JP2017122188A - Fluorescent polymer and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel fluorescent polymer which can be expected for use as e.g. light emitting materials of organic EL elements.SOLUTION: A polymer comprising a repeating unit structure having a triazine ring, as represented by the following formula, is a fluorescent polymer and can be expected for use as fluorescent materials, e.g. light emitting materials of organic EL elements.SELECTED DRAWING: None

Description

  The present invention relates to a fluorescent polymer and use thereof, and more specifically, relates to a fluorescent polymer comprising a triazine ring-containing polymer and use thereof.

An organic compound having a fluorescent chromophore is less expensive than a fluorescent inorganic compound, and the excitation wavelength and the like can be reduced by changing the skeleton of the molecule or introducing a specific substituent into the molecule. There are advantages that the emission wavelength can be changed and a recognition function for the compound to be measured can be added.
In recent years, various low-molecular compounds and high-molecular compounds have been developed as organic light-emitting materials used for organic electroluminescence (EL) elements, light-emitting spatial light modulation elements, wavelength conversion elements, fluorescent surface coating materials, and the like. ing.
In the manufacture of light emitting devices using low molecular weight compounds, the manufacturing process is limited to the vapor deposition method, whereas when using high molecular weight compounds, they can be formed into a solution and formed into a film by various coating methods. This is advantageous in terms of manufacturing cost.
In addition, the polymer compound has advantages such as easy fine coating and easy adjustment of the film thickness.

Conventionally known π-conjugated polymers such as polyparaphenylene and polyparaphenylene vinylene are known as such polymeric light-emitting materials. However, these polymers have problems of insufficient heat resistance and insufficient long-term stability of fluorescence intensity and fluorescence spectrum shape, and film formation and microfabrication are not easy.
Moreover, although the fluorescent polymer which has a pigment molecule in the side chain of an acrylate-type polymer is reported (refer patent document 1), the heat resistance of a principal chain and a pigment | dye is inadequate.
Furthermore, although an organic EL device using a polyimide having a light emitting function and a charge transport function has been reported (see Patent Documents 2 and 3), although there is no problem in terms of heat resistance, the fluorescence intensity is between polyimide molecules. Due to the strong interaction and concentration quenching associated therewith, there is a problem that it is very low compared to the fluorescence intensity of a low molecular weight compound having the same fluorescent functional group.
From such a point, development of a new fluorescent polymer which is excellent in heat resistance and exhibits good fluorescence emission is desired.

JP 2006-307129 A Japanese Patent Laid-Open No. 03-274663 Japanese Patent Laid-Open No. 04-093389

  The present invention has been made in view of such circumstances, and an object thereof is to provide a novel fluorescent polymer that can be expected to be used as a light emitting material of an organic EL element.

The inventors of the present invention can achieve high heat resistance, high transparency, high refractive index, high solubility, and low volume shrinkage when a polymer containing a repeating unit having a triazine ring and an aromatic ring is used as an electronic device. It has already been found that it is suitable as a film-forming composition for production (International Publication No. 2010/128661).
Based on this knowledge, the present inventors have conducted extensive studies, and as a result, it has been found that a predetermined linear polymer containing a repeating unit having a triazine ring and an aromatic ring exhibits fluorescence and can be used as a fluorescent material. The headline and the present invention were completed.

｛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、Ｚで置換されていてもよい、ナフチル基、アントリル基、またはピレニル基を表し、Ａｒ²は、式（２）または（３）を表す。

〔式中、Ｒ¹〜Ｒ¹²は、互いに独立して、水素原子、ハロゲン原子、カルボキシル基、スルホ基、炭素数１〜１０の分岐構造を有していてもよいアルキル基、または炭素数１〜１０の分岐構造を有していてもよいアルコキシ基を表し、Ｗ¹は、単結合、ＣＲ¹³Ｒ¹⁴（Ｒ¹³およびＲ¹⁴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ＮＲ¹⁵（Ｒ¹⁵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（４）で示される基を表す。

（式中、Ｒ¹⁶〜Ｒ¹⁹は、互いに独立して、水素原子、ハロゲン原子、カルボキシル基、スルホ基、炭素数１〜１０の分岐構造を有していてもよいアルキル基、または炭素数１〜１０の分岐構造を有していてもよいアルコキシ基を表し、Ｙ¹およびＹ²は、互いに独立して、単結合または炭素数１〜１０の分岐構造を有していてもよいアルキレン基を表す。）〕｝
２． 前記Ａｒ¹が、アントリル基またはピレニル基を表す１の蛍光性ポリマー、
３． 前記Ａｒ²が、式（３）で表される１または２の蛍光性ポリマー、
４． 前記Ａｒ²が、式（５）で表される３の蛍光性ポリマー、

