF and 30.32 g (0.30 mol) of triethylamine (TEA) were slowly added dropwise. After completion of dropping, the mixture was stirred for 2 hours while maintaining the temperature. Then, it was made to react at room temperature for 24 hours.
After completion of the reaction, the reaction mixture was suction filtered to remove triethylamine hydrochloride, and then THF was removed from the filtrate with an evaporator. The pale yellow solid was dissolved in 300 mL of toluene and washed 3 times with 500 mL of distilled water. This organic layer was transferred to a 500 mL Erlenmeyer flask and dehydrated with anhydrous sodium sulfate overnight. After removing sodium sulfate by filtration, toluene was distilled off by an evaporator to obtain pale yellow crude crystals.
The crude product was recrystallized with a toluene / hexane mixed solvent (toluene / hexane = 2/1), and the obtained crystals were dried under reduced pressure at 80 ° C. for 12 hours to obtain a pale yellow solid PTDC (yield: 28.5 g, yield: 30%). The melting point was 176 ° C. The measurement results of ¹ H-NMR, ¹³ C-NMR and FT-IR are shown below.
¹ H-NMR (400 MHz, CDCl ₃ , TMS, ppm): δ 7.27 (d, 4H, o-Ar-H), 7.32 (t, 2H, p-Ar-H), 7.42 (t, 4H, m -Ar-H).
¹³ C-NMR (101 MHz, CDCl ₃ , TMS, ppm): δ 127.0, 127.4, 129.3, 141.4, 165.7, 170.4.
FT-IR (KBr, cm ^-1 ): 3051 (Ar-H), 1550 (C = N), 1497 (C = C), 1200 (CN).

Synthesis Example 3 Synthesis of 2,4-bis (4-aminoanilino) -6-anilino-1,3,5-triazine (p-ATDA)

To a 1,000 mL three-necked flask equipped with a dropping funnel with a side tube, a Dimroth condenser, a nitrogen inlet tube and a stirrer, 1,4-dioxane 200 mL, sodium carbonate 6.36 g (0.060 mol), and p-phenylenediamine 64.88 g (0.600 mol) was added and dissolved by stirring at 1,4-dioxane reflux temperature. A solution prepared by dissolving 14.46 g (0.060 mol) of AnTDC in 200 mL of 1,4-dioxane was added dropwise to the refluxed solution over 5 hours. Thereafter, stirring was continued for 24 hours at the reflux temperature.
The reaction mixture was washed 4 times with 3 L of hot water (about 70 ° C.) and twice with distilled water. The reaction mixture was recovered by filtration, dissolved in 500 mL of acetone, added with a glass of activated carbon with a spatula, stirred at reflux temperature for 30 minutes to decolorize, and the insoluble matter was filtered. The acetone in the filtrate was distilled off with an evaporator and dried under reduced pressure at 95 ° C. overnight.
The crude product was purified by recrystallization twice using a mixed solvent of 1,4-dioxane / hexane (1,4-dioxane / hexane = 5/1). The obtained powder was dried under reduced pressure at 80 ° C. for 3 hours, and further, the powder was sufficiently crushed and then dried under reduced pressure at 170 ° C. for 6 hours to obtain p-ATDA as a light brown solid (yield: 18.5 g, Yield: 80%). The melting point of p-ATDA was 224 ° C. The measurement results of ¹ H-NMR, ¹³ C-NMR, FT-IR and elemental analysis are shown below.
¹ H-NMR (400 MHz, DMSO-d ₆ , TMS, ppm): δ 4.79 (s, 4H, NH ₂ ), 6.51 (d, 4H, Ar-H), 6.93 (t, 1H, Ar-H) , 7.22 (t, 2H, Ar-H), 7.33 (d, 4H, Ar-H), 7.78 (d, 2H, Ar-H), 8.64 (s, 2H, NH), 8.95 (s, 1H, NH ).
¹³ C-NMR (101 MHz, DMSO-d ₆ , TMS, ppm): δ 113.7, 120.2, 121.4, 122.6, 128.2, 129.0, 140.4, 144.1, 164.0, 164.2.
FT-IR (KBr, cm ^-1 ): 3391 (NH), 1624 (C = C), 1578 (C = N), 1519 (C = C).
Elemental analysis: Calcd.for C ₂₁ H ₂₀ N ₈ : C, 65.61%; H, 5.24%; N, 29.15% .found: C, 65.63%; H, 5.38%; N, 28.97%.

