JP2014098101A - Method of producing triazine ring-containing hyperbranched polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of producing a triazine ring-containing hyperbranched polymer, which facilitates reaction control and achieves high volumetric efficiency.SOLUTION: A hyperbranched polymer represented by formula (21) is produced by reacting a compound represented by formula (1) with a compound represented by formula (2). (Rand Reach independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group; X represents a halogen atom; Rto Reach independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group; and Arto Areach independently represent a divalent aryl group.)

Description

  The present invention relates to a method for producing a triazine ring-containing hyperbranched polymer.

  Various attempts have been made to improve the functionality of polymer compounds. For example, in order to increase the refractive index of a polymer compound, an aromatic ring, a halogen atom, or a sulfur atom is introduced. Among these, episulfide polymer compounds and thiourethane polymer compounds into which sulfur atoms are introduced have been put to practical use as high-refractive-index lenses for spectacles.

However, since it is difficult to design a material having a refractive index of more than 1.7 with a polymer alone, a method using an inorganic metal oxide is known as the most effective method capable of achieving a higher refractive index.
For example, a technique for increasing the refractive index using a hybrid material obtained by mixing a siloxane polymer and a fine particle dispersion material in which zirconia or titania is dispersed has been reported (Patent Document 1).
Furthermore, a method of introducing a condensed cyclic skeleton having a high refractive index into a part of the siloxane polymer has also been reported (Patent Document 2).

  There have also been many attempts to impart heat resistance to polymer compounds. Specifically, it is well known that the heat resistance of polymer compounds can be improved by introducing an aromatic ring. Yes. For example, a polyarylene copolymer having a substituted arylene repeating unit in the main chain has been reported (Patent Document 3), and this polymer compound is expected to be applied mainly to heat-resistant plastics.

On the other hand, melamine resin is well known as a triazine resin, but its decomposition temperature is much lower than that of heat-resistant materials such as graphite.
Up to now, aromatic polyimides and aromatic polyamides have been mainly used as heat-resistant organic materials composed of carbon and nitrogen. However, these materials have a linear structure, so that the heat-resistant temperature is not so high.
A triazine-based condensation material has also been reported as a nitrogen-containing polymer material having heat resistance (Patent Document 4).

  By the way, in recent years, electronic devices such as liquid crystal displays, organic electroluminescence (EL) displays, optical semiconductor (LED) elements, solid-state imaging elements, organic thin film solar cells, dye-sensitized solar cells, and organic thin film transistors (TFTs) have been developed. At the same time, high-performance polymer materials have been required.

Specific characteristics required include 1) heat resistance, 2) transparency, 3) high refractive index, and 4) high solubility.
However, the above high-refractive-index lens materials for eyeglasses generally have poor heat resistance and need to be manufactured in a temperature range of 200 ° C. or lower, and thus are not suitable for processes such as baking at 300 ° C. in the atmosphere. is there.
In addition, a polymer compound into which an aromatic ring or a triazine ring is introduced generally lacks solubility in a solvent, and thus is insoluble in a resist solvent, which is a safety solvent, while having high solubility. The materials shown are generally less transparent.

On the other hand, a material using an inorganic metal oxide has a trade-off relationship between a refractive index and transparency, and thus it is difficult to improve transparency while maintaining a high refractive index.
In addition, since this material contains fine particles with different properties, when a dry process such as etching or ashing is performed, the etching rate becomes unstable and it is difficult to form a film with a uniform film thickness. There is also a problem that the process margin becomes narrow.

By the way, hyperbranched polymers are roughly classified into hyperbranched polymers and dendrimers.
The hyperbranched polymer is, for example, a polyfunctional monomer having an irregular branch structure obtained by polymerizing an ABx type polyfunctional monomer (wherein A and B are functional groups that react with each other, and the number X of B is 2 or more). It is a branched polymer.
On the other hand, a dendrimer is a multi-branched polymer having a regular branched structure. Hyperbranched polymers are characterized by being easier to synthesize than dendrimers and easier to synthesize high molecular weight polymers.
A hyperbranched polymer having a triazine ring has been reported as a flame retardant application (Non-patent Document 1).
Further, a method for producing a triazine ring-containing hyperbranched polymer using cyanuric chloride as a raw material is known (Patent Document 5). However, in this method, it is difficult to control the reaction of cyanuric chloride, and a large amount of solvent is required. There was a problem of inefficiency.

JP 2007-246877 A JP 2008-24832 A US Pat. No. 5,886,130 JP 2000-53659 A International Publication No. 2010/128661

Journal of Applied Polymer Science, 106, 95-102 (2007)

  The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for producing a triazine ring-containing hyperbranched polymer with easy reaction control and high volumetric efficiency.

  As a result of intensive studies to achieve the above object, the present inventors have used a dihalogenotriazine compound and a tris (aminoarylamino) triazine compound as a raw material for producing a triazine ring-containing hyperbranched polymer. The present invention was completed by discovering that control is easy and that the polymerization reaction can be performed at a high concentration, so that the volumetric efficiency during the reaction can be increased.

（式中、Ｒ¹およびＲ²は、互いに独立して、水素原子、アルキル基、アルコキシ基、アリール基、またはアラルキル基を表し、Ｘはハロゲン原子を表す。）
で表されるジハロゲノトリアジン化合物と、式（２）

（式中、Ｒ³〜Ｒ⁵は、互いに独立して、水素原子、アルキル基、アルコキシ基、アリール基、またはアラルキル基を表し、Ａｒ¹〜Ａｒ³は、互いに独立して、２価のアリール基を表す。）
で表されるトリス（アミノアリールアミノ）トリアジン化合物とを反応させることを特徴とする式（２１）

（式中、Ｒ¹〜Ｒ⁵およびＡｒ¹〜Ａｒ³は前記と同じ意味を表す。）
で表されるトリアジン環含有ハイパーブランチポリマーの製造方法、
２． 前記Ａｒ¹〜Ａｒ³が、互いに独立して、式（３）〜（１９）からなる群から選ばれる少なくとも１種を表す１のトリアジン環含有ハイパーブランチポリマーの製造方法、

〔式中、Ｒ⁶〜Ｒ¹³³は、互いに独立して、水素原子、ハロゲン原子、カルボキシル基、スルホ基、炭素数１〜１０の分岐構造を有していてもよいアルキル基、または炭素数１〜１０の分岐構造を有していてもよいアルコキシ基を表し、Ｗ¹およびＷ²は、互いに独立して、単結合、ＣＲ¹³⁴Ｒ¹³⁵（Ｒ¹³⁴およびＲ¹³⁵は、互いに独立して、水素原子または炭素数１〜１０の分岐構造を有していてもよいアルキル基（ただし、これらは一緒になって環を形成していてもよい。）を表す。）、Ｃ＝Ｏ、Ｏ、Ｓ、ＳＯ、ＳＯ₂、またはＮＲ¹³⁶（Ｒ¹³⁶は、水素原子または炭素数１〜１０の分岐構造を有していてもよいアルキル基を表す。）を表し、Ｘ¹およびＸ²は、互いに独立して、単結合、炭素数１〜１０の分岐構造を有していてもよいアルキレン基、または式（２０）

（式中、Ｒ¹³⁷〜Ｒ¹⁴⁰は、互いに独立して、水素原子、ハロゲン原子、カルボキシル基、スルホ基、炭素数１〜１０の分岐構造を有していてもよいアルキル基、または炭素数１〜１０の分岐構造を有していてもよいアルコキシ基を表し、Ｙ¹およびＹ²は、互いに独立して、単結合または炭素数１〜１０の分岐構造を有していてもよいアルキレン基を表す。）〕
３． 前記Ａｒ¹〜Ａｒ³が、式（３）で表される２のトリアジン環含有ハイパーブランチポリマーの製造方法、
４． 前記Ｒ¹およびＲ²の一方が、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マーの製造方法、
５． 前記式（１）で表されるジハロゲノトリアジン化合物と、前記式（２）で表されるトリス（アミノアリールアミノ）トリアジン化合物とを、塩基および有機溶媒の存在下、８０〜１５０℃に加熱して反応させる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マーの製造方法、
６． １〜５のいずれかの製造方法で得られるトリアジン環含有ハイパーブランチポリマー、
７． ６のトリアジン環含有ハイパーブランチポリマーを含む薄膜、
８． 式（２２）で示される繰り返し単位を有することを特徴とするトリアジン環含有ハイパーブランチポリマー、

