JP6669206B2 - Composition for forming high refractive index film containing triazine ring-containing polymer - Google Patents

Description

  The present invention relates to a composition containing a triazine ring-containing polymer.

  Until now, various attempts have been made to make polymer compounds highly functional. For example, as a method for increasing the refractive index of a polymer compound, an aromatic ring, a halogen atom, and a sulfur atom have been introduced. Above all, an episulfide polymer compound and a thiourethane polymer compound into which a sulfur atom has been introduced have been put to practical use as high-refractive-index lenses for spectacles.

Further, a method using an inorganic metal oxide is known as the most influential method for achieving a higher refractive index of a polymer compound.
For example, a technique of 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 (Patent Document 1) is reported.
Furthermore, a technique of introducing a condensed cyclic skeleton having a high refractive index into a part of a siloxane polymer (Patent Document 2) has been reported.

  Also, many attempts have been made to impart heat resistance to a polymer compound.Specifically, it is well known that the heat resistance of a polymer compound can be improved by introducing an aromatic ring. I have. 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 mainly applied to heat-resistant plastics.

Melamine resins, on the other hand, are well known as triazine-based resins, but have a much lower decomposition temperature than heat-resistant materials such as graphite.
Until now, aromatic polyimides and aromatic polyamides have been mainly used as heat-resistant organic materials composed of carbon and nitrogen. However, since these materials have a linear structure, their heat-resistant temperatures are not so high.
Also, a triazine-based condensation material has been reported as a heat-resistant nitrogen-containing polymer material (Patent Document 4).

Meanwhile, in recent years, electronic devices such as 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, and an organic thin-film transistor (TFT) have been developed. At that time, high-performance polymer materials have been required.
Specific characteristics required include 1) heat resistance, 2) transparency, 3) high refractive index, 4) light resistance, 5) high solubility, and 6) low volume shrinkage.

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

  The present invention has been made in view of such circumstances, and it is an object of the present invention to provide a composition containing a triazine ring-containing polymer that can achieve a high refractive index with a polymer alone without adding a metal oxide. And

The present inventors have found that a polymer containing a repeating unit having a triazine ring and an aromatic ring can achieve high heat resistance, high transparency, high refractive index, high solubility, and low volume shrinkage by using a polymer alone. It has already been found that the composition is suitable as a film-forming composition for production (PCT / JP2010 / 057761).
Based on this finding, the inventors of the present invention have conducted intensive studies, and as a result, a predetermined linear polymer containing a repeating unit having a triazine ring and an aromatic ring has a very high refractive index. The present inventors have found that the composition is suitable as a film forming composition, and completed the present invention.

｛式中、ＲおよびＲ′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は、アリール基を示し、
Ａｒ²は、式（２）〜（１３）で示される群から選ばれる少なくとも１種を表す。

〔式中、Ｒ¹〜Ｒ⁹²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、Ｒ⁹³およびＲ⁹⁴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、Ｗ¹およびＷ²は、互いに独立して、単結合、ＣＲ⁹⁵Ｒ⁹⁶（Ｒ⁹⁵およびＲ⁹⁶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ＮＲ⁹⁷（Ｒ⁹⁷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（１４）

（式中、Ｒ⁹⁸〜Ｒ¹⁰¹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。〕｝
２． 前記Ａｒ¹が、式（１５）で表される１のトリアジン環含有重合体を含む組成物、

（式中、Ｒ¹⁰²〜Ｒ¹⁰⁶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す。）
３． 前記Ａｒ²が、式（２）、（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１または２のトリアジン環含有重合体を含む組成物
を提供する。 That is, the present invention
1. A composition comprising a triazine ring-containing polymer having a repeating unit structure represented by the following formula (1), and a thermoplastic resin or a thermosetting resin;

Wherein R and R ′ independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group;
Ar ¹ represents an aryl group,
Ar ² represents at least one selected from the group represented by formulas (2) to (13).