Synthesis Example 4 Synthesis of 2,4-bis (4-aminoanilino) -6-diphenylamino-1,3,5-triazine (p-PTDA)

In a 500 mL three-necked flask equipped with a dropping funnel with a side tube, a Dimroth condenser, a nitrogen inlet tube and a stirrer, 200 mL of 1,4-dioxane, 8.90 g (0.080 mol) of sodium carbonate, 34.62 g of p-phenylenediamine ( 0.32 mol) was added and dissolved by stirring at 1,4-dioxane reflux temperature. A solution dissolved in 100 mL of 1,4-dioxane in which 12.69 g (0.040 mol) of PTDC was dissolved was dropped into the refluxed solution over 5 hours. Thereafter, stirring was continued for 24 hours at the reflux temperature.
The reaction solution was dropped into 3 L of hot water, the precipitate was collected by suction filtration, and washed several times with hot water until the filtrate became colorless and transparent. Thereafter, the precipitate was dried under reduced pressure to remove water.
The precipitate was purified by recrystallization with a 1,4-dioxane single solvent, and the obtained powder was dried under reduced pressure at 80 ° C. for 3 hours. Was dried under reduced pressure at 210 ° C. for 2 hours to obtain p-PTDA as a light brown solid (yield: 13.3 g, yield: 72%). The melting point of p-PTDA was 261 ° C. The measurement results of ¹ H-NMR, ¹³ C-NMR, FT-IR and elemental analysis are shown below.
¹ H-NMR (400 MHz, DMSO-d ₆ , ppm): δ 4.67 (s, 4H, NH ₂ ), 6.32 (d, 4H, Ar-H), 7.07-7.41 (m, 14H, Ar-H) , 8.58 (s, 2H, NH).
¹³ C-NMR (101 MHz, DMSO-d ₆ , ppm): δ 113.5, 121.2, 125.2, 128.1, 128.5, 129.2, 143.2, 144.0, 163.5, 166.0.
FT-IR (KBr, cm ^-1 ): 3410 (NH), 1615 (C = C), 1577 (C = N), 1504 (C = C).
Elemental analysis: Calcd. For C ₂₇ H ₂₄ N ₈ : C, 70.42%; H, 5.25%; N, 24.33%. Found: C, 70.56%; H, 5.35%; N, 24.41%.

Synthesis Example 5 Synthesis of 2,4-bis (3-aminoanilino) -6-anilino-1,3,5-triazine (m-ATDA)

In a 500 mL three-necked flask equipped with a dropping funnel with a side tube, a Dimroth condenser, a nitrogen inlet tube and a stirrer, 1,4-dioxane 400 mL, sodium carbonate 6.57 g (0.062 mol), 3-nitroaniline 17.13 g (0.124 mol) and 14.95 g of AnTDC (0.062 mol) were added to 200 mL of 1,4-dioxane, and the mixture was stirred at reflux temperature for 24 hours and then 2,4-bis (3-nitroanilino) -6-anilino-1,3. , 5-triazine was synthesized.
The reaction solution was cooled to room temperature, dropped into 3 L of tap water, suction filtered, and washed twice with 500 mL of methanol. The precipitate was collected by suction filtration and dried under reduced pressure at 95 ° C. overnight.
To a 500 mL three-necked flask equipped with a three-way cock, a pressure balloon filled with hydrogen, and a Dimroth condenser, 25 g (0.065 mol) of 2,4-bis (3-nitroanilino) -6-anilino-1,3,5-triazine Then, 200 mL of DMF was added and completely dissolved, and 0.66 g (5% by mass) of Pd / C was further added and stirred at room temperature. The operation of “filling with hydrogen and degassing with a vacuum pump” was repeated five times in the flask, and the mixture was placed in a hydrogen atmosphere and stirred at 80 ° C. for 72 hours.
Pd / C was filtered off from the reaction mixture by suction filtration, and added to 3 L of distilled water. The reaction mixture was recovered by filtration, dissolved in 500 mL of acetone, added with a glass of activated carbon with a spatula, stirred at reflux temperature for 30 minutes to decolorize, and the insoluble matter was filtered. The acetone in the filtrate was distilled off with an evaporator and dried under reduced pressure at 95 ° C. overnight.
The crude product was purified by recrystallization twice using a mixed solvent of 1,4-dioxane / water (1,4-dioxane / water = 5/1). The obtained powder was dried under reduced pressure at 80 ° C. for 3 hours, and further, the powder was sufficiently crushed and then dried under reduced pressure at 150 ° C. for 6 hours to obtain a light brown solid m-ATDA (yield: 10.7 g, Yield: 43%). The melting point of m-ATDA was 185 ° C. The measurement results of ¹ H-NMR, ¹³ C-NMR, FT-IR and elemental analysis are shown below.
¹ H-NMR (400 MHz, DMSO-d ₆ , TMS, ppm): δ 4.94 (s, 4H, NH ₂ ), 6.25 (d, 2H, Ar-H), 6.90-6.98 (m, 5H, Ar- H), 7.03 (br, 2H, Ar-H), 7.27 (t, 2H, Ar-H), 7.83 (d, 2H, Ar-H), 8.89 (s, 2H, NH), 9.06 (s, 1H , NH).
¹³ C-NMR (101 MHz, DMSO-d ₆ , ppm): δ 106.8, 108.7, 109.1, 120.1, 121.7, 128.4, 128.7, 140.2, 140.4, 148.6, 164.1, 164.2.
FT-IR (KBr, cm ^-1 ): 3388 (NH), 1603 (C = C), 1580 (C = N), 1230 (CN)
Elemental analysis: Calcd. For C ₂₁ H ₂₀ N ₈ : C, 65.61%; H, 5.24%; N, 29.15% .found: C, 65.62%; H, 5.25%; N, 29.17%.