｛式中、Ｒ¹およびＲ²は、互いに独立して、水素原子、アルキル基、アルコキシ基、アリール基、またはアラルキル基を表し、Ｒ³〜Ｒ⁵は、互いに独立して、水素原子、アルキル基、アルコキシ基、アリール基、またはアラルキル基を表し、Ａｒ¹〜Ａｒ³は、互いに独立して、式（３）〜（１９）からなる群から選ばれる少なくとも１種を表す。

〔式中、Ｒ⁶〜Ｒ¹³³は、互いに独立して、水素原子、ハロゲン原子、カルボキシル基、スルホ基、炭素数１〜１０の分岐構造を有していてもよいアルキル基、または炭素数１〜１０の分岐構造を有していてもよいアルコキシ基を表し、Ｗ¹およびＷ²は、互いに独立して、単結合、ＣＲ¹³⁴Ｒ¹³⁵（Ｒ¹³⁴およびＲ¹³⁵は、互いに独立して、水素原子または炭素数１〜１０の分岐構造を有していてもよいアルキル基（ただし、これらは一緒になって環を形成していてもよい。）を表す。）、Ｃ＝Ｏ、Ｏ、Ｓ、ＳＯ、ＳＯ₂、またはＮＲ¹³⁶（Ｒ¹³⁶は、水素原子または炭素数１〜１０の分岐構造を有していてもよいアルキル基を表す。）を表し、Ｘ¹およびＸ²は、互いに独立して、単結合、炭素数１〜１０の分岐構造を有していてもよいアルキレン基、または式（２０）

（式中、Ｒ¹³⁷〜Ｒ¹⁴⁰は、互いに独立して、水素原子、ハロゲン原子、カルボキシル基、スルホ基、炭素数１〜１０の分岐構造を有していてもよいアルキル基、または炭素数１〜１０の分岐構造を有していてもよいアルコキシ基を表し、Ｙ¹およびＹ²は、互いに独立して、単結合または炭素数１〜１０の分岐構造を有していてもよいアルキレン基を表す。）〕｝
９． 式（２３）で示される繰り返し単位を有する８のトリアジン環含有ハイパーブランチポリマー、

１０． ８または９のトリアジン環含有ハイパーブランチポリマーを含む薄膜
を提供する。 That is, the present invention
1. Following formula (1)

(In the formula, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group, and X represents a halogen atom.)
A dihalogenotriazine compound represented by formula (2):

(In the formula, R ^{3 to} R ⁵ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group, and Ar ^{1 to} Ar ³ each independently represent a divalent aryl group. Represents a group.)
A tris (aminoarylamino) triazine compound represented by the formula (21):

(In the formula, R ^{1 to} R ⁵ and Ar ^{1 to} Ar ³ represent the same meaning as described above.)
A method for producing a triazine ring-containing hyperbranched polymer represented by:
2. A process for producing one triazine ring-containing hyperbranched polymer, wherein Ar ^{1 to} Ar ³ independently represent at least one selected from the group consisting of formulas (3) to (19);

[Wherein, R ^{6 to} R ¹³³ are each independently a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group which may have a branched structure having 1 to 10 carbon atoms, or a carbon number of 1 Represents an alkoxy group which may have a branched structure of 1 to 10, W ¹ and W ² are each independently a single bond, CR ¹³⁴ R ¹³⁵ (R ¹³⁴ and R ¹³⁵ are each independently hydrogen; An atom or an alkyl group which may have a branched structure having 1 to 10 carbon atoms (however, they may be combined to form a ring), C = O, O, S , SO, SO ₂ , or NR ¹³⁶ (R ¹³⁶ represents a hydrogen atom or an alkyl group which may have a branched structure having 1 to 10 carbon atoms), and X ¹ and X ² are independent of each other. An alkylene which may have a single bond or a branched structure having 1 to 10 carbon atoms. , Or the formula (20)

(Wherein R ^{137 to} R ¹⁴⁰ are each independently a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group which may have a branched structure having 1 to 10 carbon atoms, or a carbon number of 1 Represents an alkoxy group which may have a branched structure of 1 to 10, Y ¹ and Y ² each independently represent an alkylene group which may have a single bond or a branched structure of 1 to 10 carbon atoms. Represents))]
3. A method for producing a triazine ring-containing hyperbranched polymer of 2 wherein Ar ^{1 to} Ar ³ are represented by formula (3),
4). A method for producing a triazine ring-containing hyperbranched polymer according to any one of 1 to 3, wherein ^one of R ¹ and R ² is a hydrogen atom,
5. The dihalogenotriazine compound represented by the formula (1) and the tris (aminoarylamino) triazine compound represented by the formula (2) are heated to 80 to 150 ° C. in the presence of a base and an organic solvent. A method for producing a triazine ring-containing hyperbranched polymer according to any one of 1 to 4,
6). A triazine ring-containing hyperbranched polymer obtained by any one of production methods 1 to 5,
7). A thin film comprising 6 triazine ring-containing hyperbranched polymers;
8). A triazine ring-containing hyperbranched polymer having a repeating unit represented by the formula (22):

{Wherein, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group, and R ^{3 to} R ⁵ each independently represent a hydrogen atom, an alkyl group, or an alkyl group. A group, an alkoxy group, an aryl group, or an aralkyl group, and Ar ^{1 to} Ar ³ each independently represent at least one selected from the group consisting of formulas (3) to (19).

[Wherein, R ^{6 to} R ¹³³ are each independently a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group which may have a branched structure having 1 to 10 carbon atoms, or a carbon number of 1 Represents an alkoxy group which may have a branched structure of 1 to 10, W ¹ and W ² are each independently a single bond, CR ¹³⁴ R ¹³⁵ (R ¹³⁴ and R ¹³⁵ are each independently hydrogen; An atom or an alkyl group which may have a branched structure having 1 to 10 carbon atoms (however, they may be combined to form a ring), C = O, O, S , SO, SO ₂ , or NR ¹³⁶ (R ¹³⁶ represents a hydrogen atom or an alkyl group which may have a branched structure having 1 to 10 carbon atoms), and X ¹ and X ² are independent of each other. An alkylene which may have a single bond or a branched structure having 1 to 10 carbon atoms. , Or the formula (20)

(Wherein R ^{137 to} R ¹⁴⁰ are each independently a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group which may have a branched structure having 1 to 10 carbon atoms, or a carbon number of 1 Represents an alkoxy group which may have a branched structure of 1 to 10, Y ¹ and Y ² each independently represent an alkylene group which may have a single bond or a branched structure of 1 to 10 carbon atoms. Represents))}
9. 8 triazine ring-containing hyperbranched polymers having repeating units of the formula (23),

10. A thin film comprising 8 or 9 triazine ring-containing hyperbranched polymers is provided.

The method for producing a triazine ring-containing hyperbranched polymer of the present invention has advantages that the reaction is easy to control because a halogenated cyanuric compound is not used as a raw material, and that the volumetric efficiency is high because a polymerization reaction can be performed at a high concentration.
The triazine ring-containing hyperbranched polymer obtained by the production method of the present invention has characteristics of high heat resistance, high transparency, high refractive index, high solubility, and low volume shrinkage.
The hyperbranched polymer of the present invention is formed into a thin film, thereby enabling a touch panel, 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, a dye-sensitized solar cell, an organic It can be suitably used as an electronic device such as a thin film transistor (TFT) or a member for producing organic EL lighting.
In particular, a buried film and a planarizing film on a photodiode, a planarizing film before and after a color filter, a microlens, and a planarizing film and a conformal film on a microlens, which are members of a solid-state imaging device that requires a high refractive index. Can be suitably used.

1 is a ¹ H-NMR spectrum diagram of pHBPG obtained in Example 1. FIG. 2 is a ¹ H-NMR spectrum of mHBPG obtained in Example 2. FIG. 2 is a ¹ H-NMR spectrum diagram of pHBPG-A obtained in Example 3. FIG. 4 is a ¹ H-NMR spectrum diagram of mHBPG-A obtained in Example 4. FIG. 2 is a ¹ H-NMR spectrum diagram of pHBPG-B obtained in Example 5. FIG. 2 is a ¹ H-NMR spectrum diagram of mHBPG-B obtained in Example 6. FIG. 2 is a ¹ H-NMR spectrum diagram of pHBPG-P obtained in Example 7. FIG. 4 is a ¹ H-NMR spectrum diagram of mHBPG-P obtained in Example 8. FIG.