[Wherein, R ^{1 to} R ⁹² independently represent 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 to 10, R ⁹³ and R ⁹⁴ are, independently of one another, represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or an aralkyl group,, W ¹ and W ² is independently a single bond, CR ⁹⁵ R ⁹⁶ (R ⁹⁵ and R ⁹⁶ are each independently a hydrogen atom or an alkyl group which may have a branched structure having 1 to 10 carbon atoms ( However, these may form a ring together.), C ＝ O, O, S, SO, SO ₂ , or NR ⁹⁷ (R ⁹⁷ is a hydrogen atom or a carbon atom having 1 carbon atom. Represents an alkyl group which may have a branched structure of 10 to 10 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 formula (14)

(Wherein, R ^{98 to} R ¹⁰¹ each independently represent 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 10 to 10, and 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. Represents a group represented by: ]｝
2. A composition wherein Ar ¹ comprises the triazine ring-containing polymer of 1 represented by the formula (15):

(Wherein, R ^{102 to} R ¹⁰⁶ 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 from 10 to 10.)
3. A composition is provided, wherein Ar ² comprises at least one or two triazine ring-containing polymers selected from the group represented by formulas (2), (12) and (13).

According to the present invention, a triazine ring-containing polymer that can achieve high heat resistance, high transparency, high refractive index, high solubility, and low volume shrinkage alone without using a metal oxide can be provided.
By using the polymer skeleton of the present invention, high heat resistance and high transparency can be maintained even when a secondary amine is used as a polymer spacer, and it has been thought that heat resistance and transparency are impaired. Even when a monomer unit is used, there is a possibility that physical properties can be controlled only by changing the polymer skeleton to the polymer of the present invention.
Since the polymer alone does not contain a metal oxide and can exhibit a high refractive index, even when a dry process such as etching or ashing is performed, the etch rate becomes constant, and a film having a uniform thickness can be obtained. The process margin when manufacturing a device is expanded.
In addition, the properties of the triazine ring-containing polymer of the present invention can be controlled by changing the type of the monomer that is a starting material during synthesis.
Further, the triazine ring-containing polymer of the present invention can be used as a high heat resistant insulating material.
Films prepared using the triazine ring-containing polymer of the present invention having the above-described characteristics include liquid crystal displays, organic electroluminescence (EL) displays, optical semiconductor (LED) devices, solid-state imaging devices, organic thin-film solar cells, It can be suitably used as a member when producing an electronic device such as a dye-sensitized solar cell or an organic thin film transistor (TFT).
In particular, a buried film and a flattening film on a photodiode, a flattening film before and after a color filter, a microlens, a flattening film and a conformal film on a microlens, which are members of a solid-state imaging device required to have a high refractive index. It can be suitably used as

FIG. 4 is a chart showing a ¹ H-NMR spectrum of a polymer compound [1] obtained in Synthesis Example 2. FIG. 9 is a chart showing a ¹ H-NMR spectrum of a polymer compound [2] obtained in Synthesis Example 3.

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

In the above formula, R and R ′ 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 consideration of further increasing the heat resistance of the polymer, and 1 to 3 carbon atoms. Is even more preferred. 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 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- Tyl-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 and a 2-ethyl-3-methyl-cyclopropyl group.

Although the carbon number of the alkoxy group is not particularly limited, it is preferably 1 to 20, and more preferably 1 to 10 and more preferably 1 to 3 in consideration of further increasing the heat resistance of the polymer. preferable. 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 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, 1,2,2-trimethyl-n-propoxy, 1-ethyl-1-methyl-n-propoxy, 1-ethyl-2-methyl-n-propoxy and the like. No.

The carbon number of the aryl group is not particularly limited, but is preferably 6 to 40, and more preferably 6 to 16 carbon atoms, and more preferably 6 to 13 in consideration of further increasing the heat resistance of the polymer. preferable.
Specific examples of the aryl group include a phenyl group, an o-chlorophenyl group, an m-chlorophenyl group, a p-chlorophenyl group, an o-fluorophenyl group, a p-fluorophenyl group, an o-methoxyphenyl group, and a p-methoxy group. Phenyl group, p-nitrophenyl group, p-cyanophenyl group, α-naphthyl group, β-naphthyl group, o-biphenylyl group, m-biphenylyl group, p-biphenylyl group, 1-anthryl group, 2-anthryl group, Examples thereof include a 9-anthryl group, a 1-phenanthryl group, a 2-phenanthryl group, a 3-phenanthryl group, a 4-phenanthryl group, and a 9-phenanthryl group.

