JP2012097175A - Triazine ring-containing polymer and film-forming composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a triazine ring-containing polymer which achieves high heat resistance, high transparency, high refractive index, high solubility, and low volume shrinkage by itself without addition of a metal oxide, and to provide a film-forming composition containing the triazine ring-containing polymer.SOLUTION: A polymer containing a repeating unit structure having a triazine ring, for example a repeating unit structure represented by formula (20) exerts high heat resistance, high transparency, high refractive index, high solubility, and low volume shrinkage by itself.

Description

  The present invention relates to a triazine ring-containing polymer and a film-forming composition containing the same.

  Various attempts have been made to improve the functionality of polymer compounds. For example, as a method for increasing the refractive index of a polymer compound, attempts have been made to introduce an aromatic ring, a halogen atom, or a sulfur atom. 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 exceeding 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, but 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).

Recently, 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, 4) high solubility, and 5) low volume shrinkage.
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 etch rate becomes unstable and it is difficult to obtain 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, an ABx type polyfunctional monomer (where A and B are functional groups that react with each other, and the number X of B is 2 or more) that has an irregular branched structure obtained by polymerizing. It is a branched polymer.
On the other hand, a dendrimer is a highly 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).

JP 2007-246877 A JP 2008-24832 A US Pat. No. 5,886,130 JP 2000-53659 A

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

  The present invention has been made in view of the above circumstances, and a triazine that can achieve high heat resistance, high transparency, high refractive index, high solubility, and low volume shrinkage by itself without adding a metal oxide. An object of the present invention is to provide a ring-containing polymer and a film-forming composition containing the same.

The present inventors have found that a hyperbranched polymer including a repeating unit having a triazine ring and an aromatic ring has a refractive index exceeding 1.7, and the polymer alone has high heat resistance, high transparency, high refractive index, and high solubility. It has already been found that it can achieve low volume shrinkage and is suitable as a film-forming composition for producing electronic devices (PCT / JP2010 / 057761).
Based on this knowledge, the present inventors have conducted further studies. As a result, the triazine ring polymer having a thioether bond at the linking site in the main chain exhibits a high refractive index and good solubility in various organic solvents. As a result, the present invention was completed.

〔式中、Ａｒは、芳香環および複素環のいずれか一方または双方を含む２価の有機基を表す。〕
２． 前記Ａｒが、式（２）〜（１８）で示され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重合体、

〔式中、Ｒ¹〜Ｒ¹²⁸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、スルホン基、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、ＣＲ¹²⁹Ｒ¹³⁰（Ｒ¹²⁹およびＲ¹³⁰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ＮＲ¹³¹（Ｒ¹³¹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（１９）

（式中、Ｒ¹³²〜Ｒ¹³⁵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、スルホン基、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。）
で示される基を表す。〕
３． 前記Ａｒが、前記式（９）、（１０）、（１２）および（１３）で示される群から選ばれる少なくとも１種である２のトリアジン環含有重合体、
４． 前記式（９）および（１０）中におけるＷ¹およびＷ²が、Ｓである３のトリアジン環含有重合体、
５． 前記繰り返し単位構造が、式（２０）で示される１のトリアジン環含有重合体、

６． 少なくとも１つの末端が、アルキル基、アラルキル基、アリール基、アルキルアミノ基、アルコキシシリル基含有アルキルアミノ基、アラルキルアミノ基、アリールアミノ基、アルコキシ基、アラルキルオキシ基、アリールオキシ基、アルキルチオ基、アラルキルチオ基、アリールチオ基、またはエステル基でキャップされている１〜５のいずれかのトリアジン環含有重合体、
７． 少なくとも１つのトリアジン環末端を有し、このトリアジン環末端が、アルキル基、アラルキル基、アリール基、アルキルアミノ基、アルコキシシリル基含有アルキルアミノ基、アラルキルアミノ基、アリールアミノ基、アルコキシ基、アラルキルオキシ基、アリールオキシ基、アルキルチオ基、アラルキルチオ基、アリールチオ基、またはエステル基でキャップされている６のトリアジン環含有重合体、
８． １〜７のいずれかのトリアジン環含有重合体を含む膜形成用組成物、
９． ８の膜形成用組成物から得られる膜、
１０． １〜７のいずれかのトリアジン環含有重合体を含む膜、
１１． 基材と、この基材上に形成された９または１０の膜とを備える電子デバイス、
１２． 基材と、この基材上に形成された９または１０の膜とを備える光学部材、
１３． ９または１０の膜を少なくとも１層備える、電荷結合素子または相補性金属酸化膜半導体からなる固体撮像素子、
１４． ９または１０の膜をカラーフィルター上の平坦化層として備える固体撮像素子、
１５． ８の膜形成用組成物からなる、固体撮像素子用レンズ材料、平坦化材料または埋め込み材料
を提供する。 That is, the present invention
1. A triazine ring-containing polymer comprising a repeating unit structure represented by the following formula (1):