Hereinafter, the present invention will be described in more detail.
As described above, the method for producing a triazine ring-containing hyperbranched polymer according to the present invention includes a dihalogenotriazine compound represented by the formula (1) and a tris (aminoarylamino) triazine compound represented by the formula (2): To obtain a hyperbranched polymer represented by the formula (21).

  As this method, for example, as shown in Scheme 1, a dihalogenotriazine compound of the formula (1) and a tris (aminoarylamino) triazine compound of the formula (2) are reacted in an appropriate organic solvent. And a method leading to a hyperbranched polymer of the formula (21), and as shown in Scheme 2, a dihalogenotriazine compound of the formula (1) and a tris (aminoarylamino) triazine compound of the formula (2), etc. After making it a molar reaction intermediate, the method of polymerizing this and leading to the hyperbranched polymer of formula (21) can be mentioned. In particular, in view of an industrial viewpoint, the production method according to Scheme 1 that can be synthesized in a short process is more preferable.

（式中、Ｒ¹〜Ｒ⁵、Ａｒ¹〜Ａｒ³は上記と同じ意味を表す。）

(In the formula, R ^{1 to} R ⁵ and Ar ^{1 to} Ar ³ represent the same meaning as described above.)

（式中、Ｒ¹〜Ｒ⁵、Ａｒ¹〜Ａｒ³は上記と同じ意味を表す。）

(In the formula, R ^{1 to} R ⁵ and Ar ^{1 to} Ar ³ represent the same meaning as described above.)

In the methods of Schemes 1 and 2, the amount of each raw material charged is arbitrary as long as the desired hyperbranched polymer is obtained, but the amount of the formula (2) relative to 1 equivalent of the dihalogenotriazine compound of the formula (1) The tris (aminoarylamino) triazine compound is preferably 0.01 to 10 equivalents.
In the production method of the present invention, the molecular weight of the obtained hyperbranched polymer can be easily adjusted by appropriately adjusting the amount of each raw material.

As the organic solvent used for the reaction, various solvents usually used for this kind of reaction can be used. For example, ether solvents such as tetrahydrofuran and dioxane; dimethyl sulfoxide; N, N-dimethylformamide, 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, 1,3-dimethyl-2-imidazolidinone, N, N-dimethylpropionic acid amide, N, N-dimethylisobutyramide, N-methylformamide, N, N′-dimethylpro Amide solvents such as alkylene urea, and mixed solvents thereof.
Among these, N, N-dimethylformamide, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolidinone, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, and a mixed system thereof are preferable. N-dimethylacetamide, N-methyl-2-pyrrolidone, and mixtures thereof are preferred.

  In the reactions of Schemes 1 and 2, the reaction temperature may be appropriately set in the range from the melting point of the solvent to be used to the boiling point of the solvent, but is preferably about 0 to 200 ° C., and the second stage of Scheme 1 and Scheme 2 In the reaction of 80, 150 to 150 ° C. is more preferable, and in the first stage reaction of Scheme 2, 0 to 50 ° C. is more preferable.

In each of the above reactions, the blending order of each component is arbitrary, but in any reaction, the tris (aminoarylamino) triazine compound of the formula (2) is dissolved in an organic solvent, and the compound of the formula (1) is dissolved therein. A method of adding a halogenotriazine compound is preferred.
Components added later may be added neat or in a solution dissolved in an organic solvent as described above, but the latter method is preferred in view of ease of operation and ease of reaction control. It is.
The addition may be gradually added by dropping or the like, or may be added all at once.

In the reactions of Schemes 1 and 2 and the second stage reaction of Scheme 2, various bases usually used at the time of polymerization or after polymerization may be added.
Specific examples of the base include potassium carbonate, potassium hydroxide, sodium carbonate, sodium hydroxide, sodium bicarbonate, sodium ethoxide, sodium acetate, lithium carbonate, lithium hydroxide, lithium oxide, potassium acetate, magnesium oxide, calcium oxide. , Barium hydroxide, trilithium phosphate, trisodium phosphate, tripotassium phosphate, cesium fluoride, aluminum oxide, ammonia, trimethylamine, triethylamine, diisopropylamine, diisopropylethylamine, N-methylpiperidine, 2,2,6, Examples include 6-tetramethyl-N-methylpiperidine, pyridine, 4-dimethylaminopyridine, N-methylmorpholine, and the like. These may be used alone or in combination of two or more.
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 the dihalogenotriazine compound of the formula (1). These bases may be used as an aqueous solution.
In any of the scheme methods, after completion of the reaction, the product can be easily purified by a reprecipitation method or the like.
In the polymer obtained, it is preferable that no raw material components remain, but some raw materials may remain as long as the effects of the present invention are not impaired.

  The tris (aminoarylamino) triazine compound of the formula (2) and the dihalogenotriazine compound of the formula (1) used as raw materials are prepared by a known method using a cyanuric halide such as cyanuric chloride and a diarylamine compound or an amine compound. It can be obtained by reaction.

Next, the substituent will be described.
In the above formula (1), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group.
In the present invention, the number of carbon atoms of the alkyl group is not particularly limited, but is preferably 1 to 20, and more preferably 1 to 10 carbon atoms in view of further improving the heat resistance of the polymer. Is even more preferable. Further, the structure may be any of a chain, a branch, and a ring.

  Specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, s-butyl, t-butyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl. N-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2 , 2-dimethyl-n-propyl, 1-ethyl-n-propyl, cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclobutyl, 1,2-dimethyl-cyclopropyl, 2,3- Dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, n-hexyl, 1-methyl-n-pen 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3- Dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n- Butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, Cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclo Til, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl-cyclobutyl, 2,4-dimethyl-cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl 2-n-propyl-cyclopropyl, 1-isopropyl-cyclopropyl, 2-isopropyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2, 3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl, 2-ethyl-3-methyl-cyclopropyl Groups and the like.

  Although it does not specifically limit as carbon number of the said alkoxy group, 1-20 are preferable, when it considers raising the heat resistance of a polymer more, C1-C10 is more preferable, and 1-3 are much more. preferable. Further, the structure of the alkyl moiety may be any of a chain, a branch, and a ring.

  Specific examples of the alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, s-butoxy, t-butoxy, n-pentoxy, 1-methyl-n-butoxy, 2-methyl-n. -Butoxy, 3-methyl-n-butoxy, 1,1-dimethyl-n-propoxy, 1,2-dimethyl-n-propoxy, 2,2-dimethyl-n-propoxy, 1-ethyl-n-propoxy, n -Hexyloxy, 1-methyl-n-pentyloxy, 2-methyl-n-pentyloxy, 3-methyl-n-pentyloxy, 4-methyl-n-pentyloxy, 1,1-dimethyl-n-butoxy, 1,2-dimethyl-n-butoxy, 1,3-dimethyl-n-butoxy, 2,2-dimethyl-n-butoxy, 2,3-dimethyl-n-butoxy 3,3-dimethyl-n-butoxy, 1-ethyl-n-butoxy, 2-ethyl-n-butoxy, 1,1,2-trimethyl-n-propoxy, 1,2,2-trimethyl-n-propoxy 1-ethyl-1-methyl-n-propoxy, 1-ethyl-2-methyl-n-propoxy group and the like.

Although it does not specifically limit as carbon number of the said aryl group, 6-40 are preferable, and when it considers raising the heat resistance of a polymer more, 6-16 are more preferable, and 6-13 are much more preferable.
Specific examples of the aryl group include phenyl, o-chlorophenyl, m-chlorophenyl, p-chlorophenyl, o-fluorophenyl, p-fluorophenyl, o-methoxyphenyl, p-methoxyphenyl, p-nitrophenyl, p-cyanophenyl, α-naphthyl, β-naphthyl, o-biphenylyl, m-biphenylyl, p-biphenylyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4 -Phenanthryl, 9-phenanthryl group, etc. are mentioned.

Although it does not specifically limit as carbon number of an aralkyl group, C7-C20 is preferable and the linear, branched, and cyclic | annular form may be sufficient as the alkyl part.
Specific examples thereof include benzyl, p-methylphenylmethyl, m-methylphenylmethyl, o-ethylphenylmethyl, m-ethylphenylmethyl, p-ethylphenylmethyl, 2-propylphenylmethyl, 4-isopropylphenylmethyl, Examples include 4-isobutylphenylmethyl, α-naphthylmethyl group and the like.

Among these, as R ¹ and R ² , one is preferably a hydrogen atom and the other is an aryl group, and a combination of a hydrogen atom and a phenyl group is more preferable.
X represents a halogen atom, and examples of the halogen atom include fluorine, chlorine, bromine and iodine atoms. Among them, a chlorine atom is preferable.
Suitable examples of the compound represented by the formula (1) include, but are not limited to, those represented by the following formula.