Although the number of carbon atoms of the aralkyl group is not particularly limited, it is preferably 7 to 20 carbon atoms, and the alkyl portion thereof may be any of straight-chain, branched and cyclic.
Specific examples thereof include a benzyl group, a p-methylphenylmethyl group, an m-methylphenylmethyl group, an o-ethylphenylmethyl group, an m-ethylphenylmethyl group, a p-ethylphenylmethyl group, and a 2-propylphenylmethyl group. , 4-isopropylphenylmethyl group, 4-isobutylphenylmethyl group, α-naphthylmethyl group and the like.

Ar ² represents at least one selected from the group represented by formulas (2) to (13), and particularly preferably at least one selected from formulas (2), (12) and (13).

R ^{1 to} R ⁹² each independently represent 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 a 1 to 10 carbon atom. R ⁹³ and R ⁹⁴ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group; and W ¹ and W ² represent Independently of each other, a single bond, CR ⁹⁵ R ⁹⁶ (R ⁹⁵ and R ⁹⁶ are each independently a hydrogen atom or an alkyl group which may have a branched structure having 1 to 10 carbon atoms (however, May form a ring together.), C ＝ O, O, S, SO, SO ₂ , or NR ⁹⁷ (R ⁹⁷ is a hydrogen atom or a carbon atom having 1 to 10 carbon atoms.) Represents an alkyl group which may have a branched structure.) Represents
Examples of the alkyl group, the alkoxy group, the aryl group, and the aralkyl group are the same as those described above.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

X ¹ and X ² each independently represent a single bond, an alkylene group having 1 to 10 carbon atoms which may have a branched structure, or a group represented by the formula (14).

R ^{98 to} R ¹⁰¹ each independently represent 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 a 1 to 10 carbon atom. have a branched structure represents a alkoxy group which may, Y ¹ and Y ² independently of one another, represents a single bond or an alkylene group which may have a branched structure of 1 to 10 carbon atoms.
Examples of the halogen atom, alkyl group, and alkoxy group include 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, a pentamethylene group, and the like.

Specific examples of the above Ar ² include those represented by the following formulas, but are not limited thereto.

Ar ¹ is an aryl group, and specific examples thereof include the same as the above-described aryl group. In the present invention, a group represented by the formula (15) is preferable.

R ^{102 to} R ¹⁰⁶ each independently represent 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 a 1 to 10 carbon atom. Represents an alkoxy group which may have a branched structure.
Examples of the halogen atom, alkyl group, and alkoxy group include the same as those described above.
Each of R ^{102 to} R ¹⁰⁶ is preferably a hydrogen atom.

  Suitable repeating unit structures include those represented by the following formula (16) or (17), but are not limited thereto.

The weight average molecular weight of the triazine ring-containing polymer in the present invention is not particularly limited, but is preferably 500 to 100,000, and from the viewpoint of further improving heat resistance and lowering the shrinkage ratio, It is preferably at least 000, and more preferably at most 10,000 from the viewpoint of further increasing the solubility and decreasing the viscosity of the obtained solution.
In addition, the weight average molecular weight in the present invention is an average molecular weight obtained by gel permeation chromatography (hereinafter, referred to as GPC) analysis in terms of standard polystyrene.

The method for producing the triazine ring-containing polymer of the present invention will be described by way of an example.
The triazine ring-containing polymer of the present invention can be obtained by reacting a dihalogenated triazine compound having an arylamino group with a diaminoaryl compound.
For example, as shown in the following Scheme 1, a linear polymer having a repeating structure (16 ′) is obtained by using a dihalogenated triazine (18) having a phenylamino group and an m-phenylenediamine compound (19) in a suitable organic solvent. In the reaction.
The compounds represented by the formulas (18) and (19) can be obtained, for example, as commercial products manufactured by Aldrich or Tokyo Kasei Kogyo Co., Ltd., and can be easily prepared according to a standard method of synthetic organic chemistry. Can be manufactured.
By using this method, the 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 adapted to environmental considerations in recent years, and can reduce CO ₂ emissions. Further, stable production is possible even if the production scale is greatly increased, and the stable supply system at the industrial level is not impaired.

（式中、Ｘは、互いに独立してハロゲン原子を表す。Ｒは上記と同じ意味を表す。）

(In the formula, X independently represents a halogen atom. R represents the same meaning as described above.)