[In the formula, Ar represents a divalent organic group containing one or both of an aromatic ring and a heterocyclic ring. ]
2. 1 triazine ring-containing polymer in which Ar represents at least one selected from the group represented by formulas (2) to (18);

[Wherein, R ^{1 to} R ¹²⁸ are each independently a hydrogen atom, a halogen atom, a carboxyl group, a sulfone group, an alkyl group which may have a branched structure having 1 to 10 carbon atoms, or 1 carbon atom. 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 ¹²⁹ R ¹³⁰ (R ¹²⁹ and R ¹³⁰ 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 ¹³¹ (R ¹³¹ 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. And an alkyle which may have a single bond or a branched structure having 1 to 10 carbon atoms. Group, or a group of the formula (19)

(In the formula, R ^{132 to} R ¹³⁵ are each independently a hydrogen atom, a halogen atom, a carboxyl group, a sulfone group, an alkyl group which may have a branched structure of 1 to 10 carbon atoms, or 1 carbon atom. 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. To express.)
Represents a group represented by ]
3. 2 triazine ring-containing polymers, wherein Ar is at least one selected from the group represented by formulas (9), (10), (12) and (13),
4). 3 triazine ring-containing polymers in which W ¹ and W ² in the above formulas (9) and (10) are S,
5. The triazine ring-containing polymer having one repeating unit structure represented by the formula (20):

6). At least one terminal is an alkyl group, aralkyl group, aryl group, alkylamino group, alkoxysilyl group-containing alkylamino group, aralkylamino group, arylamino group, alkoxy group, aralkyloxy group, aryloxy group, alkylthio group, aralkyl Any one of the triazine ring-containing polymers capped with a thio group, an arylthio group, or an ester group;
7). Having at least one triazine ring end, and the triazine ring end is an alkyl group, an aralkyl group, an aryl group, an alkylamino group, an alkoxysilyl group-containing alkylamino group, an aralkylamino group, an arylamino group, an alkoxy group, an aralkyloxy group 6 triazine ring-containing polymers capped with groups, aryloxy groups, alkylthio groups, aralkylthio groups, arylthio groups, or ester groups,
8). A film-forming composition comprising the triazine ring-containing polymer of any one of 1 to 7;
9. A film obtained from the film-forming composition of 8;
10. A film comprising any one of the triazine ring-containing polymers of 1 to 7,
11. An electronic device comprising a substrate and 9 or 10 films formed on the substrate;
12 An optical member comprising a substrate and 9 or 10 films formed on the substrate;
13. A solid-state imaging device comprising a charge-coupled device or a complementary metal oxide semiconductor, comprising at least one layer of 9 or 10;
14 A solid-state imaging device comprising 9 or 10 films as a planarizing layer on a color filter;
15. The lens material for a solid-state image sensor, the planarization material, or the embedding material which consists of a film forming composition of 8 is provided.

According to the present invention, it is possible to provide a triazine ring-containing polymer that can achieve high heat resistance, high transparency, high refractive index, high solubility, and low volume shrinkage independently without using a metal oxide.
By using the polymer skeleton of the present invention, high heat resistance and high transparency can be maintained even when a thioether bond is used as a polymer spacer.
The hyperbranched polymer of the present invention exhibits a high refractive index because the triazine ring and the aryl (Ar) portion are gathered densely and the sulfur atom content is increased by adopting a hyperbranched structure. It is thought that.
Moreover, although it is a high molecular weight compound, it is excellent in solubility in various organic solvents, and also has excellent handling properties because it has a low viscosity when dissolved in a solvent.
And, since it can express a high refractive index with a polymer alone without containing a metal oxide, even when a dry process such as etching or ashing is performed, the etch rate becomes constant, and a film with a uniform film thickness can be obtained. Increases process margin when manufacturing devices.
A film produced using the triazine ring-containing polymer of the present invention having the above-described 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).
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 diagram showing a ¹ H-NMR spectrum of a polymer compound [3] obtained in Example 1. FIG. It is a figure which shows the TG-DTA measurement result in Example 2.

Hereinafter, the present invention will be described in more detail.
The triazine ring-containing polymer according to the present invention includes a repeating unit structure represented by the formula (1).

Ar is not particularly limited as long as it is a divalent organic group containing one or both of an aromatic ring and a heterocyclic ring. In the present invention, Ar is represented by formulas (2) to (18). At least one is preferred, and in particular, at least one represented by formulas (9), (10), (12) and (13) is preferred.
In the case of formulas (9) and (10), those in which W ¹ and W ² are S (sulfur atom) are suitable.

R ^{1 to} R ¹²⁸ are independently of each other a hydrogen atom, a halogen atom, a carboxyl group, a sulfone group, an alkyl group that may have a branched structure having 1 to 10 carbon atoms, or a group 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 ¹²⁹ R ¹³⁰ (R ¹²⁹ and R ¹³⁰ 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 ¹³¹ (R ¹³¹ represents a hydrogen atom or an alkyl group which may have a branched structure having 1 to 10 carbon atoms).