Synthesis Example 6 Synthesis of 2,4-bis (3-aminoanilino) -6-diphenylamino-1,3,5-triazine (m-PTDA)

In a 500 mL three-necked flask equipped with a dropping funnel with a side tube, a Dimroth condenser, a nitrogen inlet tube and a stirrer, 400 mL of 1,4-dioxane, 6.57 g (0.062 mol) of sodium carbonate, 17.13 g of 3-nitroaniline ( 0.124 mol) and 19.66 g (0.062 mol) of PTDC were added and stirred at reflux temperature for 24 hours to synthesize 2,4-bis (3-nitroanilino) -6-diphenylamino-1,3,5-triazine. did.
The reaction solution was cooled to room temperature, dropped into 3 L of tap water, suction filtered, and washed twice with 500 mL of methanol. The precipitate was collected by suction filtration and dried under reduced pressure at 95 ° C. overnight.
The crude product is dissolved in 500 mL of 1,4-dioxane, the soluble component is concentrated by an evaporator, and then a mixed solvent of 1,4-dioxane / hexane (1,4-dioxane / hexane = 5/1) is used. The resulting powder was dried under reduced pressure at 95 ° C. for 12 hours.
To a 500 mL three-necked flask equipped with a three-way cock, a pressure balloon filled with hydrogen, and a Dimroth condenser, 25 g (0.048 mol) of 2,4-bis (3-nitroanilino) -6-diphenylamino-1,3,5-triazine ), 200 mL of DMF was added and completely dissolved, and 0.66 g (5% by mass) of Pd / C was further added and stirred at room temperature. The operation of “filling with hydrogen and degassing with a vacuum pump” was repeated five times in the flask, and the mixture was placed in a hydrogen atmosphere and stirred at 80 ° C. for 72 hours.
Pd / C was filtered off from the reaction mixture by suction filtration, and added to 3 L of distilled water. The reaction mixture was recovered by filtration, dissolved in 500 mL of acetone, added with a glass of activated carbon with a spatula, stirred at reflux temperature for 30 minutes to decolorize, and the insoluble matter was filtered. The acetone in the filtrate was distilled off with an evaporator and dried under reduced pressure at 95 ° C. overnight.
The crude product was purified by recrystallization twice using a mixed solvent of 1,4-dioxane / water (1,4-dioxane / water = 5/1). The obtained powder was dried under reduced pressure at 80 ° C. for 3 hours, and further, the powder was sufficiently crushed and then dried under reduced pressure at 160 ° C. for 6 hours to obtain a light brown solid m-ATDA (yield: 18.8 g, Yield: 85%). The melting point of m-PTDA was 194 ° C. The measurement results of ¹ H-NMR, ¹³ C-NMR, FT-IR and elemental analysis are shown below.
¹ H-NMR (400 MHz, DMSO-d ₆ , TMS, ppm): δ 4.62 (s, 4H, NH ₂ ), 6.14 (s, 2H, Ar-H), 6.73 (br, 6H, Ar-H) , 7.25 (t, 2H, Ar-H), 7.35-7.44 (m, 8H, Ar-H), 8.82 (s, 2H, NH).
¹³ C-NMR (101 MHz, DMSO-d ₆ , ppm): δ 105.6, 108.2, 108.5, 125.7, 126.4, 128.5, 129.0, 140.5, 144.2, 148.3, 163.8, 166.2.
FT-IR (KBr, cm ^-1 ): 3386 (NH), 3033 (Ar-H), 1549 (C = N), 1498 (C = C).
Elemental analysis: Calcd. For C ₂₇ H ₂₄ N ₈ : C, 70.42%; H, 5.25%; N, 24.33% .found: C, 70.63%; H, 5.28%; N, 24.32%.