As the organic solvent, various solvents usually used in this type of reaction can be used. For example, tetrahydrofuran, dioxane, N, N-dimethylformamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, tetramethylurea , Hexamethylphosphoramide, N, N-dimethylacetamide, N-methyl-2-piperidone, N, N-dimethylethyleneurea, N, N, N ', N'-tetramethylmalonamide, N-methylcaprolactam , N-acetylpyrrolidine, N, N-diethylacetamide, N-ethyl-2-pyrrolidone, N, N-dimethylpropionamide, N, N-dimethylisobutylamide, N-methylformamide, N, N'-dimethylpropylene Examples include amide solvents such as urea, and mixtures thereof. That.
Among them, N, N-dimethylformamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, and a mixed system thereof are preferable, and particularly, N, N-dimethylacetamide, N-methyl-2-pyrrolidone Is preferred.

In the above reaction, the reaction temperature may be appropriately set in the range from the melting point of the solvent used to the boiling point of the solvent, but is preferably about 0 to 150 ° C, more preferably 60 to 100 ° C.
The order of mixing the components is arbitrary.
In addition, at the time of compounding, it may be added gradually by dropping or the like, or may be added all at once.

In the above reaction, various bases usually used during or after the polymerization may be added.
Specific examples of the base include potassium carbonate, potassium hydroxide, sodium carbonate, sodium hydroxide, sodium hydrogen carbonate, sodium ethoxide, sodium acetate, triethylamine, lithium carbonate, lithium hydroxide, lithium oxide, potassium acetate, and 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 , 6,6-tetramethyl-N-methylpiperidine, pyridine, 4-dimethylaminopyridine, N-methylmorpholine and the like.
The amount of the base to be added is preferably 1 to 100 equivalents, more preferably 1 to 10 equivalents, per 1 equivalent of the triazine compound (18). These bases may be used in the form of an aqueous solution.
It is preferable that no raw material components remain in the obtained polymer, 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.

The above-described triazine ring-containing polymer of the present invention can be used as a composition mixed with another compound, 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 to dissolve the polymer may be the same as or different from the solvent used during the polymerization. This solvent is not particularly limited as long as compatibility with the polymer is not impaired, and one or more solvents can be arbitrarily selected and used.

  Specific examples of such a solvent 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 Leneglycol 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, -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, dimethylsulfo 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 concentration is preferably 0.1 to 50% by mass, and more preferably 0.1 to 20% by mass.

In the film-forming composition of the present invention, as long as the effects of the present invention are not impaired, 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 are included. Is also good.
Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene octyl phenol ether, polyoxyethylene nonyl phenol 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 and polyoxyethylene Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as bitane monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; EF303, EF352 (manufactured by Mitsubishi Materials Denshi Kasei Co., Ltd. (formerly Gemco), trade names MegaFac F171, F173, R-08, R-30, F-553, F-554 (manufactured by DIC Corporation) ), Florado FC430, FC431 (manufactured by Sumitomo 3M Limited), trade names Asahigard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by 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 part by mass based on 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 a compound include a melamine compound having a cross-linking substituent such as a methylol group and a methoxymethyl group, a substituted urea compound, a compound having a cross-linking substituent such as an epoxy group or an oxetane group, and a blocked isocyanate. , A compound having an acid anhydride, a compound having a (meth) acrylic group, a phenoplast compound, etc., from the viewpoint of heat resistance and storage stability, an epoxy group, a blocked isocyanate group, and a (meth) acrylic compound. Compounds containing groups are preferred.
Further, the blocked isocyanate group is preferable in that it is crosslinked by a urea bond and has a carbonyl group so that the refractive index does not decrease.
These compounds may have at least one cross-linking substituent when used for terminal treatment of a polymer, and have at least two cross-linking substituents when used for cross-linking 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 opened and crosslinked by an addition reaction with the triazine ring-containing polymer of the present invention. 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 Lithritol polyglycidyl ether and the like.