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Although it does not specifically limit as carbon number of the said alkyl 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 may be any of a chain, a branch, and a ring.

  Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, cyclobutyl group, and 1-methyl. -Cyclopropyl group, 2-methyl-cyclopropyl 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, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, cyclopentyl group, 1-methyl-cyclobutyl group, 2-methyl -Cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group, 2-ethyl -Cyclopropyl 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-methyl-cyclopentyl group, 2-methyl-cyclopentyl group, 3 -Methyl-cyclopentyl group, 1- Til-cyclobutyl group, 2-ethyl-cyclobutyl group, 3-ethyl-cyclobutyl group, 1,2-dimethyl-cyclobutyl group, 1,3-dimethyl-cyclobutyl group, 2,2-dimethyl-cyclobutyl group, 2,3- Dimethyl-cyclobutyl group, 2,4-dimethyl-cyclobutyl group, 3,3-dimethyl-cyclobutyl group, 1-n-propyl-cyclopropyl group, 2-n-propyl-cyclopropyl group, 1-isopropyl-cyclopropyl group 2-isopropyl-cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, 1,2,3-trimethyl-cyclopropyl group, 2,2,3-trimethyl-cyclopropyl group, 1-ethyl-2 -Methyl-cyclopropyl group, 2-ethyl-1-methyl-cyclopropyl group, 2-ethyl-2-methyl-cyclo A propyl group, 2-ethyl-3-methyl-cyclopropyl group, etc. are mentioned.

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 group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, s-butoxy group, t-butoxy group, n-pentoxy 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 Ru-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 , 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.

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 (19).

R ^{132 to} R ¹³⁵ are independently of each other a hydrogen atom, a halogen atom, a carboxyl group, a sulfone group, an alkyl group that may have a branched structure having 1 to 10 carbon atoms, or a group having 1 to 10 carbon atoms. An alkoxy group that may have a branched structure is represented, and Y ¹ and Y ² each independently represent an alkylene group that may have a single bond or a branched structure having 1 to 10 carbon atoms.
Examples of the halogen atom, alkyl group and alkoxy group are the same as those described above.
Examples of the alkylene group which may have a branched structure having 1 to 10 carbon atoms include a methylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, and a pentamethylene group.

  Specific examples of the aryl group represented by the above formulas (2) to (18) include, but are not limited to, those represented by the following formula.

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

  Furthermore, the aryl group shown by a following formula is more preferable from the point of expressing a higher refractive index.

  These aryl sites are 1,4-benzenedithiol, 1,3-benzenedithiol, 1,2-benzenedithiol, 2-methyl-1,4- as dithiol compounds to be reacted with cyanuric halide in the production method described later. Benzenedithiol, 2-ethyl-1,4-benzenedithiol, 2-methoxy-1,4-benzenedithiol, 2-chloro-1,4-benzenedithiol, dimercaptodiphenylsulfide (4,4'-thiobisbenzenethiol) ), Bis- (4-mercapto-3-methylphenyl) sulfide, bis- (4-mercapto-3-methoxyphenyl) sulfide, bis- (4-mercapto-3-chlorophenyl) sulfide, 3,4'-dimercapto Diphenyl sulfide, 1,4-bis- (4-mercaptofe Lucio) benzene or the like can be introduced by using as a raw material.

  Suitable examples of the repeating unit structure include, but are not limited to, those represented by the following formula.

The weight average molecular weight of the triazine ring-containing polymer of the present invention is not particularly limited, but is preferably 500 to 500,000, more preferably 500 to 100,000, further improving heat resistance, and shrinkage rate. Is preferably 2,000 or more, more preferably 50,000 or less, more preferably 30,000 or less, and more preferably 30,000 or less from the viewpoint of further increasing the solubility and decreasing the viscosity of the obtained solution. 000 or less is more preferable.
In addition, the weight average molecular weight in this invention is an average molecular weight obtained by standard polystyrene conversion by gel permeation chromatography (henceforth GPC) analysis.

An example is given and demonstrated about the manufacturing method of the triazine ring containing polymer (hyperbranched polymer) of this invention.
The triazine ring-containing polymer of the present invention can be obtained by reacting cyanuric halide with an aryl dithiol compound. For example, as shown in the following scheme 1, the hyperbranched polymer having a repeating structure (20) is , Cyanuric halide (21), and aryldithiol compound (22) can be obtained by reacting in a suitable organic solvent.

（式中、Ｘは、互いに独立してハロゲン原子を表す。）

(In formula, X represents a halogen atom mutually independently.)

By using the above method, the hyperbranched polymer of the present invention can be produced inexpensively, easily and safely. Since this production method is significantly shorter than the reaction time for synthesizing a general polymer, it is a production method suitable for environmental considerations in recent years and can reduce CO ₂ emissions. Moreover, stable production is possible even if the production scale is greatly increased, and the stable supply system at the industrialization level is not impaired.