（式中、Ａｒは、アリール基を表す。）

(In the formula, Ar represents an aryl group.)

（式中、Ｒは、水素原子、塩素原子、フッ素原子、メトキシ基、ニトロ基またはシアノ基を表す。）

(In the formula, R represents a hydrogen atom, a chlorine atom, a fluorine atom, a methoxy group, a nitro group or a cyano group.)

On the other hand, in the above formula (2), R ^{3 to} R ⁵ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group. Specific examples of these groups are as described above. Although the same thing is mentioned, Preferably it is a hydrogen atom.
Ar ^{1 to} Ar ³ represent a divalent aryl group, and specific examples thereof are not particularly limited, but in the present invention, in particular, from the groups represented by formulas (3) to (19) At least one selected is preferred.
Ar ^{1 to} Ar ³ may be different groups, or two may be the same group and the remaining groups may be different, or all may be the same group. Then, it is preferable that all are the same, and it is particularly preferable that all of Ar ^{1 to} Ar ³ are phenylene groups represented by the formula (3).

R ^{6 to} R ¹³³ are each independently a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group which may have a branched structure having 1 to 10 carbon atoms, or a carbon atom having 1 to 10 carbon atoms. Represents an alkoxy group which may have a branched structure, W ¹ and W ² are each independently a single bond, CR ¹³⁴ R ¹³⁵ (R ¹³⁴ and R ¹³⁵ are each independently a hydrogen atom or carbon; An alkyl group optionally having a branched structure of 1 to 10 (note that these may be combined to form a ring), C = O, O, S, SO, SO ₂ or NR ^136, (R ¹³⁶ represents. an alkyl group which may have a hydrogen atom or a branched structure having 1 to 10 carbon atoms) represent,
Examples of the alkyl group, alkoxy group, and halogen atom are the same as those described above.

X ¹ and X ² each independently represent a single bond, an alkylene group which may have a branched structure having 1 to 10 carbon atoms, or a group represented by the formula (20).

R ^{137 to} R ¹⁴⁰ are each independently a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group which may have a branched structure having 1 to 10 carbon atoms, or a carbon number having 1 to 10 carbon atoms. Represents an alkoxy group which may have a branched structure, Y ¹ and Y ² each independently represent a single bond or an alkylene group which may have a branched structure having 1 to 10 carbon atoms, Examples of the halogen atom, alkyl group and alkoxy group are the same as described above.
Examples of the alkylene group that may have a branched structure having 1 to 10 carbon atoms include methylene, ethylene, propylene, trimethylene, tetramethylene, and pentamethylene groups.

  Specific examples of the aryl group represented by the above formulas (3) to (19) include those represented by the following formula, but are not limited thereto.

  Among these, an aryl group represented by the following formula is more preferable because a polymer having a higher refractive index can be obtained.

In addition, a rigid structure having a cyclic skeleton such as a fluorene skeleton or a carbazole skeleton is preferable because the aryl portion tends to gather densely and the electron density is improved from the standpoint of developing a high refractive index. Since the benzene ring also has a small structure, the aryl portion is easy to gather densely, which is preferable because the electron density is improved.
In addition, as a linking group of a benzene ring such as W ¹ , a functional group such as a carbonyl-containing group or an amine having a high hydrogen bonding ability forms a hydrogen bond with a hydrogen atom of another amine moiety in the polymer. It is preferable because the aryl portions are more likely to gather densely and the electron density is improved.
From the above viewpoint, an aryl group represented by the following formula is preferable.

In view of further improving the solubility in a highly safe solvent such as a resist solvent, the aryl group is preferably a benzene ring (phenylene group).
Suitable examples of the compound represented by the formula (2) include, but are not limited to, those represented by the following formula.

（式中、Ｒ³〜Ｒ⁵は、上記と同じ意味を表す。）

(Wherein R ^{3 to} R ⁵ represent the same meaning as described above.)

（式中、Ｒ³〜Ｒ⁵は、上記と同じ意味を表す。）

(Wherein R ^{3 to} R ⁵ represent the same meaning as described above.)

  Accordingly, suitable repeating unit structures of the obtained hyperbranched polymer include those represented by the following formulas, particularly those represented by formulas (23) to (25), but are not limited thereto. is not.

（式中、ＲおよびＲ³〜Ｒ⁵は、上記と同じ意味を表す。）

(In the formula, R and R ^{3 to} R ⁵ have the same meaning as described above.)

The weight average molecular weight (Mw) of the triazine ring-containing hyperbranched polymer obtained by the production method of the present invention is not particularly limited, but is preferably 500 to 500,000, more preferably 500 to 100,000. 2,000 or more are preferable from the viewpoint of improving heat resistance and reducing the shrinkage rate, and 50,000 or less is preferable from the viewpoint of further improving the solubility and decreasing the viscosity of the obtained solution. 1,000 or less is more preferable, and 10,000 or less is even more preferable.
The weight average molecular weight (Mw) and the number average molecular weight (Mn) are average molecular weights obtained in terms of standard polystyrene by gel permeation chromatography (hereinafter referred to as GPC) analysis.
Moreover, the refractive index at 550 nm of the hyperbranched polymer is preferably 1.65 or more, more preferably 1.70 or more, still more preferably 1.75 or more, and further preferably 1.80 or more.

In the hyperbranched polymer of the present invention, a part of at least one terminal amino group may be capped with an alkyl, aralkyl, aryl, acyl, imide group, etc., among which capped with an acyl group or an imide group. It is preferable. By capping (part of) the terminal amino group, the solubility of the hyperbranched polymer in the organic solvent can be further improved.
Specific examples of the acyl group include acetyl and benzoyl groups.
Specific examples of the imide group include maleimide and phthalimide groups.
Specific examples of the aralkyl group include benzyl, p-methylphenylmethyl, m-methylphenylmethyl, o-ethylphenylmethyl, m-ethylphenylmethyl, p-ethylphenylmethyl, 2-propylphenylmethyl, 4-isopropylphenyl. Examples thereof include methyl, 4-isobutylphenylmethyl, α-naphthylmethyl group and the like.
Examples of the alkyl group include the same groups as those described above.

These groups can be easily introduced by using a compound that binds to the terminal amino group and gives the corresponding cap structure. For example, as shown in Scheme 3, the hyperbranched polymer of formula (21) is dehydrated. By treating with acetic acid, a hyperbranched polymer (25) in which at least one terminal amino group is capped with an acetyl group is obtained.
At this time, the reaction conditions are not particularly limited, and conventionally known conditions may be used.

（式中、Ｒ¹〜Ｒ⁵、Ａｒ¹〜Ａｒ³は上記と同じ意味を表す。）

(In the formula, R ^{1 to} R ⁵ and Ar ^{1 to} Ar ³ represent the same meaning as described above.)

The triazine ring-containing hyperbranched polymer of the present invention described above can be suitably used as a material for a film-forming composition, and can be particularly suitably used as a polymer varnish in which the polymer is dissolved in various solvents.
The solvent used for dissolving the hyperbranched polymer may be the same as or different from the solvent used during the polymerization.

  Specific examples of such solvents include toluene, p-xylene, o-xylene, m-xylene, ethylbenzene, styrene, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol, propylene glycol monoethyl ether. , Ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol methyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, diethylene glycol diethyl ether, dipro Lenglycol monomethyl ether, diethylene glycol monomethyl ether, dipropylene glycol monoethyl ether, diethylene glycol monoethyl ether, triethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol, 1-octanol, ethylene glycol, hexylene glycol, trimethylene glycol, 1 -Methoxy-2-butanol, cyclohexanol, diacetone alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, propylene glycol, benzyl alcohol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, γ-butyrolactone, acetone, methyl ethyl ketone, methyl isopropyl keto , Diethyl ketone, methyl isobutyl ketone, methyl normal butyl ketone, cyclohexanone, ethyl acetate, isopropyl acetate, normal propyl acetate, isobutyl acetate, normal butyl acetate, ethyl lactate, methanol, ethanol, isopropanol, tert-butanol, allyl alcohol, normal Propanol, 2-methyl-2-butanol, isobutanol, normal butanol, 2-methyl-1-butanol, 1-pentanol, 2-methyl-1-pentanol, 2-ethylhexanol, 1-octanol, ethylene glycol, Hexylene glycol, trimethylene glycol, 1-methoxy-2-butanol, diacetone alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, propylene glycol Benzyl alcohol, tetrahydrofuran, 1,4-dioxane, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, N-cyclohexyl-2-pyrrolidinone and the like are mentioned. From the viewpoint of the solubility and storage stability of the polymer, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monobutyl ether are more preferable. And cyclohexanone. These may be used alone or in combination of two or more.