５． １〜４のいずれかの蛍光性ポリマーを含む蛍光性コーティング膜形成用組成物、
６． １〜４のいずれかの蛍光性ポリマーを含む発光材料、
７． １〜４のいずれかの蛍光性ポリマーを含む色素、
８． １〜４のいずれかの蛍光性ポリマーを含む色・波長変換材料、
９． １〜４のいずれかの蛍光性ポリマーを含む有機系太陽電池、
１０． ６の発光材料を含む発光層を備えた有機エレクトロルミネッセンス素子
を提供する。 That is, the present invention
1. A fluorescent polymer comprising a triazine ring-containing polymer containing a repeating unit structure represented by the following formula (1):

{In the formula, R and R 'each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group, and Ar ¹ may be substituted with Z, a naphthyl group, an anthryl group Represents a group or a pyrenyl group, and Ar ² represents the formula (2) or (3).

[Wherein, R ^{1 to} R ¹² are each independently a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group which may have a branched structure having 1 to 10 carbon atoms, or 1 carbon atom. Represents an alkoxy group which may have a branched structure of 1 to 10, W ¹ is a single bond, CR ¹³ R ¹⁴ (R ¹³ and R ¹⁴ are each independently a hydrogen atom or a C 1-10 carbon atom; An alkyl group which may have a branched structure (however, these may be combined to form a ring), C═O, O, S, SO, SO ₂ , or NR ¹⁵ (R ¹⁵ 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 each independently a single bond, a carbon number An alkylene group which may have 1 to 10 branched structures, or a group represented by formula (4) Represent.

(In the formula, R ^{16 to} R ¹⁹ are each independently a hydrogen atom, a halogen atom, a carboxyl group, a sulfo 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. Represents))}
2. 1 fluorescent polymer in which Ar ¹ represents an anthryl group or pyrenyl group;
3. Ar ² is a fluorescent polymer of 1 or 2 represented by formula (3),
4). The Ar ² is a fluorescent polymer of 3 represented by the formula (5):

5. A composition for forming a fluorescent coating film, comprising any one of the fluorescent polymers of 1-4;
6). A luminescent material comprising any one of the fluorescent polymers 1 to 4;
7). A dye comprising any one of the fluorescent polymers of 1-4,
8). A color / wavelength conversion material comprising any one of the fluorescent polymers 1 to 4;
9. An organic solar cell comprising any one of the fluorescent polymers of 1-4,
10. An organic electroluminescent device comprising a light emitting layer containing 6 light emitting materials is provided.

The fluorescent polymer of the present invention has characteristics such as high heat resistance, high transparency, high refractive index, high solubility, and low volume shrinkage, and has a good absolute quantum yield at a wavelength of about 400 to 500 nm. Show.
Such a fluorescent polymer of the present invention includes a fluorescent material of a composition for forming a fluorescent coating film, a light emitting material used for an organic EL device, a dye material used for a dye laser, a color / wavelength conversion material, an organic thin film It can be suitably used as a dye used for organic solar cells such as solar cells and dye-sensitized solar cells, fluorescent materials, fluorescent materials used for fluorescent labels such as biomarkers, and the like.

It is a figure which shows the fluorescence spectrum of the compound obtained by the synthesis examples 1 and 2 and Examples 1-1, 1-2.

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

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

  Specific examples of the alkyl group include methyl 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.

Although it does not specifically limit as carbon number of the said aryl group, 6-40 are preferable, and when it considers raising the heat resistance of a polymer more, 6-16 are more preferable, and 6-13 are much more preferable.
Specific examples of the aryl group include 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 include 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group and the like.

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

Ar ² represents a divalent organic group represented by the formula (2) or (3), and among them, a divalent organic group represented by the formula (3) is preferable.

R ^{1 to} R ¹² are independently of each other a hydrogen atom, a halogen atom, a carboxyl group, a sulfo 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 represents a single bond, CR ¹³ R ¹⁴ (R ¹³ and R ¹⁴ each independently represents a hydrogen atom or a branched structure having 1 to 10 carbon atoms; An alkyl group which may have (however, these may be combined to form a ring)), C═O, O, S, SO, SO ₂ , or NR ¹⁵ (R ¹⁵ represents a hydrogen atom or an alkyl group which may have a branched structure having 1 to 10 carbon atoms.
Examples of these alkyl groups and alkoxy groups 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 which may have a branched structure having 1 to 10 carbon atoms, or a group represented by the formula (4).

In the above formula, R ^{16 to} R ¹⁹ are each independently a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group that may have a branched structure having 1 to 10 carbon atoms, or a carbon number of 1 Represents an alkoxy group which may have a branched structure of 1 to 10, Y ¹ and Y ² each independently represent an alkylene group which may have a single bond or a branched structure of 1 to 10 carbon atoms. Represent.
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 Ar ² include, but are not limited to, those represented by the following formula.