In the method of Scheme 1 above, the amount of each raw material charged is arbitrary as long as the target polymer is obtained, but the aryldithiol compound (22) 0.01 relative to 1 equivalent of the cyanuric halide (21). 10 equivalents are preferable, but it is preferable to avoid using 3 equivalents of the aryldithiol compound (22) to 2 equivalents of cyanuric halide (21). By shifting the equivalent of the functional group, formation of a gelled product can be prevented.
In order to obtain a hyperbranched polymer (hyperbranched polymer) having triazine ring ends of various molecular weights, the aryldithiol compound (22) should be used in an amount of less than 3 equivalents relative to 2 equivalents of cyanuric halide (21). preferable.
On the other hand, in order to obtain a hyperbranched polymer (hyperbranched polymer) having a thiol terminal of various molecular weights, it should be used in an amount less than 2 equivalents of cyanuric halide (21) relative to 3 equivalents of the aryldithiol compound (22) Is preferred.
Thus, the molecular weight of the resulting hyperbranched polymer (hyperbranched polymer) can be easily adjusted by appropriately adjusting the amount of the aryldithiol compound (22) or the cyanuric halide (21).

As said organic solvent, the various solvent normally used in this kind of reaction can be used, for example, tetrahydrofuran, dioxane, dimethylsulfoxide; 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, N, N-dimethylpropionic acid amide, N, N-dimethylisobutyramide, N-methylformamide, N, N′-dimethylpropylene Amide solvents such as urea, and mixed solvents thereof That.
Among these, N, N-dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, and mixed solvents thereof are preferable, and N, N-dimethylacetamide, N-methyl-2-pyrrolidone are particularly preferable. Is preferred.

  In the reaction of the reaction of Scheme 1, 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. -10 to 50 ° C is even more preferable.

In the reaction of Scheme 1 above, the order of mixing the components is arbitrary, but the solution containing the cyanuric halide (21) or aryldithiol compound (22) and the organic solvent is heated to 60 to 150 ° C, preferably 80 to 150 ° C. The method of heating and adding the aryldithiol compound (22) or cyanuric halide (21) to the solution at this temperature is optimal.
In this case, either a component previously dissolved in a solvent or a component added later may be used, but a method of adding cyanuric halide (21) to a heated solution of the aryldithiol compound (22) is preferable.
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 Scheme 1, after mixing both compounds in a heated state, the target triazine ring-containing polymer does not gel even when reacted in one step (without increasing the temperature stepwise). Can be obtained.

In the reaction of Scheme 1 above, various bases usually used during polymerization or after polymerization may be added.
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, ammonia, trimethylamine, triethylamine, diisopropylmethylamine, diisopropylethylamine, N-methylpiperidine, 2,2, Examples include 6,6-tetramethyl-N-methylpiperidine, pyridine, 4-dimethylaminopyridine, N-methylmorpholine and the like.
1-100 equivalent is preferable with respect to 1 equivalent of cyanuric halide (21), and, as for the addition amount of a base, 1-10 equivalent is more preferable. These bases may be used as an aqueous solution.
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.
After completion of the reaction, the product can be easily purified by a reprecipitation method or the like.

In the present invention, at least one of the halogen atoms of the terminal triazine ring is substituted with an alkyl group, an aralkyl group, an aryl group, an alkylamino group, an alkoxysilyl group-containing alkylamino group, an aralkylamino group, an arylamino group, The cap may be capped with an alkoxy group, an aralkyloxy group, an aryloxy group, an alkylthio group, an aralkylthio group, an arylthio group, an ester group, or the like.
Among these, an alkylamino group, an alkoxysilyl group-containing alkylamino group, an aralkylamino group, an arylamino group, an alkylthio group, and an arylthio group are preferable, and an alkylamino group, an arylamino group, an alkylthio group, and an arylthio group are more preferable.
Examples of the ester group include methoxycarbonyl group, ethoxycarbonyl group, etc., alkyl group, aralkyl group, aryl group, alkylamino group, alkoxysilyl group-containing alkylamino group, aralkylamino group, arylamino group, alkoxy group, aralkyl. Examples of the oxy group and aryloxy group are the same as those described above.
Examples of the alkylthio group include a methylthio group, an ethylthio group, and a propylthio group.
Examples of the aralkylthio group include a benzylthio group.
Examples of the arylthio group include a phenylthio group and a p-tolylthio group.
These groups can be easily introduced by substituting a halogen atom on the triazine ring with a compound that gives a corresponding substituent. For example, p-toluenethiol is added as shown in the following scheme 2. To obtain a hyperbranched polymer (23) having an arylthio group at at least one terminal.

（式中、Ｘは上記と同じ意味を表す。）

(Wherein X represents the same meaning as described above.)