Synthesis Example 7 Synthesis of 2-chloro-4,6-dimethoxy-1,3,5-triazine (CDMT)

A 500 mL three-necked flask equipped with a stirrer, a thermometer, a nitrogen inlet tube and a Dimroth condenser tube was charged with 44.2 g (0.525 mol) of sodium bicarbonate and 160 mL of methanol and cooled to 0 ° C. Cyanuric chloride 46.1g (0.25 mol) was added there, and it stirred at 0 degreeC for 5 minutes. Thereafter, the temperature was raised to 20 ° C., and the mixture was stirred in a water bath for 1 hour and further at 60 ° C. for 3.5 hours.
It cooled to room temperature with the water bath, the reaction solution was moved to the 500 mL eggplant flask, and methanol was distilled off with the evaporator. The white solid in the eggplant flask was dissolved in 200 mL of ethyl acetate, transferred to a 1 L separatory funnel, and washed three times with 400 mL of water. The organic phase was put into a 300 mL Erlenmeyer flask, and the organic phase was dehydrated with anhydrous sodium sulfate overnight, then sodium sulfate was removed by natural filtration, and ethyl acetate was distilled off with an evaporator.
The obtained crude product was recrystallized with hexane and dried under reduced pressure at room temperature for 6 hours to obtain CDMT as a white solid (yield: 37.0 g, yield: 84%). The measurement results of ¹ H-NMR, ¹³ C-NMR, FT-IR and elemental analysis are shown below.
¹ H-NMR (400 MHz, CDCl ₃ -d, ppm): δ 4.06 (s, 6H, OCH3).
¹³ C-NMR (101 MHz, CDCl ₃ -d, ppm): δ 56.0 (OCH ₃ ), 172.5 (N = CO), 172.6 (N = C-Cl).
FT-IR (KBr, cm ^-1 ): 2949 (CH), 1560 (C = N), 1363 (NC), 808 (C-Cl).
Elemental analysis: Calcd. For (C ₅ H ₆ ClN ₃ O ₂ ); C 34.20%, H 3.44%, N 23.93, found; C 34.03%, H 3.52%, N 23.61%.

[Synthesis Example 8] Synthesis of 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium chloride (DMT-MM)

A stirrer and 10.0 g (57.0 mmol) of CDMT were placed in a 300 mL eggplant flask and dissolved in THF (160 mL). N-methylmorpholine 5.24g (51.8mmol) was added here, and it stirred at room temperature for 30 minutes.
The precipitate deposited in the reaction solution was collected by suction filtration, and dried under reduced pressure at room temperature for 1 hour to obtain a crude product of DMT-MM as a colorless solid.
The crude product was purified by recrystallization from a methanol / diethyl ether mixed solvent (methanol / diethyl ether = 1/3) and dried under reduced pressure at room temperature overnight to obtain a colorless solid DMT-MM (yield). : 7.89 g, yield: 50%). The melting point of DMT-MM was 115 to 116 ° C. The measurement results of ¹ H-NMR, FT-IR and elemental analysis are shown below.
¹ H-NMR (400 MHz, MeOD-d ₄ , TMS, ppm): 3.53 (s, 3H), 3.81-3.93 (m, 4H), 4.06 (m, 2H), 4.18 (s, 6H), 4.53 ( m, 2H)
FT-IR (KBr, cm ^-1 ): 2987 (CH), 1540 (C = N), 1376 (NC), 1131 (CO).
Elemental analysis: Calcd.for C ₁₀ H ₁₇ ClN ₄ O ₃ : C, 43.40%; H, 6.19%; N, 20.25% .found: C, 43.12%; H, 6.20%; N, 20.08%.