  In addition, as commercial products, epoxy resins having at least two epoxy groups, YH-434 and YH434L (manufactured by Toto Kasei Co., Ltd.), and epoxy resins having a cyclohexene oxide structure, Epolid GT-401 and GT -403, GT-301, GT-302, Celloxide 2021, 3000 (manufactured by Daicel Chemical Industries, Ltd.), a bisphenol A type epoxy resin, Epicoat (currently, jER) 1001, 1002, 1003, 1004, 1007, 1009, 1010, 828 (all manufactured by Japan Epoxy Resin Co., Ltd.) and Epicoat (currently jER) 807, a bisphenol F type epoxy resin (produced by Japan Epoxy Resin Co., Ltd.) Epicoat, a phenolic novolak type epoxy resin jER) 152, 154 (all manufactured by Japan Epoxy Resin Co., Ltd.), EPPN201, 202 (all manufactured by Nippon Kayaku Co., Ltd.), EOCN-102, 103S, cresol novolac type epoxy resin 104S, 1020, 1025, and 1027 (all manufactured by Nippon Kayaku Co., Ltd.), Epicoat (currently jER) 180S75 (manufactured by Japan Epoxy Resin Co., Ltd.), Denacol EX- which is an alicyclic epoxy resin 252 (manufactured by Nagase ChemteX Corporation), CY175, CY177, CY179 (manufactured by CIBA-GEIGY AG), Araldite CY-182, CY-192, and CY-184 (manufactured by CIBA-GEIGY A.G.) G), Epicron 200, Epicron 400 (above, manufactured by DIC Corporation), Epicoat (currently jER) 87 872 (manufactured by Japan Epoxy Resin Co., Ltd.), ED-5661, ED-5662 (manufactured by Celanese Coating Co., Ltd.), Denacol EX-611, EX-, which is an aliphatic polyglycidyl ether 612, EX-614, EX-622, EX-411, EX-512, EX-522, EX-421, EX-313, EX-314, EX-321 (Nagase Chemtex And the like can also be used.

The acid anhydride compound is a carboxylic acid anhydride obtained by dehydrating and condensing two molecules of a carboxylic acid, and when exposed to a high temperature at the time of thermosetting, the anhydride ring is opened and the triazine ring-containing compound of the present invention is opened. The crosslinking reaction proceeds with the polymer by the addition reaction.
Specific examples of the acid anhydride compound include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, and maleic anhydride. Acids, succinic anhydride, octyl succinic anhydride, dodecenyl succinic anhydride, etc. having one acid anhydride group in the molecule; 1,2,3,4-cyclobutanetetracarboxylic dianhydride, pyromellitic acid Anhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic acid Dianhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride 1,2,3,4-butanetetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride , 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, etc. And those having two acid anhydride groups.

The (meth) acrylic compound has two or more (meth) acrylic groups in one molecule, and when exposed to a high temperature during thermosetting, 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 trimethacrylate. Methylolpropane triacrylate, ethoxylated trimethylolpropane trimethacrylate, ethoxylated glycerin triacrylate, ethoxylated glycerin trimethacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetramethacrylate, ethoxylated dipentaerythritol hexaacrylate, polyglycerin mono Ethylene oxide polyacryle Polyglycerin polyethylene glycol polyacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, trimethylolpropane triacrylate, trimethyl Methylolpropane trimethacrylate, tricyclodecane dimethanol diacrylate, tricyclodecane dimethanol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, and the like.

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

  As a compound containing a blocked isocyanate, an isocyanate group (-NCO) has two or more blocked isocyanate groups in one molecule blocked by an appropriate protecting group, and when exposed to a high temperature during thermosetting, The protecting group (block portion) is dissociated by thermal dissociation, and the generated isocyanate group causes a crosslinking reaction with the resin. For example, two or more groups represented by the following formulas in one molecule (for these 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 a compound having two or more isocyanate groups per molecule with a suitable blocking agent.
Examples of the compound having two or more isocyanate groups in one molecule include polyisocyanates of isophorone diisocyanate, 1,6-hexamethylene diisocyanate, methylene bis (4-cyclohexyl isocyanate), and trimethylhexamethylene diisocyanate, and dimers thereof. , Trimers, and reaction products thereof 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, o-nitrophenol Phenols such as, p-chlorophenol, 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 and benzophenone oxime. Pyrazoles such as pyrazole, 3,5-dimethylpyrazole and 3-methylpyrazole; and thiols such as dodecanethiol and benzenethiol.

  The compound containing the blocked isocyanate is also available as a commercial product, and specific examples thereof include B-830, B-815N, B-842N, B-870N, B-874N, B-882N, and B-882N. -7005, B-7030, B-7075, B-5010 (all manufactured by Mitsui Chemical Polyurethanes, Inc.), 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 KK) and the like.