At this time, the monothiol compound is charged simultaneously, that is, by reacting the cyanuric halide compound with the aryldithiol compound in the presence of the monothiol compound, the rigidity of the hyperbranched polymer is relaxed. A soft hyperbranched polymer with a low degree can be obtained.
The hyperbranched polymer obtained by this method has excellent solubility in a solvent (inhibition of aggregation) and crosslinkability with a crosslinking agent, and is particularly used when used as a composition in combination with a crosslinking agent described later. It is advantageous.

  Examples of the monothiol compound include alkyl monothiols such as methyl mercaptan, ethyl mercaptan, propyl mercaptan, and butyl mercaptan; aralkyl monothiols such as benzyl mercaptan; aryl monothiols such as thiophenol and p-toluenethiol.

In this case, the amount of the thiol compound used is preferably 0.05 to 500 equivalents, more preferably 0.05 to 120 equivalents, and even more preferably 0.05 to 50 equivalents with respect to 1 equivalent of the halogenated cyanuric compound.
The reaction temperature in this case is also preferably -20 to 50 ° C, more preferably -10 to 20 ° C. Thereafter, in order to promote the reaction, it is preferable to carry out the reaction by raising the temperature at once (in one step).
In addition, you may perform reaction which makes a halogenated cyanuric compound and an aryl dithiol compound react in presence of such a monothiol compound using the organic solvent similar to the above-mentioned.

The polymer of the present invention described above can be used as a composition mixed with other compounds, and examples thereof include a composition with a leveling agent, a surfactant, a crosslinking agent, a resin and the like.
These compositions can be used as a film-forming composition, and can be suitably used as a film-forming composition (also referred to as a polymer varnish) dissolved in various solvents.
The solvent used for dissolving the polymer may be the same as or different from the solvent used during the polymerization. The solvent is not particularly limited as long as the compatibility with the polymer is not impaired, and one kind or a plurality of kinds can be arbitrarily selected and used.
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-methoxy-2-propanol , Tetrahydrofuran, 1,4-dioxane, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethylsulfone Sid, N- cyclohexyl-2-pyrrolidinone and the like. These may be used singly or may be used 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.

As long as the effects of the present invention are not impaired, the film-forming composition of the present invention contains other components other than the triazine ring-containing polymer and the solvent, for example, a leveling agent, a surfactant, a crosslinking agent, and the like. Also 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 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, F-553, F-554 (DIC Corporation) ) Fluorosurfactant such as FLORARD FC430, FC431 (Sumitomo 3M Co., Ltd.), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd.) Agent Ganosiloxane 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 ( 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 polymer. Even more preferred.

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 polymer of the present invention.
Examples of such compounds include melamine compounds having a crosslinkable substituent such as a methylol group and methoxymethyl group, substituted urea compounds, compounds containing a crosslinkable substituent such as an epoxy group or an oxetane group, and blocked isocyanates. A compound containing acid, a compound having an acid anhydride, a compound having a (meth) acryl group, a phenoplast compound, and the like, but from the viewpoint of heat resistance and storage stability, an epoxy group, a blocked isocyanate group, (meth) acrylic Compounds containing groups are preferred.
The blocked isocyanate group is also preferable from the viewpoint that the refractive index does not decrease because it is crosslinked by a urea bond and has a carbonyl group.
These compounds only need to have at least one cross-linking substituent when used for polymer terminal treatment, and have at least two cross-linking substituents when used for cross-linking treatment between polymers. There is a need.

As an epoxy compound, it has two or more epoxy groups in one molecule, and when exposed to a high temperature during thermosetting, the epoxy is ring-opened and crosslinked with the triazine ring-containing polymer of the present invention by an addition reaction. The reaction proceeds.
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, pentae Examples include lithitol polyglycidyl ether.

  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 Corporation), CY175, CY177, CY179 (above, manufactured by CIBA-GEIGY A.G), Araldite CY-182, CY-192, CY-184 (above, CIBA-GEIGY A.G) G), Epicron 200, 400 (above, manufactured by DIC Corporation), Epicote (currently jER) 71, 872 (above, manufactured by Japan Epoxy Resin Co., Ltd.), ED-5661, ED-5862 (above, made 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 Chem) Tex Co., Ltd.) can also be used.

The acid anhydride compound is a carboxylic acid anhydride obtained by dehydrating and condensing two molecules of carboxylic acid. When exposed to a high temperature during thermosetting, the anhydride ring is opened and the triazine ring of the present invention is contained. A crosslinking reaction proceeds with the polymer by an addition reaction.
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 and the like 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-butanetetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride And those having one acid anhydride group.