  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 40% by mass.

In this invention, unless the effect of this invention is impaired, other components other than a hyperbranched polymer and a solvent, for example, a leveling agent, surfactant, a crosslinking agent, etc. may be contained.
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 Polyoxyethylene alkyl allyl ethers such as ethers; polyoxyethylene / polyoxypropylene block copolymers; sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate Sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethyleneso Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as bitane monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, trade name EFTOP EF301, EF303, EF352 (Mitsubishi Materials Electronic Chemicals Co., Ltd. (formerly Gemco Co., Ltd.), trade names MegaFuck F171, F173, R-08, R-30 (DIC Co., Ltd.), Florard FC430, FC431 (Sumitomo) Fluorosurfactants such as 3M Co., Ltd., trade names Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd.), and organosiloxane polymers P341 (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 (BIC Chemie Japan) Etc.).

  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 still more preferably 0.01 to 0.5 parts by mass with respect to 100 parts by mass of the hyperbranched polymer. preferable.

As a cross-linking agent, a melamine compound having a cross-linking substituent such as a methylol group or a methoxymethyl group, a substituted urea compound, a compound containing a cross-linking substituent such as an epoxy group or an oxetane group, or a blocked isocyanate A compound having an acid anhydride, a compound having a (meth) acryl group, a phenoplast compound, and the like. From the viewpoint of heat resistance and storage stability, an epoxy group, a blocked isocyanate group, and a (meth) acryl group are included. The compound to contain is preferable, and especially the compound which has a block isocyanate group, and the polyfunctional epoxy compound and / or polyfunctional (meth) acryl compound which give the composition which can be photocured without using an initiator are preferable.
These compounds only need to have at least one crosslink-forming substituent when used for the terminal treatment of the hyperbranched polymer, and at least two crosslinkers when used for the cross-linking treatment between hyperbranched polymers. It is necessary to have a substituent.

The polyfunctional epoxy compound is not particularly limited as long as it has two or more epoxy groups in one molecule.
Specific examples thereof 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, pentaerythris Ritol polyglycidyl ether and the like can be mentioned.

  In addition, as commercially available products, epoxy resins having at least two epoxy groups, YH-434, YH434L (manufactured by Tohto Kasei Co., Ltd.), epoxy resins having a cyclohexene oxide structure, Epolide GT-401 and GT -403, GT-301, GT-302, Celoxide 2021, 3000 (manufactured by Daicel Chemical Industries, Ltd.), bisphenol A type epoxy resin, Epicoat (currently jER) 1001, 1002, 1003, 1004, 1007, 1009, 1010, 828 (Japan Epoxy Resin Co., Ltd.), Bisphenol F type epoxy resin, Epicoat (currently jER) 807 (Japan Epoxy Resin Co., Ltd.) , Epicote (currently a phenol novolac type epoxy resin) jER) 152, 154 (above, manufactured by Japan Epoxy Resin Co., Ltd.), EPPN 201, 202 (above, manufactured by Nippon Kayaku Co., Ltd.), cresol novolac type epoxy resin, EOCN-102, 103S, 104S, 1020, 1025, 1027 (Nippon Kayaku Co., Ltd.), Epicort (currently jER) 180S75 (Japan Epoxy Resin Co., Ltd.), alicyclic epoxy resin, Denacol EX- 252 (manufactured by Nagase ChemteX Corp.), CY175, CY177, CY179 (above, made by CIBA-GEIGY A.G), Araldite CY-182, CY-192, CY-184 (above, CIBA-GEIGY A. G), Epicron 200, 400 (above, manufactured by DIC Corporation), Epicort (currently jER) 87 872 (above, manufactured by Japan Epoxy Resin Co., Ltd.), ED-5661, ED-5862 (above, manufactured by Celanese Coating Co., Ltd.), aliphatic polyglycidyl ether, Denacol EX-611, EX- 612, EX-614, EX-622, EX-411, EX-512, EX-522, EX-522, EX-421, EX-313, EX-314, EX-321 (Nagase ChemteX) Etc.) can also be used.

The polyfunctional (meth) acrylic compound is not particularly limited as long as it has two or more (meth) acrylic groups in one molecule.
Specific examples include ethylene glycol diacrylate, ethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, ethoxylated bisphenol A diacrylate, ethoxylated bisphenol A dimethacrylate, ethoxylated trimethylolpropane triacrylate, and ethoxylated. Trimethylolpropane trimethacrylate, ethoxylated glycerol triacrylate, ethoxylated glycerol trimethacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetramethacrylate, ethoxylated dipentaerythritol hexaacrylate, polyglycerol monoethylene oxide polyacrylate, polyglycerol Polyethylene Glycol polyacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, Examples include tricyclodecane dimethanol diacrylate, tricyclodecane dimethanol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, and the like.

  In addition, the polyfunctional (meth) acrylic compound can be obtained as a commercial product, and specific examples thereof include NK ester A-200, A-400, A-600, A-1000, A-1000. 9300 (tris (2-acryloyloxyethyl) isocyanurate), A-9300-1CL, A-TMPT, UA-53H, 1G, 2G, 3G, 4G, 9G, 14G, 23G, ABE-300, A-BPE-4, A-BPE-6, A-BPE-10, A-BPE-20, A-BPE-30, BPE-80N, BPE- 100N, BPE-200, BPE-500, BPE-900, BPE-1300N, A-GLY-3E, A-GLY-9E, A-GLY-20E, A-TMPT-3EO, Same AT PT-9EO, ATM-4E, ATM-35E (manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD (registered trademark) DPEA-12, PEG400DA, THE-330, RP-1040 (above, Nippon Kayaku Co., Ltd.), M-210, M-350 (above, Toagosei Co., Ltd.), KAYARAD (registered trademark) DPHA, NPGDA, PET 30 (above, Nippon Kayaku Co., Ltd.) NK ester A-DPH, A-TMPT, A-DCP, A-HD-N, TMPT, DCP, NPG, HD-N (above, Shin-Nakamura Chemical Co., Ltd.), NK oligo U-15HA (manufactured by Shin-Nakamura Chemical Co., Ltd.), NK polymer vanaresin GH-1203 (manufactured by Shin-Nakamura Chemical Co., Ltd.), and the like.

  The acid anhydride compound is not particularly limited as long as it is a carboxylic acid anhydride obtained by dehydration condensation of two molecules of carboxylic acid. Specific examples thereof include phthalic anhydride, tetrahydrophthalic anhydride, hexahydroanhydride. One in the molecule such as phthalic acid, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, maleic anhydride, succinic anhydride, octyl succinic anhydride, dodecenyl succinic anhydride Having an acid anhydride group; 1,2,3,4-cyclobutanetetracarboxylic dianhydride, pyromellitic anhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene Succinic dianhydride, bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic dianhydride, 5- (2,5-di Xoxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 1,2,3,4-butanetetracarboxylic dianhydride, 3,3 ′, 4,4 ′ -Benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 1, Examples thereof include those having two acid anhydride groups in the molecule such as 3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride.

  As a compound containing a blocked isocyanate, when the isocyanate group (—NCO) has two or more blocked isocyanate groups blocked by an appropriate protective group in one molecule, and is exposed to a high temperature during thermosetting The protective group (block part) is not particularly limited as long as it is dissociated by thermal dissociation and the resulting isocyanate group causes a crosslinking reaction with the resin. For example, a group represented by the following formula Examples thereof include compounds having two or more in the molecule (note that these groups may be the same or different from each other).

（式中、Ｒ_bはブロック部の有機基を表す。）

(In the formula, R _b represents an organic group in the block part.)

Such a compound can be obtained, for example, by reacting an appropriate blocking agent with a compound having two or more isocyanate groups in one molecule.
Examples of the compound having two or more isocyanate groups in one molecule include, for example, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, methylene bis (4-cyclohexyl isocyanate), polyisocyanate of trimethylhexamethylene diisocyanate, and dimers thereof. , Trimers, and reaction products of these with diols, triols, diamines, or triamines.
Examples of the blocking agent include alcohols such as methanol, ethanol, isopropanol, n-butanol, 2-ethoxyhexanol, 2-N, N-dimethylaminoethanol, 2-ethoxyethanol, and cyclohexanol; phenol and o-nitrophenol. , P-chlorophenol, phenols such as o-, m- or p-cresol; lactams such as ε-caprolactam, oximes such as acetone oxime, methyl ethyl ketone oxime, methyl isobutyl ketone oxime, cyclohexanone oxime, acetophenone oxime, benzophenone oxime And pyrazoles such as pyrazole, 3,5-dimethylpyrazole and 3-methylpyrazole; thiols such as dodecanethiol and benzenethiol.