[2] Synthesis of triazine ring-containing hyperbranched polyamide [Example 1] Synthesis of 4-ethynylaniline-terminated triazine ring-containing hyperbranched polyamide (p-AHBPA-4EAn)

A 50 mL two-necked flask equipped with a stirrer, a dropping funnel and a nitrogen inlet tube was dried with a heat gun under a nitrogen stream, and 0.210 g (1.0 mmol) of TMA, 25 mL of NMP, and 0.304 g (3.0 mmol) of TEA were added, After completely dissolving, the mixture was cooled to 0 ° C., 0.830 g (3.3 mmol) of DMT-MM was added, and activation was performed for 30 minutes. Thereafter, 0.384 g (1.0 mmol) of p-ATDA dissolved in 20 mL of NMP was added dropwise over 30 minutes. After completion of dropping, the reaction was carried out at 0 ° C. for 6 hours.
After completion of the reaction, 0.352 g (3.0 mmol) of 4-ethynylaniline was added to the resulting solution, and the mixture was further reacted at 0 ° C. for 3 hours.
The reaction solution was put into 500 mL of methanol to precipitate a polymer. The precipitated polymer was collected by suction filtration and dried under reduced pressure overnight at room temperature. After drying, the polymer was dissolved in 4 mL of DMF and reprecipitated with methanol. The precipitated polymer was collected by suction filtration, and dried under reduced pressure at room temperature overnight to give a pale yellow powder of 4-ethynylaniline-terminated triazine ring-containing hyperbranched polyamide p-AHBPA-4EAn (yield: 0.579 g, yield). : 88%). It was confirmed by ¹ H-NMR measurement that end-capping was completed. The measurement results of FT-IR and GPC are shown below.
FT-IR (KBr, cm ^-1 ): 3287 (NH), 3060 (Ar-H), 1660 (C = O, amido group), 1549 (C = N), 1514 (C = C), 1411 (C = C), 1311 (ArC-N).
GPC: Mn = 20,000, Mw = 83,000, Mw / Mn = 4.2

Example 2 Synthesis of Hyperbranched Polyamide (p-PHBPA-4EAn) Containing 4-Ethynylaniline-Terminated Triazine Ring

A 50 mL two-necked flask equipped with a stirrer, a dropping funnel and a nitrogen introducing tube was dried with a heat gun under a nitrogen stream, and 0.210 g (1.0 mmol) of TMA, 25 mL of NMP, and 0.304 g of TEA (3.0 mmol) were added. After complete dissolution, the solution was cooled to 0 ° C., 0.830 g (3.3 mmol) of DMT-MM was added, and activation was performed for 30 minutes. Thereafter, 0.461 g (1.0 mmol) of p-PTDA dissolved in 20 mL of NMP was added dropwise over 30 minutes. After completion of dropping, the reaction was carried out at 0 ° C. for 6 hours.
After completion of the reaction, 0.352 g (3.0 mmol) of 4-ethynylaniline was added to the resulting solution, and the mixture was further reacted at 0 ° C. for 3 hours.
The reaction solution was put into 500 mL of methanol to precipitate a polymer. The precipitated polymer was collected by suction filtration and dried under reduced pressure overnight at room temperature. After drying, the polymer was dissolved in 4 mL of DMF and reprecipitated with methanol. The precipitated polymer was collected by suction filtration, and dried under reduced pressure at room temperature overnight to obtain 4-brynylaniline-terminated triazine ring-containing hyperbranched polyamide p-PHBPA-4EAn (yield: 0.434 g). Yield: 60%). It was confirmed by ¹ H-NMR measurement that end-capping was completed. The measurement results of FT-IR and GPC are shown below.
FT-IR (KBr, cm ^-1 ): 3299 (NH), 3060 (Ar-H), 1666 (C = O, amido group), 1550 (C = N), 1510 (C = C), 1405 (C = C), 1308 (ArC-N).
GPC: Mn = 20,000, Mw = 107,000, Mw / Mn = 5.3

Example 3 Synthesis of 3-ethynylaniline-terminated triazine ring-containing hyperbranched polyamide (m-AHBPA-3EAn)