As a (meth) acrylic compound, it has two or more (meth) acrylic groups in one molecule, and when exposed to a high temperature during thermosetting, it undergoes an addition reaction with the triazine ring-containing polymer of the present invention. The crosslinking reaction proceeds.
Examples of the compound having a (meth) acryl group include ethylene glycol diacrylate, ethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, ethoxylated bisphenol A diacrylate, ethoxylated bisphenol A dimethacrylate, and ethoxylated tri Methylolpropane triacrylate, ethoxylated trimethylolpropane trimethacrylate, ethoxylated glycerin triacrylate, ethoxylated glycerin trimethacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetramethacrylate, ethoxylated dipentaerythritol hexaacrylate, polyglycerol mono Ethylene oxide polyacrylate Polyglycerin polyethylene glycol polyacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, trimethylolpropane triacrylate, tri Examples include methylolpropane trimethacrylate, tricyclodecane dimethanol diacrylate, tricyclodecane dimethanol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, and the like.

  The compound having the (meth) acryl group is available as a commercial product, and specific examples thereof include NK ester A-200, A-400, A-600, A-1000, A-1000. 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, A-TMPT-9EO, ATM-4E, ATM-35E Co., Ltd.), KAYAARA (Registered trademark) DPEA-12, PEG400DA, THE-330, RP-1040 (manufactured by Nippon Kayaku Co., Ltd.), M-210, M-350 (manufactured by Toagosei Co., Ltd.), KAYARAD (registered trademark) DPHA, NPGDA, PET30 (manufactured by Nippon Kayaku Co., Ltd.), NK ester A-DPH, A-TMPT, A-DCP, A-HD-N, TMPT, DCP, NPG, and HD-N (manufactured by Shin-Nakamura Chemical Co., Ltd.).

  As a compound containing a blocked isocyanate, the isocyanate group (—NCO) has two or more blocked isocyanate groups blocked by an appropriate protective group in one molecule, and when exposed to a high temperature during thermosetting, The protecting group (block portion) is dissociated by thermal dissociation, and the resulting isocyanate group causes a crosslinking reaction with the resin. For example, two or more groups represented by the following formula in one molecule (note these The 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 portion.)

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.

As an aminoplast compound, it has two or more methoxymethylene groups in one molecule, and when exposed to a high temperature during thermosetting, it undergoes a crosslinking reaction by a demethanol condensation reaction with the triazine ring-containing polymer of the present invention. Is something that progresses.
Examples of melamine compounds include Cymel series such as hexamethoxymethyl melamine CYMEL (registered trademark) 303, tetrabutoxymethyl glycoluril 1170, tetramethoxymethyl benzoguanamine 1123 (above, manufactured by Nihon Cytec Industries, Ltd.), Nicalac (registered trademark) MW-30HM, MW-390, MW-100LM, MX-750LM, which are methylated melamine resins, MX-270, MX-280, MX-290, which are methylated urea resins. (Nicarak series, etc., manufactured by Sanwa Chemical Co., Ltd.).
The oxetane compound has two or more oxetanyl groups in one molecule and undergoes a crosslinking reaction by an addition reaction with the triazine ring-containing polymer of the present invention when exposed to a high temperature during thermosetting. It is.
Examples of the compound having an oxetane group include OXT-221, OX-SQ-H, and OX-SC (manufactured by Toagosei Co., Ltd.) containing an oxetane group.

The phenoplast compound has two or more hydroxymethylene groups in one molecule and undergoes a crosslinking reaction by dehydration condensation reaction with the triazine ring-containing polymer of the present invention when exposed to a high temperature during thermosetting. It is a progression.
Examples of the phenoplast compound include 2,6-dihydroxymethyl-4-methylphenol, 2,4-dihydroxymethyl-6-methylphenol, bis (2-hydroxy-3-hydroxymethyl-5-methylphenyl) methane, Bis (4-hydroxy-3-hydroxymethyl-5-methylphenyl) methane, 2,2-bis (4-hydroxy-3,5-dihydroxymethylphenyl) propane, bis (3-formyl-4-hydroxyphenyl) methane Bis (4-hydroxy-2,5-dimethylphenyl) formylmethane, α, α-bis (4-hydroxy-2,5-dimethylphenyl) -4-formyltoluene and the like.
The phenoplast compound can also be obtained as a commercial product. Specific examples thereof include 26DMPC, 46DMOC, DM-BIPC-F, DM-BIOC-F, TM-BIP-A, BISA-F, and BI25X-DF. , BI25X-TPA (manufactured by Asahi Organic Materials Co., Ltd.) and the like.

These crosslinking agents may be used alone or in combination of two or more. The amount of the crosslinking agent used is preferably 1 to 100 parts by mass with respect to 100 parts by mass of the triazine ring-containing polymer, but considering the solvent resistance, the lower limit is preferably 10 parts by mass, more preferably 20 parts by mass. Furthermore, in consideration of controlling the refractive index, the upper limit is preferably 50 parts by mass, more preferably 30 parts by mass.
By using the cross-linking agent, the cross-linking agent and the reactive terminal substituent of the hyperbranched polymer may react to express effects such as improvement in film density, heat resistance, and heat relaxation ability. .
In addition, the said other component can be added at the arbitrary processes at the time of preparing the composition of this invention.