  A compound containing a blocked isocyanate is also available as a commercial product. Specific examples thereof include B-830, B-815N, B-842N, B-870N, B-874N, B-882N, B -7005, B-7030, B-7075, B-5010 (Mitsui Chemical Polyurethane Co., Ltd.), Duranate (registered trademark) 17B-60PX, TPA-B80E, MF-B60X, MF-K60X, E402-B80T (above, manufactured by Asahi Kasei Chemicals Corporation), Karenz MOI-BM (registered trademark) (above, manufactured by Showa Denko Co., Ltd.), and the like.

The aminoplast compound is not particularly limited as long as it has two or more methoxymethylene groups in one molecule. For example, hexamethoxymethylmelamine CYMEL (registered trademark) 303, tetrabutoxymethylglycoluril 1170 Cymel series such as Tetramethoxymethylbenzoguanamine 1123 (manufactured by Nippon Cytec Industries, Ltd.), Nicalac (registered trademark) MW-30HM, which is a methylated melamine resin, MW-390, MW-100LM, Examples thereof include melamine compounds such as MX-750LM, Nicarac series such as MX-270 and MX-280, which are methylated urea resins, and MX-280 and MX-290 (manufactured by Sanwa Chemical Co., Ltd.).
The oxetane compound is not particularly limited as long as it has two or more oxetanyl groups in one molecule. For example, OXT-221, OX-SQ-H, OX-SC containing oxetane groups (above And Toa Gosei Co., Ltd.).

The film-forming composition can be applied to a substrate, then heated as necessary to evaporate the solvent, and then heated or irradiated with light to form a desired cured 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 be used.
The firing temperature is not particularly limited for the purpose of evaporating the solvent, and can be performed at 40 to 400 ° C., for example.
The baking method is not particularly limited, and for example, it 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 conditions for the light irradiation are not particularly limited, and an appropriate irradiation energy and time may be adopted depending on the triazine ring-containing polymer and the crosslinking agent to be used.

  The film containing the hyperbranched polymer of the present invention thus obtained can achieve high heat resistance, high transparency, high refractive index, high solubility, and low volume shrinkage, so that a liquid crystal display, organic electroluminescence ( EL), a touch panel, an optical semiconductor (LED) element, a solid-state imaging element, an organic thin film solar cell, a dye-sensitized solar cell, an organic thin film transistor (TFT), etc. In particular, a buried film and a planarizing film on a photodiode, a planarizing film before and after a color filter, a microlens, and a planarizing film and a conformal film on a microlens, which are members of a solid-state imaging device that requires a high refractive index. Can be suitably used.

[ ¹ H-NMR]
Apparatus: Bruker AC400P NMR (400 MHz with hydrogen nucleus)
Measurement solvent: CDCl ₃ -d ₁ or DMSO-d ₆
Reference substance: Tetramethylsilane (TMS) (δ0.0ppm)
[ ¹³ C-NMR]
Apparatus: Bruker AC400P NMR (100 MHz with carbon nucleus)
Measurement solvent: CDCl ₃ -d ₁ or DMSO-d ₆
Reference substance: Tetramethylsilane (TMS) (δ0.0ppm)
[GPC]
Equipment: HLC-8220 GPC manufactured by Tosoh Corporation
Column: Tosoh α-M double-connected Column temperature: 40 ° C
Solvent: NMP (including 0.01M LiBr)
Detector: UV (254 nm)
Calibration curve: Standard polystyrene [Ellipsometer]
Apparatus: Multi-angle-of-incidence spectroscopic ellipsometer VASE manufactured by JA Woollam Japan
[Differential thermal balance (TG-DTA)]
Apparatus: Seiko Instruments Inc. SCC5200 TG / DTA 320
Temperature increase rate: 10 ° C / min Measurement temperature: 25-800 ° C
[DSC]
Device: DSC-60 manufactured by Shimadzu Corporation
Temperature increase rate: 20 ° C / min

[1] Synthesis of Triazine Triamine [Synthesis Example 1] Synthesis of 2,4,6-tris (p-aminoanilino) 1,3,5-triazine (1) 2,4,6-tris (p-nitroanilino) 1 Of 3,3,5-triazine

Cyanuric chloride (18.4 g, 100 mmol), 4-nitroaniline (41.4 g, 300 mmol) and 1,4-dioxane (300 mL) were placed in a 500 mL three-necked flask equipped with a stir bar, Dimroth and calcium chloride tube. After stirring and dissolving, the mixture was heated to reflux for 12 hours.
The reaction solution was poured into a large amount of water, and the precipitate was collected by suction filtration. The collected precipitate was dried at 150 ° C. under reduced pressure to obtain a crude product.
The crude product was placed in tetrahydrofuran (hereinafter referred to as THF) and refluxed with heating, filtered and dried under reduced pressure at 150 ° C. to obtain a purified product.

Shape: yellow powder crystal Yield: 45.0 g
Yield: 92%
Decomposition point: 476-477 ° C
¹ H-NMR (400 MHz, DMSO-d ₆ , δ (ppm))
8.12 (d, 6H, o-Ar-H), 8.23 (d, 6H, m-Ar-H), 10.32 (d, 3H, NH)
¹³ C-NMR (101 MHz, DMSO-d ₆ , δ (ppm))
119.93, 125.15, 141.84, 146.58, 164.30
Elemental analysis
Calcd. For C ₂₁ H ₁₅ N ₉ O ₆
Calcd. C: 51.54, H: 3.09, N: 25.76 (%)
Found C: 51.71, H: 3.29, N: 25.50 (%)

(2) Synthesis of 2,4,6-tris (p-aminoanilino) 1,3,5-triazine

Into a 500 mL three-necked flask equipped with a Dimroth, a stirrer, a three-way cock and a hydrogen balloon, DMF (300 mL) and the 2,4,6-tris (p-nitroanilino) -1,3,5- Triazine (24.5 g, 50.0 mmol) and palladium carbon (5%) (3.0 g) were added and dissolved by stirring. Then, hydrogen was charged into the system, heated at 80 ° C., and stirred for 72 hours. did.
The reaction solution was suction filtered to remove palladium carbon, the filtrate was poured into a large amount of water, and the precipitate was collected by suction filtration. The collected precipitate was dried at 150 ° C. under reduced pressure to obtain a crude product.
The crude product was dissolved in THF, filtered through celite, the filtrate was concentrated with an evaporator and dried under reduced pressure at 100 ° C. Activated carbon and dioxane (200 mL) were added to the crude product, and the mixture was heated to reflux for 1 hour, and then the filtrate was concentrated again with an evaporator. This operation was repeated three times to perform decolorization. The crude product was dried under reduced pressure at 150 ° C. and further recrystallized with a 1,4-dioxane / water mixed solvent to obtain a purified product.

Shape: Pale yellow powder crystal Yield: 8.0 g
Yield: 40%
Melting point: 291-293 ° C
¹ H-NMR (400 MHz, DMSO-d ₆ , δ (ppm))
4,74 (s, 6H, NH ₂ ), 6.48 (d, 6H, o-Ar-H), 7.33 (d, 6H, m-Ar-H), 8.48 (s, 3H, NH)
¹³ C-NMR (101 MHz, DMSO-d ₆ , δ (ppm))
114.23, 122.72, 129.8, 144.23, 164.50
Elemental analysis
Calcd. For C ₂₁ H ₂₁ N ₉
Calcd. C: 63.14, H: 5.30, N: 31.56 (%)
Found C: 63.15, H: 5.42, N: 31.48 (%)

Synthesis Example 2 Synthesis of 2,4,6-tris (m-aminoanilino) -1,3,5-triazine (1) 2,4,6-tris (m-nitroanilino) -1,3,5-triazine Synthesis of

  A purified product of the target compound was obtained in the same manner as in Synthesis Example 1 (1) except that 4-nitroaniline was changed to 3-nitroaniline.