A 50 mL two-necked flask equipped with a stirrer, a dropping funnel and a nitrogen introduction tube was dried with a heat gun under a nitrogen stream, and TMA 0.210 g (1.0 mmol), m-ATDA 0.423 g (1.1 mmol), 3-ethynyl Aniline 0.105 g (0.9 mmol), NMP 10 mL, and TEA 0.304 g (3.0 mmol) were added and completely dissolved, then cooled to 0 ° C., and DMT-MM 0.830 g (3.3 mmol) was added at 0 ° C. The reaction was performed for 6 hours.
The reaction solution was concentrated by distillation under reduced pressure and charged into 800 mL of methanol to precipitate a polymer. The precipitated polymer was collected by suction filtration and dried under reduced pressure overnight at room temperature. After drying, the polymer was dissolved in 4 mL of NMP and reprecipitated with methanol. The precipitated polymer was collected by suction filtration, and dried under reduced pressure at room temperature overnight to give a pale yellow powder of 3-ethynylaniline-terminated triazine ring-containing hyperbranched polyamide m-AHBPA-3EAn (yield: 0.451 g, yield). : 66%). It was confirmed by ¹ H-NMR measurement that end-capping was completed. The measurement results of FT-IR and GPC are shown below.
¹ H-NMR (400 MHz, DMSO-d ₆ , ppm): δ10.76-10.78 (NH), 10.42 (NH), 9.33 (NH), 8.67-8.91 (Ar-H), 7.84-7.87 (Ar- H), 7.02-7.51 (Ar-H), 3.87 (≡CH).
FT-IR (KBr, cm ^-1 ): 3291 (≡CH), 3070 (Ar-H), 1664 (C = O amido group), 1548 (C = N), 1507 (C = C), 1415 (C = C), 1305 (ArC-N).
GPC: Mn = 30,000, Mw = 98,000, Mw / Mn = 3.2

[Example 4] Synthesis of hyperbranched polyamide (m-PHBPA-3EAn) containing 3-ethynylaniline-terminated triazine ring

A 50 mL two-necked flask equipped with a stirrer, a dropping funnel and a nitrogen introducing tube was dried with a heat gun under a nitrogen stream, and TMA 0.210 g (1.0 mmol), m-PTDA 0.507 g (1.1 mmol), 3-ethynyl Aniline 0.105 g (0.9 mmol), NMP 10 mL, and TEA 0.304 g (3.0 mmol) were added and completely dissolved, then cooled to 0 ° C., and DMT-MM 0.830 g (3.3 mmol) was added at 0 ° C. The reaction was performed for 6 hours.
The reaction solution was concentrated by distillation under reduced pressure and charged into 800 mL of methanol to precipitate a polymer. The precipitated polymer was collected by suction filtration and dried under reduced pressure overnight at room temperature. After drying, the polymer was dissolved in 4 mL of NMP and reprecipitated with methanol. The precipitated polymer was collected by suction filtration, and dried under reduced pressure at room temperature overnight to give a pale yellow powder of 3-ethynylaniline-terminated triazine ring-containing hyperbranched polyamide m-PHBPA-3EAn (yield: 0.529 g, yield). : 73%). It was confirmed by ¹ H-NMR measurement that end-capping was completed. The measurement results of FT-IR and GPC are shown below.
¹ H-NMR (400 MHz, DMSO-d ₆ , ppm): 10.69 (NH), 10.42 (NH), 9.33 (NH), 8.57-8.80 (Ar-H), 7.01-7.99 (Ar-H), 3.87 (≡CH).
FT-IR (KBr, cm ^-1 ): 3294 (≡CH), 3062 (Ar-H), 1668 (C = O amido group), 1546 (C = N), 1486 (C = C), 1412 (C = C), 1305 (ArC-N).
GPC: Mn = 20,000, Mw = 69,000, Mw / Mn = 3.5

Example 5 Synthesis of 4-ethynylaniline-terminated triazine ring-containing hyperbranched polyamide (m-PHBPA-4EAn)