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 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. 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 causing the reaction to proceed on the substrate.
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 film made of the composition of the present invention thus obtained can achieve high heat resistance, high transparency, high refractive index, high solubility, and low volume shrinkage, 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, organic thin film transistors (TFTs).

In addition, you may mix | blend other resin (thermoplastic resin or thermosetting resin) with the composition of this invention as needed.
Specific examples of the resin are not particularly limited. Examples of the thermoplastic resin include polyolefin resins such as PE (polyethylene), PP (polypropylene), EVA (ethylene-vinyl acetate copolymer), EEA (ethylene-ethyl acrylate copolymer); PS (polystyrene) Polystyrene resins such as HIPS (high impact polystyrene), AS (acrylonitrile-styrene copolymer), ABS (acrylonitrile-butadiene-styrene copolymer), MS (methyl methacrylate-styrene copolymer); polycarbonate resin; Polyvinyl resin; Polyamide resin; (Meth) acrylic resin such as PMMA (polymethyl methacrylate); PET (polyethylene terephthalate), polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate Polyester resins such as PLA (polylactic acid), poly-3-hydroxybutyric acid, polycaprolactone, polybutylene succinate, polyethylene succinate / adipate; polyphenylene ether resin; modified polyphenylene ether resin; polyacetal resin; polysulfone resin; Polyglycolic acid; modified starch; cellulose acetate, cellulose triacetate; chitin, chitosan; lignin , Polyurethane resin, epoxy resin and the like.
These resins may be used alone or in combination of two or more, and the amount used is preferably 1 to 10,000 parts by mass with respect to 100 parts by mass of the triazine ring-containing polymer. Preferably it is 1-1000 mass parts.

For example, a composition with a (meth) acrylic resin can be obtained by blending a (meth) acrylate compound into the composition and polymerizing the (meth) acrylate compound.
Examples of (meth) acrylate compounds include methyl (meth) acrylate, ethyl (meth) acrylate, ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (Meth) acrylate, polypropylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri Oxyethyl (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, tricyclodecanyl di (meth) acrylate, trimethylolpropane trioxypropyl (meth) Acrylate, tris-2-hydroxyethyl isocyanurate tri (meth) acrylate, tris-2-hydroxyethyl isocyanurate di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, pentaerythritol di (meth) acrylate, Glycerol methacrylate acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane trimethacrylate, allyl (meth) acrylate, vinyl (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, urethane (meth) acrylate, etc. Is mentioned.

Polymerization of these (meth) acrylate compounds can be carried out by light irradiation or heating in the presence of a photo radical initiator or a heat radical initiator.
Examples of the photo radical polymerization initiator include acetophenones, benzophenones, Michler's benzoylbenzoate, amyloxime ester, tetramethylthiuram monosulfide, and thioxanthones.
In particular, photocleavable photoradical polymerization initiators are preferred. The photocleavable photoradical polymerization initiator is described in the latest UV curing technology (p. 159, publisher: Kazuhiro Takahisa, publisher: Technical Information Association, Inc., published in 1991).
Examples of commercially available radical photopolymerization initiators include, for example, trade names: C.I. 1116, 1173, manufactured by BASF, Inc. Product name: Lucillin TPO, manufactured by UCB, Inc. Product name: Ubekrill P36, manufactured by Fratteri Lamberti, Inc. Product names: Ezacure KIP150, KIP65LT, KIP100F, KT37, KT55, KTO46, KIP75 / B, etc. It is done.

It is preferable to use a photoinitiator in the range of 0.1-15 mass parts with respect to 100 mass parts of (meth) acrylate compounds, More preferably, it is the range of 1-10 mass parts.
Examples of the solvent used for the polymerization include the same solvents as those exemplified above for the film-forming composition.

EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to the following Example. In addition, each measuring apparatus used in the Example is as follows.
[ ¹ H-NMR]
Apparatus: Varian NMR System 400NB (400MHz)
JEOL-ECA700 (700MHz)
Measuring solvent: DMSO-d6
Reference substance: Tetramethylsilane (TMS) (δ0.0ppm)
[GPC]
Equipment: HLC-8320 GPC manufactured by Tosoh Corporation
Column: Shodex KF-802.5L + KF-803L
Column temperature: 40 ° C
Solvent: Tetrahydrofuran 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)]
Device: TG-8120, manufactured by Rigaku Corporation
Temperature increase rate: 10 ° C / min Measurement temperature: 25 ° C-750 ° C

[Example 1] Synthesis of polymer compound [3]