Shape: Pale yellow powder crystal Yield: 44.0 g
Yield: 90%
Melting point: 323-324 ° C
¹ H-NMR (400 MHz, DMSO-d ₆ , δ (ppm))
7.57-7.62 (t, 3H, o-Ar-H), 7.86-7.89 (m, 3H, m-Ar-H), 8.22 (s, 3H, o-Ar-H), 8.64 (s, 3H, p -Ar-H), 9.96 (s, 3H, NH)
¹³ C-NMR (101 MHz, DMSO-d ₆ , δ (ppm))
115.0, 117.2, 126.8, 130.3, 141.2, 148.4, 164.5

(2) Synthesis of 2,4,6-tris (m-aminoanilino) -1,3,5-triazine

  2,4,6-tris (p-nitroanilino) -1,3,5-triazine was changed to 2,4,6-tris (m-nitroanilino) -1,3,5-triazine obtained above. Except for the above, a purified product of the target product was obtained in the same manner as in Synthesis Example 1 (2).

Shape: White powder Yield: 12.0 g
Yield: 60%
Melting point: 138-140 ° C
¹ H-NMR (400 MHz, DMSO-d ₆ , δ (ppm))
4.93 (s, 6H, Ar-NH ₂ ), 6.22-6.25 (m, 3H, Ar-H), 6.91-6.93 (t, 6H, Ar-H), 7.09 (s, 3H, o-Ar-H) , 8.78 (s, 3H, NH)
¹³ C-NMR (101 MHz, DMSO-d ₆ , δ (ppm))
107.1, 109.0, 109.4, 129.1, 140.1, 149.0, 164.5
Elemental analysis
Calcd. For C ₂₁ H ₂₁ N ₉
Calcd. C: 63.14, H: 5.30, N: 31.56 (%)
Found C: 62.93, H: 5.48, N: 31.44 (%)

[2] Synthesis of triazine dichloride [Synthesis Example 3] Synthesis of 6-anilino-1,3,5-triazine-2,4-dichloride

Cyanuric chloride (18.4 g, 100 mmol) and THF (100 mL) were added to a 300 mL three-necked flask equipped with a stirrer, a dropping funnel with a side tube, a thermometer, and a calcium chloride tube, and completely dissolved. I let you. Aniline (9.31 g, 100 mmol) dissolved in THF (100 mL) was slowly added dropwise thereto, followed by stirring at room temperature for 2 hours. Thereafter, sodium carbonate (5.30 g, 50.0 mmol) dissolved in distilled water was slowly added dropwise, and the mixture was further stirred for 2 hours. After confirming that the reaction solution was neutral, the reaction was terminated.
The reaction solution was separated with saturated brine, and the organic layer was recovered. Anhydrous magnesium sulfate was added, and the mixture was stirred overnight and dehydrated. The filtrate was recovered by natural filtration, and THF was distilled off with an evaporator to obtain a crude product.
The crude product was recrystallized with a toluene / hexane mixed solvent, and the obtained crystal was dried under reduced pressure at 80 ° C. for 12 hours to obtain a purified product.

Shape: White needle crystal Yield: 22.0 g
Yield: 91%
Melting point: 137-138 ° C
¹ H-NMR (400 MHz, CDCl ₃ , TMS, δ (ppm))
7.22 (t, 1H, p-Ar-H), 7.40 (t, 2H, m-Ar-H), 7.53 (d, 2H, o-Ar-H), 7.86 (s, 1H, NH)
¹³ C-NMR (101 MHz, CDCl ₃ , δ (ppm))
121.0, 125.8, 129.2, 135.6, 164.0, 170.1, 171.3
FT-IR (KBr (cm ^-1 ))
3353 (NH), 1609 (C = C), 1552 (C = N), 1219 (CN)
Elemental analysis
Calcd. For C ₉ H ₆ Cl ₂ N ₄
Calcd. C: 44.84, H: 2.51, N: 23.24 (%)
Found C ： 45.09, H ： 2.55, N ： 23.05 (%)

[3] Synthesis of triazine-based hyperbranched polymer [Example 1] Synthesis of pHBPG

A 100 mL three-necked flask equipped with a stirrer, a condenser and a nitrogen introduction tube was replaced with a nitrogen stream, and then 2,4,6-tris (p-aminoanilino) -1,3 obtained in Synthesis Example 1 was used. , 5-triazine (0.40 g, 1.0 mmol) was placed in the flask and completely dissolved in NMP (10 mL). Further, 6-anilino-1,3,5-triazine-2,4-dichloride (0.24 g, 1.0 mmol) obtained in Synthesis Example 3 was added, and the mixture was stirred at room temperature for 4 hours and then raised to 110 ° C. Warmed and stirred for 12 hours.
After completion of the reaction, the reaction solution was poured into dilute aqueous ammonia, and the precipitate was collected by suction filtration. The obtained precipitate was washed with water, filtered, and dried under reduced pressure with a desiccator. After drying, it was dissolved in NMP (10 mL), reprecipitated with methanol, and dried again under reduced pressure with a desiccator to obtain white powdery pHBPG (0.36 g, 64%). The number average molecular weight (Mn) by GPC of pHBPG was 8,700, the weight average molecular weight (Mw) was 50,000, and the polydispersity Mw / Mn was 5.7.
The ¹ H-NMR spectrum of the obtained pHBPG is shown in FIG.

[Example 2] Synthesis of mHBPG

2,4,6-tris (p-aminoanilino) -1,3,5-triazine was converted to 2,4,6-tris (m-aminoanilino) -1,3,5-triazine obtained in Synthesis Example 2. A white powdery mHBPG (0.34 g, 59%) was obtained in the same manner as in Example 1 except for the change.
The number average molecular weight (Mn) of mHBPG by GPC was 6,500, the weight average molecular weight (Mw) was 12,000, and the polydispersity Mw / Mn was 1.9.
The ¹ H-NMR spectrum of the obtained mHBPG is shown in FIG.

[4] Synthesis of terminally modified triazine ring-containing hyperbranched polymer [Example 3] Synthesis of pHBPG-A (acetylated pHBPG)

After completion of the reaction of Example 1, the reaction solution was allowed to cool to room temperature, acetic anhydride (0.31 g, 3.0 mmol) was added, and the mixture was stirred at 100 ° C. for 3 hr.
The reaction solution was poured into dilute aqueous ammonia, and the precipitate was collected by suction filtration. The obtained precipitate was washed with water, filtered, and dried under reduced pressure with a desiccator. After drying, it was dissolved in NMP (10 mL), reprecipitated with methanol, and dried again under reduced pressure with a desiccator to obtain pHBPG-A (0.36 g, 59%) as a white powder. The number average molecular weight (Mn) by GPC of pHBPG-A was 10,000, the weight average molecular weight (Mw) was 45,000, and the polydispersity Mw / Mn was 4.4.
The ¹ H-NMR spectrum of the resulting pHBPG-A is shown in FIG.

Example 4 Synthesis of mHBPG-A (acetylated mHBPG)

After completion of the reaction in Example 2, the same operation as in Example 3 was performed to obtain mHBPG-A (0.25 g, 41%) as a white powder. The number average molecular weight (Mn) of mHBPG-A by GPC was 9,200, the weight average molecular weight (Mw) was 17,000, and the polydispersity Mw / Mn was 1.8.
The ¹ H-NMR spectrum of the obtained mHBPG-A is shown in FIG.

[Example 5] Synthesis of pHBPG-B (benzoylated pHBPG)

After completion of the reaction in Example 1, the reaction solution was cooled to 0 ° C. in an ice bath, benzoyl chloride (0.42 g, 3.0 mmol) was added, and the mixture was stirred at room temperature for 3 hours, and reprecipitation was performed from acetone. In the same manner as in Example 3, white powdery pHBPG-B (0.32 g, 48%)
Got. The number average molecular weight (Mn) by GPC of pHBPG-B was 8,300, the weight average molecular weight (Mw) was 45,000, and the polydispersity Mw / Mn was 5.4.
The ¹ H-NMR spectrum of the obtained pHBPG-B is shown in FIG.

Example 6 Synthesis of mHBPG-B (benzoylated mHBPG)

After completion of the reaction of Example 2, the same operation as in Example 5 was performed to obtain mHBPG-B (0.24 g, 36%) as a white powder.
The number average molecular weight (Mn) by mPC of mHBPG-B was 8,000, the weight average molecular weight (Mw) was 14,000, and the polydispersity Mw / Mn was 1.8.
The ¹ H-NMR spectrum of the obtained mHBPG-B is shown in FIG.