The aminoplast compound has two or more methoxymethylene groups in one molecule, and when exposed to a high temperature during thermosetting, causes a crosslinking reaction with the triazine ring-containing polymer of the present invention by a demethanol condensation reaction. Progresses.
Examples of the melamine-based compound include Cymel series such as hexamethoxymethylmelamine CYMEL (registered trademark) 303, tetrabutoxymethylglycoluril 1170, tetramethoxymethylbenzoguanamine 1123 (all manufactured by Nippon Cytec Industries, Ltd.), and the like. Micalac (registered trademark) MW-30HM, MW-390, MW-100LM, and MX-750LM that are methylated melamine resins, MX-270, MX-280, and MX-290 that are methylated urea resins (Above, manufactured by Sanwa Chemical Co., Ltd.).
Oxetane compounds having two or more oxetanyl groups in one molecule, and when exposed to a high temperature during thermosetting, a crosslinking reaction proceeds with an addition reaction with the triazine ring-containing polymer of the present invention. It is.
Examples of the compound having an oxetane group include OXT-221, OX-SQ-H, and OX-SC (all manufactured by Toagosei Co., Ltd.) containing an oxetane group.

The phenoplast compound has two or more hydroxymethylene groups in one molecule, and when exposed to a high temperature during thermosetting, a crosslinking reaction with the triazine ring-containing polymer of the present invention is caused by a dehydration condensation reaction. It is something that goes on.
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 is also available as a commercial product, and specific examples thereof include 26DMPC, 46DMOC, DM-BIPC-F, DM-BIOC-F, TM-BIP-A, BISA-F, and BI25X-DF. And BI25X-TPA (all manufactured by Asahi Organic Materials Industry Co., Ltd.).

These crosslinking agents may be used alone or in combination of two or more. The amount of the crosslinking agent to be 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. In consideration of controlling the refractive index, the upper limit is preferably 50 parts by mass, more preferably 30 parts by mass.
When the crosslinking agent reacts with the reactive terminal substituent of the triazine ring-containing polymer by using the crosslinking agent, and can exert effects such as improvement of film density, improvement of heat resistance, improvement of heat relaxation ability, and the like. There is.
The above-mentioned other components can be added at any step when preparing the composition of the present invention.

The film-forming composition of the present invention can be applied to a substrate, and then, if necessary, heated to form a desired film.
The method of applying the composition is arbitrary, and examples thereof include a spin coating method, a dip method, a flow coating method, an ink jet method, a spray method, a bar coating method, a gravure coating method, a slit coating method, a roll coating method, a transfer printing method, and a brush. Coating, a blade coating method, an air knife coating method and the like can be employed.

As the base material, silicon, glass on which indium tin oxide (ITO) is formed, glass on which indium zinc oxide (IZO) is formed, polyethylene terephthalate (PET), plastic, glass, quartz, ceramics And the like, and a flexible base material having flexibility can also be used.
The firing temperature is not particularly limited for the purpose of evaporating the solvent, and may be, for example, 40 to 400 ° C. In these cases, two or more temperature changes may be applied for the purpose of developing a higher uniform film-forming property or promoting the reaction on the substrate.
The firing method is not particularly limited. For example, the firing may be performed using a hot plate or an oven under an appropriate atmosphere such as an atmosphere, an inert gas such as nitrogen, or a vacuum.
The sintering temperature and the sintering time may be selected under conditions suitable for the target electronic device process step, and the sintering conditions may be selected so that the physical properties of the obtained film conform to the required characteristics of the electronic device.

  The thus-obtained film comprising the composition of the present invention 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) ) It can be suitably used as a member for producing electronic devices such as displays, optical semiconductor (LED) elements, solid-state imaging devices, organic thin-film solar cells, dye-sensitized solar cells, and 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), and 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 chloride resin; Polyamide resin; Polyimide resin; (Meth) acrylic resin such as PMMA (Polymethyl methacrylate); PET (Polyethylene terephthalate), Polybutylene terephthalate, Polyethylene naphthalate, Polybutylene naphthalate Polyester resin 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; polyphenylene sulfide resin; Polyvinyl alcohol resin; Polyglycolic acid; Modified starch; Cellulose acetate, Cellulose triacetate; Chitin, Chitosan; Lignin, and the like, and examples of thermosetting resins include phenolic resins, urea resins, melamine resins, and unsaturated polyester resins. , 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 from 1 to 10,000 parts by mass with respect to 100 parts by mass of the triazine ring-containing polymer. Preferably it is 1 to 1,000 parts by mass.