4,4'-thiobisbenzenethiol (4.12 g, 0.0165 mol, manufactured by Aldrich) and p-toluenethiol (1.86 g, 0.015 mol, Tokyo Chemical Industry) in a 200 mL four-necked flask at room temperature under nitrogen Kogyo Co., Ltd.) was added and dissolved in N-methylpyrrolidone (41.3 mL), sodium hydroxide (6.21 g, 0.045 mol) was added, and the mixture was stirred in an ice bath for 20 minutes. Thereafter, cyanuric chloride (2.77 g, 0.015 mol, manufactured by Evonik Degussa) dissolved in N-methylpyrrolidone (27.7 mL) was added to initiate polymerization. After 1 hour, the reaction solution was reprecipitated in a mixed solution of 414 g of ion-exchanged water and 138 g of methanol. The precipitate was filtered and dried at 150 ° C. for 8 hours to obtain 6.39 g of the target polymer [3] (hereinafter referred to as TTB-SH).
The ¹ H-NMR of TTB-SH is shown in FIG. The obtained TTB-SH is a compound having a structural unit represented by the formula (1). The weight average molecular weight Mw measured by polystyrene conversion by GPC of TTB-SH was 1,900, and the polydispersity Mw / Mn was 3.09.

[Example 2] Measurement of 5% weight loss of TTB-SH 6.45 mg of TTB-SH obtained in Example 1 was added to a platinum pan, and measurement was performed at a temperature increase rate of 15 ° C / min with TG-DTA. The result is shown in FIG. The 5% weight loss was 328 ° C.

[Example 3] Refractive Index Measurement TTB-SH (0.1 g) obtained in Example 1 was dissolved in 0.9 g of N-methylpyrrolidone to obtain a light yellow transparent solution. The obtained polymer varnish was spin-coated on a glass substrate at 200 rpm for 5 seconds and 2000 rpm for 30 seconds using a spin coater, and heated at 100 ° C. for 1 minute and 200 ° C. for 5 minutes to remove the solvent and obtain a film. . When the refractive index of the obtained film was measured, the refractive index at 550 nm was 1.800.

Claims (15)

The triazine ring containing polymer characterized by including the repeating unit structure represented by following formula (1).

[In the formula, Ar represents a divalent organic group containing one or both of an aromatic ring and a heterocyclic ring. ] The triazine ring-containing polymer according to claim 1, wherein Ar represents at least one selected from the group represented by formulas (2) to (18).

[Wherein, R ^{1 to} R ¹²⁸ are each independently a hydrogen atom, a halogen atom, a carboxyl group, a sulfone group, an alkyl group which may have a branched structure having 1 to 10 carbon atoms, or 1 carbon atom. 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 ¹²⁹ R ¹³⁰ (R ¹²⁹ and R ¹³⁰ 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 ¹³¹ (R ¹³¹ 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. And an alkyle which may have a single bond or a branched structure having 1 to 10 carbon atoms. Group, or a group of the formula (19)

(In the formula, R ^{132 to} R ¹³⁵ are each independently a hydrogen atom, a halogen atom, a carboxyl group, a sulfone group, an alkyl group which may have a branched structure of 1 to 10 carbon atoms, or 1 carbon atom. 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. To express.)
Represents a group represented by ]   The triazine ring-containing polymer according to claim 2, wherein Ar is at least one selected from the group represented by formulas (9), (10), (12) and (13). The triazine ring-containing polymer according to claim 3, wherein W ¹ and W ² in the formulas (9) and (10) are S. The triazine ring-containing polymer according to claim 1, wherein the repeating unit structure is represented by the formula (20).

  At least one terminal is an alkyl group, aralkyl group, aryl group, alkylamino group, alkoxysilyl group-containing alkylamino group, aralkylamino group, arylamino group, alkoxy group, aralkyloxy group, aryloxy group, alkylthio group, aralkyl The triazine ring-containing polymer according to any one of claims 1 to 5, which is capped with a thio group, an arylthio group, or an ester group.   Having at least one triazine ring end, and the triazine ring end is an alkyl group, an aralkyl group, an aryl group, an alkylamino group, an alkoxysilyl group-containing alkylamino group, an aralkylamino group, an arylamino group, an alkoxy group, an aralkyloxy group The triazine ring-containing polymer according to claim 6, which is capped with a group, an aryloxy group, an alkylthio group, an aralkylthio group, an arylthio group, or an ester group.   The composition for film formation containing the triazine ring containing polymer of any one of Claims 1-7.   A film obtained from the film-forming composition according to claim 8.   The film | membrane containing the triazine ring containing polymer of any one of Claims 1-7.   An electronic device comprising a substrate and the film according to claim 9 or 10 formed on the substrate.   An optical member comprising a substrate and the film according to claim 9 or 10 formed on the substrate.   A solid-state imaging device comprising a charge-coupled device or a complementary metal oxide semiconductor, comprising at least one layer of the film according to claim 9.   A solid-state imaging device comprising the film according to claim 9 as a planarizing layer on a color filter.   A lens material, a planarizing material or an embedding material for a solid-state imaging device, comprising the film-forming composition according to claim 8.

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