[Example 7] Synthesis of pHBPG-P (phthalimidated pHBPG)

After the reaction of Example 1 was completed, the reaction solution was allowed to cool to room temperature, phthalic anhydride (0.44 g, 3.0 mmol) was added, and the mixture was stirred at room temperature for 2 hours, and then pyridine (0.08 g, 1.0 mmol) and Acetic anhydride (0.31 g, 3.0 mmol) was added, and the mixture was stirred at room temperature, 40 ° C., 60 ° C., and 80 ° C. for 2 hours each, and further at 100 ° C. for 12 hours.
The reaction solution was poured into water, and the precipitate was collected by suction filtration and dried under reduced pressure with a desiccator. After drying, it was dissolved in NMP (10 mL), reprecipitated with acetone, and again dried under reduced pressure with a desiccator to obtain a light yellow powdery pHBPG-P (0.40 g, 57%). The number average molecular weight (Mn) by GPC of pHBPG-P was 11,200, the weight average molecular weight (Mw) was 33,000, and the polydispersity Mw / Mn was 3.0.
The ¹ H-NMR spectrum of the obtained pHBPG-P is shown in FIG.

[Example 8] Synthesis of mHBPG-P (phthalimidized mHBPG)

After completion of the reaction of Example 2, the same operation as in Example 7 was performed to obtain mHBPG-P (0.32 g, 46%) as a pale yellow powder. The number average molecular weight (Mn) of mHBPG-P by GPC was 8,200, the weight average molecular weight (Mw) was 13,000, and the polydispersity Mw / Mn was 1.6.
The ¹ H-NMR spectrum of the obtained mHBPG-P is shown in FIG.

[5] Solubility test 10 mg of each hyperbranched polymer obtained in each of the above examples was dissolved in 5 mL of various organic solvents at room temperature, the solubility was confirmed, and evaluated according to the following criteria. The results are shown in Table 1.
+: Dissolution ±: Partial dissolution or swelling-: Insoluble

ＮＭＰ：Ｎ−メチル−２−ピロリドン
ＤＭＳＯ：ジメチルスルホキシド
ＤＭＡｃ：Ｎ，Ｎ−ジメチルアセトアミド
γ−ＢＬ：γ−ブチロラクトン
ＣＨ：シクロヘキサノン
ＴＨＦ：テトラヒドロフラン

NMP: N-methyl-2-pyrrolidone DMSO: dimethyl sulfoxide DMAc: N, N-dimethylacetamide γ-BL: γ-butyrolactone CH: cyclohexanone THF: tetrahydrofuran

  As shown in Table 1, it can be seen that the meta type is more excellent in solubility in organic solvents than the para type hyperbranched polymer. Further, it can be seen that in both the para type and the meta type, the terminal modification improves the solubility in an organic solvent, and in particular, in the meta type, the solubility improves with increasing solubility in cyclohexanone and THF.

[6] For each hyperbranched polymer obtained in various physical properties measured above embodiments, the glass transition temperature (T _g), the heat resistance in air and in nitrogen [5% weight loss temperature (T ₅₎ and 10% by weight Decrease temperature, (T ₁₀ )], cutoff wavelength (λ _cutoff ) and refractive index (n _D ) at 589 nm were measured. The results are summarized in Table 2.
The cut-off wavelength and the refractive index were measured using a polymer thinned by the following procedure.
[Production of thin film]
The hyperbranched polymer obtained in each of the above examples was dissolved in NMP to prepare a polymer varnish. The obtained polymer varnish was spin-coated on a quartz plate or glass plate at 200 rpm for 60 seconds using a spin coater, baked at 100 ° C. for 30 minutes to remove the solvent, and a 400-1000 nm thin film was produced.

a)Determined by DSC in nitrogen at a heating rate of 20 ℃/min. b)5wt% and 10wt% decomposition temperatures determined by TG at a heating rate 10 ℃/min. c) Cutoff wavelength. d)Refractive index at 589 nm.

a) Determined by DSC in nitrogen at a heating rate of 20 ° C / min.b) 5wt% and 10wt% decomposition temperatures determined by TG at a heating rate 10 ° C / min.c) Cutoff wavelength.d) Refractive index at 589 nm .

  As shown in Table 2, it can be seen that the hyperbranched polymer obtained in each example has excellent heat resistance, good transparency, and high refractive index.

Claims (10)

Following formula (1)

(In the formula, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group, and X represents a halogen atom.)
A dihalogenotriazine compound represented by formula (2):

(In the formula, R ^{3 to} R ⁵ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group, and Ar ^{1 to} Ar ³ each independently represent a divalent aryl group. Represents a group.)
A tris (aminoarylamino) triazine compound represented by the formula (21):

(In the formula, R ^{1 to} R ⁵ and Ar ^{1 to} Ar ³ represent the same meaning as described above.)
The manufacturing method of the triazine ring containing hyperbranched polymer represented by these. The method for producing a triazine ring-containing hyperbranched polymer according to claim ^1, wherein Ar ^{1 to} Ar ³ independently represent at least one selected from the group consisting of formulas (3) to (19).

[Wherein, R ^{6 to} R ¹³³ are each independently a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group which may have a branched structure having 1 to 10 carbon atoms, or a carbon number of 1 Represents an alkoxy group optionally having 10 to 10 branched structures,
W ¹ and W ² are each independently a single bond, CR ¹³⁴ R ¹³⁵ (R ¹³⁴ and R ¹³⁵ may be independently of each other a hydrogen atom or a branched structure having 1 to 10 carbon atoms. Alkyl group (however, these may be combined to form a ring)), C═O, O, S, SO, SO ₂ , or NR ¹³⁶ (R ¹³⁶ is a hydrogen atom or Represents an alkyl group which may have a branched structure having 1 to 10 carbon atoms),
X ¹ and X ² are each independently a single bond, an alkylene group which may have a branched structure having 1 to 10 carbon atoms, or the formula (20)

(Wherein R ^{137 to} R ¹⁴⁰ are each independently a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group which may have a branched structure having 1 to 10 carbon atoms, or a carbon number of 1 Represents an alkoxy group optionally having 10 to 10 branched structures,
Y ¹ and Y ² each independently represent an alkylene group which may have a single bond or a branched structure having 1 to 10 carbon atoms. )] The method for producing a triazine ring-containing hyperbranched polymer according to claim 2, wherein Ar ^{1 to} Ar ³ are represented by Formula (3). One of said R < ¹ > and R < ² > is a hydrogen atom, The manufacturing method of the triazine ring containing hyperbranched polymer of any one of Claims 1-3.   The dihalogenotriazine compound represented by the formula (1) and the tris (aminoarylamino) triazine compound represented by the formula (2) are heated to 80 to 150 ° C. in the presence of a base and an organic solvent. The method for producing a triazine ring-containing hyperbranched polymer according to any one of claims 1 to 4.   A triazine ring-containing hyperbranched polymer obtained by the production method according to claim 1.   A thin film comprising the triazine ring-containing hyperbranched polymer according to claim 6. A triazine ring-containing hyperbranched polymer having a repeating unit represented by the formula (22):

{Wherein, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group.
R ^{3 to} R ⁵ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group, and Ar ^{1 to} Ar ³ independently of each other represent formulas (3) to (19) Represents at least one selected from the group consisting of

[Wherein, R ^{6 to} R ¹³³ are each independently a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group which may have a branched structure having 1 to 10 carbon atoms, or a carbon number of 1 Represents an alkoxy group optionally having 10 to 10 branched structures,
W ¹ and W ² are each independently a single bond, CR ¹³⁴ R ¹³⁵ (R ¹³⁴ and R ¹³⁵ may be independently of each other a hydrogen atom or a branched structure having 1 to 10 carbon atoms. Alkyl group (however, these may be combined to form a ring)), C═O, O, S, SO, SO ₂ , or NR ¹³⁶ (R ¹³⁶ is a hydrogen atom or Represents an alkyl group which may have a branched structure having 1 to 10 carbon atoms),
X ¹ and X ² are each independently a single bond, an alkylene group which may have a branched structure having 1 to 10 carbon atoms, or the formula (20)

(Wherein R ^{137 to} R ¹⁴⁰ are each independently a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group which may have a branched structure having 1 to 10 carbon atoms, or a carbon number of 1 Represents an alkoxy group optionally having 10 to 10 branched structures,
Y ¹ and Y ² each independently represent an alkylene group which may have a single bond or a branched structure having 1 to 10 carbon atoms. )]} The triazine ring-containing hyperbranched polymer according to claim 8 having a repeating unit represented by the formula (23).

  A thin film comprising the triazine ring-containing hyperbranched polymer according to claim 8 or 9.

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