A 50-mL two-necked flask equipped with a stirrer, a dropping funnel and a nitrogen introduction tube was dried with a heat gun under a nitrogen stream, and TMA 0.210 g (1.0 mmol), m-PTDA 0.507 g (1.1 mmol), 4-ethynyl Aniline 0.105 g (0.9 mmol), NMP 10 mL, and TEA 0.304 g (3.0 mmol) were added and completely dissolved, then cooled to 0 ° C., and DMT-MM 0.830 g (3.3 mmol) was added at 0 ° C. The reaction was performed for 6 hours.
The reaction solution was concentrated by distillation under reduced pressure and charged into 800 mL of methanol to precipitate a polymer. The precipitated polymer was collected by suction filtration and dried under reduced pressure overnight at room temperature. After drying, the polymer was dissolved in 4 mL of NMP and reprecipitated with methanol. The precipitated polymer was collected by suction filtration, and dried under reduced pressure at room temperature overnight, whereby 4-brynylaniline-terminated triazine ring-containing hyperbranched polyamide m-PHBPA-4EAn (yield: 0.486 g, yield) : 67%). It was confirmed by ¹ H-NMR measurement that end-capping was completed. The measurement results of FT-IR and GPC are shown below.
¹ H-NMR (400 MHz, DMSO-d ₆ , ppm): 10.71 (NH), 10.58 (NH), 9.39 (NH), 9.23 (NH), 8.72 (Ar-H), 6.88-8.19 (Ar-H ), 3.95 (≡CH).
FT-IR (KBr, cm ^-1 ): 3290 (≡CH), 3063 (Ar-H), 1666 (C = O amido group), 1548 (C = N), 1510 (C = C), 1410 (C = C), 1307 (ArC-N)
GPC: Mn = 19,000, Mw = 57,000, Mw / Mn = 3.0

[3] Solubility test 5 mL of each of the following solvents was added to the polymers (10 mg) obtained in Examples 1 to 5 and left at room temperature for 24 hours to visually confirm whether or not they were dissolved. Moreover, about what did not melt | dissolve at room temperature, it heated until it became 60 degreeC, and it was confirmed whether it melt | dissolved. Solvents purchased without purification were used as they were. The results are shown in Table 1. In addition, the used solvent is as follows.
N-methyl-2-pyrrolidone (NMP)
N, N-dimethylacetamide (DMAc)
1,3-dimethyl-2-imidazolidinone (DMI)
γ-butyrolactone (γ-BL)
Tetrahydrofuran (THF)
Cyclopentanone (CPN)
Cyclohexanone (CHN)

  As shown in Table 1, all polymers showed good solubility at room temperature in aprotic polar solvents such as NMP and DMAc.

[4] Dissolution test after heat treatment The polymer powder obtained in Examples 1 to 5 was dried under reduced pressure at 100 ° C. for 1 hour and 200 ° C. for 1 hour to prepare a 100 ° C. heat treatment sample and a 200 ° C. heat treatment sample, respectively. did. To the obtained polymer (10 mg), 5 mL of each of the following solvents was added and left at room temperature for 24 hours to visually confirm whether or not the polymer was dissolved. Moreover, about what did not melt | dissolve at room temperature, it heated until it became 60 degreeC, and it was confirmed whether it melt | dissolved. Solvents purchased without purification were used as they were. The results are shown in Table 2. In addition, the used solvent is as follows.
N-methyl-2-pyrrolidone (NMP)
N, N-dimethylacetamide (DMAc)
1,3-dimethyl-2-imidazolidinone (DMI)
γ-butyrolactone (γ-BL)
Tetrahydrofuran (THF)
Cyclopentanone (CPN)
Cyclohexanone (CHN)

  As shown in Table 2, the sample heat-treated at 200 ° C. became insoluble in all the solvents with respect to the solvent that was soluble in the sample heat-treated at 100 ° C. From this, a cross-linking reaction of the ethynyl group occurred by heat treatment at 200 ° C., and an insoluble polymer was generated.

[5] Thermogravimetric analysis The polymer obtained in Examples 1 to 5 was dissolved in DMAc or THF at a concentration of 15% by mass, applied to a glass plate, dried at 200 ° C. under reduced pressure for 1 hour, and peeled off from the glass plate. Thus, a heat-crosslinked polymer was produced.
The glass transition temperature (T _g ) of the thermally crosslinked polymer was measured using DSC at a heating rate of 10 ° C./min. In addition, the 5% weight loss temperature (T _d5 ) and 10% weight loss temperature (T _d10 ) of each polymer were measured at a heating rate of 10 ° C./min (in air or in a nitrogen stream) using TG / DTA. did. Furthermore, the carbonization rate (Char Yield) of each polymer at 800 ° C. was measured under a nitrogen stream. The results are shown in Table 3.

  As shown in Table 3, the glass transition temperature of the thermally crosslinked polymer could not be measured, but the 10% weight loss temperatures in air and nitrogen were 420 ° C to 470 ° C and 429 ° C to 460 ° C, respectively. It showed high heat resistance at ℃.