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, and propylene glycol diacrylate. (Meth) acrylate, polypropylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropanetri 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, Glycerin 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.

The polymerization of these (meth) acrylate compounds can be performed by light irradiation or heating in the presence of a photoradical initiator or a thermal radical initiator.
Examples of the photoradical polymerization initiator include acetophenones, benzophenones, Michler's benzoylbenzoate, amiloxime ester, tetramethylthiuram monosulfide, and thioxanthone.
Particularly, a photo-cleavable photo-radical polymerization initiator is preferable. The photo-cleavable photo-radical polymerization initiator is described in the latest UV curing technology (p. 159, publisher: Kazuhiro Takasu, publisher: Technical Information Association, 1991).
Examples of commercially available photoradical polymerization initiators include, for example, trade names of Irgacure 184, 369, 651, 500, 819, 907, 784, 2959, CGI1700, CGI1750, CGI1850, CG24-61, Darocur, manufactured by Ciba Japan KK 1116, 1173, manufactured by BASF, trade name: Lucirin TPO, manufactured by UCB, trade name: Jubecryl P36, manufactured by Fratteli Lamberti, trade name: Ezacure KIP150, KIP65LT, KIP100F, KT37, KT55, KTO46, KIP75 / B, etc. Can be

The photopolymerization initiator is preferably used in an amount of 0.1 to 15 parts by mass, more preferably 1 to 10 parts by mass, based on 100 parts by mass of the (meth) acrylate compound.
As the solvent used for the polymerization, those similar to the solvents exemplified for the above-mentioned composition for film formation can be mentioned.

Hereinafter, the present invention will be described more specifically with reference to Synthesis Examples and Examples, but the present invention is not limited to the following Examples. The measuring devices used in the examples are as follows.
^[1 H-NMR]
Apparatus: Varian NMR System 400NB (400MHz)
JEOL-ECA700 (700MHz)
Measurement solvent: DMSO-d6
Reference substance: tetramethylsilane (TMS) (δ0.0 ppm)
[GPC]
Equipment: HLC-8200 GPC manufactured by Tosoh Corporation
Column: Shodex KF-804L + KF-805L
Column temperature: 40 ° C
Solvent: tetrahydrofuran (hereinafter, THF)
Detector: UV (254 nm)
Calibration curve: Standard polystyrene [Ellipsometer]
Apparatus: JA Woollam Japan, Incident Angle Spectroscopic Ellipsometer VASE
[Differential thermal balance (TG-DTA)]
Apparatus: TG-8120 manufactured by Rigaku Corporation
Heating rate: 10 ° C / min Measurement temperature: 25 ° C-750 ° C

[Synthesis Example 1] Synthesis of monomer compound

  In a 500 mL four-necked flask, 2,4,6-trichloro-1,3,5-triazine (25.0 g, 138 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 190 mL of THF was charged, and the system was purged with nitrogen. This was cooled to 0 ° C., and aniline (12.8 g, 138 mmol, manufactured by Junsei Chemical Co., Ltd.) dissolved in 190 mL of THF was added dropwise with stirring over 30 minutes. After dropping, stirring was continued for 2 hours. The reaction solution was transferred to a separating funnel, and an aqueous solution of potassium carbonate (19.04 g, 138 mmol) dissolved in 171 mL of ion-exchanged water was added to wash the THF layer. After removing the aqueous layer, THF was distilled off under reduced pressure, and the obtained solid was washed with ion-exchanged water to obtain 27.8 g of a target monomer compound.

[Synthesis Example 2] Synthesis of polymer compound [1]

In a 100 mL four-necked flask, m-phenylenediamine (1.35 g, 12.44 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.) is put, dissolved in 17 mL of dimethylacetamide (hereinafter, DMAc), and heated to 100 ° C. in an oil bath. did. Thereafter, the monomer compound obtained in Synthesis Example 1 (3.00 g, 12.44 mmol) dissolved in 26 mL of DMAc was added to initiate polymerization. The mixture was reacted for 2 hours, allowed to cool to room temperature, and then reprecipitated in a mixed solution of a 28% aqueous ammonia solution (2.27 g) dissolved in 160 mL of water and 54 mL of methanol. The precipitate was filtered, redissolved in 35 mL of dimethylformamide (hereinafter, DMF), and reprecipitated in 170 mL of ion-exchanged water. The obtained precipitate was filtered and dried in a vacuum dryer at 120 ° C. for 6 hours to obtain 2.25 g of the desired polymer compound [1]. FIG. 1 shows the measurement result of the ¹ H-NMR spectrum. The obtained polymer compound [1] is a compound having a structural unit represented by the formula (1). The weight average molecular weight Mw of the polymer compound [1] measured by GPC in terms of polystyrene was 3,100, and the polydispersity Mw / Mn was 1.60. The 5% weight loss temperature by TG-DTA was 340 ° C.

<Coating and refractive index measurement>
The polymer compound [1] obtained in Synthesis Example 2 was dissolved in cyclohexanone / ion-exchanged water (96/4 (parts by mass / parts by mass)) so as to be 10% by mass, and a spin coater was used on a glass substrate. Then, pre-baking was performed for 2 minutes on a hot plate at 150 ° C., and then main firing was performed for 5 minutes on a hot plate at 250 ° C. in the atmosphere to obtain a film. When the refractive index and the film thickness of the obtained film were measured, the refractive index at 550 nm was 1.7507, the refractive index at 633 nm was 1.7330, and the film thickness was 260 nm.

[Synthesis Example 3] Synthesis of polymer compound [2]

In a 100 mL four-necked flask, 4,4′-diaminobenzanilide (2.27 g, 10.0 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.) was added, dissolved in 17 mL of DMAc, and heated to 100 ° C. in an oil bath. Thereafter, the monomer compound (2.40 g, 10.0 mmol) obtained in Synthesis Example 1 dissolved in 30 mL of DMAc was added to initiate polymerization. The mixture was reacted for 3 hours, allowed to cool to room temperature, and reprecipitated in a mixed solution of 28% aqueous ammonia (1.27 g) dissolved in 276 mL of water and 94 mL of methanol. The precipitate was filtered, redissolved in 47 mL of DMF, and reprecipitated in 276 mL of ion-exchanged water. The obtained precipitate was filtered and dried at 120 ° C. for 6 hours with a vacuum dryer to obtain 3.23 g of the target polymer compound [2]. FIG. 2 shows the measurement results of the ¹ H-NMR spectrum. The obtained polymer compound [2] is a compound having a structural unit represented by the formula (2). The weight average molecular weight Mw of the polymer compound [2] measured by GPC in terms of polystyrene was 5,000, and the polydispersity Mw / Mn was 3.97. The 5% weight loss temperature by TG-DTA was 346 ° C.

<Coating and refractive index measurement>
[Example 1]
The polymer compound [2] obtained in Synthesis Example 3 was dissolved in N-methylpyrrolidone / butylcellulose (98/2 (parts by mass / parts by mass)) so as to be 5% by mass, and a spin coater was applied on a glass substrate. And preliminarily baked for 2 minutes on a hot plate at 150 ° C., and then main baked for 5 minutes on a hot plate at 250 ° C. in the atmosphere to obtain a film. When the refractive index and the film thickness of the obtained film were measured, the refractive index at 550 nm was 1.8532, the refractive index at 633 nm was 1.8233, and the film thickness was 46 nm.

  As described above, it is found that the obtained polymer compounds [1] and [2] have a very high refractive index exceeding 1.75 at 550 nm.

Claims (3)

A high refractive index exceeding 1.75 at a wavelength of 550 nm for producing an electronic device, comprising a triazine ring-containing polymer having a repeating unit structure represented by the following formula (1) and a thermoplastic resin or a thermosetting resin. Composition for forming rate film .

Wherein R and R ′ independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group;
Ar ¹ represents an aryl group,
Ar ² represents at least one selected from the group represented by formulas (2) , (12) and (13) .

[Wherein, R ^{1 to} R ⁴ and R ^{77 to} R ⁹² each independently represent a hydrogen atom, a halogen atom, a carboxyl group, a sulfone group, or an alkyl which may have a branched structure having 1 to 10 carbon atoms. R ⁹³ and R ⁹⁴ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group; a representative. ]｝ The composition for forming a high refractive index film according to claim 1, wherein the Ar ¹ is represented by the formula (15).

(Wherein, R ^{102 to} R ¹⁰⁶ 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 from 10 to 10.) The repeating units of the formula (16) or (17) a high refractive index film-forming composition of the represented Ru claim 1 or 2, wherein at.

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