[6] Light transmission measurement Each polymer obtained in Examples 1 to 5 was dissolved in distilled DMAc or THF to prepare a 15% by mass polymer varnish. This was applied to a quartz plate and heat-treated at 200 ° C. for 1 hour to produce a thermally crosslinked polymer thin film having a strong film thickness shown in Table 4 below. The cut-off wavelength (λ _cutoff ) and 80% transmission wavelength (λ _80% ) of the thermally crosslinked polymer thin film were measured using an ultraviolet-visible spectrophotometer. In addition, the refractive index (n _F , n _d , n _C ) of F-line (486 nm), d-line (588 nm) and C-line (656 nm) of the thermally crosslinked polymer thin film is measured, and the Abbe number (ν) is calculated. did. The results are shown in Table 4.

As shown in Table 4, the cut-off wavelength of the thermally crosslinked polymer thin film was 291 to 384 nm and was excellent in transparency. The refractive index (n _d ) was a sufficiently high value from 1.72 to 1.78. Furthermore, when the solubility test of these thermally crosslinked polymer thin films in DMAc or THF was performed, they were insoluble and strong thin films.

Claims (12)

A triazine ring-containing hyperbranched polyamide containing a structural unit represented by the following formula (1) and having a benzenetricarboxylic acid terminal or amine terminal sealed with an end-capping compound having an ethynyl group.

Wherein R ^{1 to} R ⁴ are each independently a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or an aralkyl group, and R ⁵ and R ⁶ are each independently a hydrogen atom, an alkyl group or an aryl group. In this case, at least one of R ⁵ and R ⁶ is an alkyl group or an aryl group, and Ar ¹ and Ar ² are each independently an arylene group having 6 to 20 carbon atoms.)   The tribranched ring-containing hyperbranched polyamide according to claim 1, wherein the end-capping compound is ethynylaniline. The triazine ring-containing hyperbranched polyamide according to claim 1 or 2, wherein Ar ¹ and Ar ² are phenylene groups. R < ¹ > -R < ⁴ > is a hydrogen atom, The triazine ring containing hyperbranched polyamide of any one of Claims 1-3. R < ⁵ > is a hydrogen atom and R < ⁶ > is a phenyl group, The triazine ring containing hyperbranched polyamide of any one of Claims 1-4. R < ⁵ > and R < ⁶ > are both phenyl groups, The triazine ring containing hyperbranched polyamide of any one of Claims 1-4.   The composition for film formation containing the triazine ring containing hyperbranched polyamide of any one of Claims 1-6.   The film | membrane containing the triazine ring containing hyperbranched polyamide of any one of Claims 1-6.   An electronic device comprising a base material and the film according to claim 8 formed on the base material.   An optical member comprising a substrate and the film according to claim 8 formed on the substrate. By the step of polycondensing a benzenetricarboxylic acid represented by the following formula (3), a diamine compound represented by the following formula (4) and an end-capping compound having an ethynyl group in an organic solvent using a condensing agent. A method for producing a triazine ring-containing hyperbranched polyamide comprising a structural unit represented by the following formula (1) and having a benzenetricarboxylic acid terminal or amine terminal sealed with an end-capping compound having an ethynyl group.

Wherein R ^{1 to} R ⁴ are each independently a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or an aralkyl group, and R ⁵ and R ⁶ are each independently a hydrogen atom, an alkyl group or an aryl group. In this case, at least one of R ⁵ and R ⁶ is an alkyl group or an aryl group, and Ar ¹ and Ar ² are each independently an arylene group having 6 to 20 carbon atoms.) By the step of polycondensing a benzene tricarboxylic acid trihalide represented by the following formula (3 ′), a diamine compound represented by the following formula (4) and an end-capping compound having an ethynyl group in an organic solvent, the following formula: A method for producing a triazine ring-containing hyperbranched polyamide comprising the structural unit represented by (1) and having a benzenetricarboxylic acid terminal or amine terminal sealed with an end-capping compound having an ethynyl group.

Wherein R ^{1 to} R ⁴ are each independently a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or an aralkyl group, and R ⁵ and R ⁶ are each independently a hydrogen atom, an alkyl group or an aryl group. In which at least one of R ⁵ and R ⁶ is an alkyl group or an aryl group, Ar ¹ and Ar ² are each independently an arylene group having 6 to 20 carbon atoms, and X is independently Represents a halogen atom.)