Ar ¹ represents a naphthyl group, anthryl group, or pyrenyl group which may be substituted with Z.
Examples of the naphthyl group include an α-naphthyl group and a β-naphthyl group.
Examples of the anthryl group include a 1-anthryl group, a 2-anthryl group, and a 9-anthryl group.
Examples of the pyrenyl group include a 1-pyrenyl group, a 2-pyrenyl group, and a 4-pyrenyl group.
Z represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogen atom, a cyano group, a nitro group, a carboxyl group, or a sulfo group. As these alkyl group, alkoxy group, and halogen atom, Examples thereof are the same as those exemplified above.

  Among these, from the viewpoint of increasing the absolute quantum yield of the fluorescent polymer, an anthryl group and a pyrenyl group which may be substituted with Z are preferable, and an unsubstituted 2-anthryl group and 1-pyrenyl group are more preferable. .

  Suitable examples of the repeating unit structure include, but are not limited to, those represented by the following formulas (5) to (8).

The weight average molecular weight of the triazine ring-containing polymer which is the fluorescent polymer of the present invention is not particularly limited, but is preferably 500 to 100,000, and further improves heat resistance and lowers the shrinkage rate. From the point, 2,000 or more is preferable, and 10,000 or less is preferable from the viewpoint of further increasing the solubility and decreasing the viscosity of the obtained solution.
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 which is a fluorescent polymer of this invention.
The triazine ring-containing polymer can be obtained by reacting a dihalogenated triazine compound having a predetermined arylamino group such as an anthrylamino group with a diaminoaryl compound.
For example, as shown in the following scheme 1, the linear polymer having a repeating structure (6 ′) is a dihalogenated triazine (9) having a 2-anthrylamino group and an aryldiamine compound (10) having a fluorene structure. Can be obtained by reacting in a suitable organic solvent.
The compound represented by the formula (10) can be obtained, for example, as a commercial product such as that manufactured by Aldrich, and the compound represented by the formula (9) includes a cyanuric halide and a predetermined arylamine compound. It can be easily produced according to the usual method of organic synthetic chemistry used.

（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 represents a halogen atom independently of each other. R represents the same meaning as described above.)

As the organic solvent, various solvents usually used in this kind of reaction can be used, for example, tetrahydrofuran, dioxane, N, N-dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, tetramethylurea. , Hexamethylphosphoramide, N, N-dimethylacetamide, N-methyl-2-piperidone, N, N-dimethylethyleneurea, N, N, N ′, N′-tetramethylmalonic acid amide, N-methylcaprolactam N-acetylpyrrolidine, N, N-diethylacetamide, N-ethyl-2-pyrrolidone, N, N-dimethylpropionic acid amide, N, N-dimethylisobutyramide, N-methylformamide, N, N′-dimethylpropylene 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 a mixed system thereof are preferable, and N, N-dimethylacetamide, N-methyl-2-pyrrolidone are particularly preferable. Is preferred.

In the above reaction, the reaction temperature may be appropriately set in the range from the melting point of the solvent to be used to the boiling point of the solvent, but is preferably about 0 to 250 ° C, more preferably 100 to 200 ° C.
The blending order of each component is arbitrary.
Moreover, in the case of a mixing | blending, you may add gradually by dripping etc., or you may add all at once.

In the above reaction, 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 bicarbonate, sodium ethoxide, sodium acetate, triethylamine, lithium carbonate, lithium hydroxide, lithium oxide, potassium acetate, magnesium oxide. , Calcium oxide, barium hydroxide, trilithium phosphate, trisodium phosphate, tripotassium phosphate, cesium fluoride, aluminum oxide, ammonia, trimethylamine, triethylamine, diisopropylamine, diisopropylethylamine, N-methylpiperidine, 2,2 , 6,6-tetramethyl-N-methylpiperidine, pyridine, 4-dimethylaminopyridine, N-methylmorpholine and the like.
1-100 equivalent is preferable with respect to 1 equivalent of triazine compound (9), and, as for the addition amount of a base, 1-10 equivalent is more preferable. These bases may be used as an aqueous solution.
Although it is preferable that the raw material component does not remain in the obtained polymer, a part of the raw material may remain as long as the effect of the present invention is not impaired.
After completion of the reaction, the product can be easily purified by a reprecipitation method or the like.

The fluorescent polymer comprising the triazine ring-containing polymer of the present invention described above is a fluorescent layer or a composition for forming a light emitting layer such as a composition for forming a fluorescent coating film or a composition for forming a light emitting layer such as an organic EL device. These compositions can be suitably used as a polymer varnish dissolved in various solvents.
The solvent used to dissolve the fluorescent polymer may be the same as or different from the solvent used during 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 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.

In the 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 that is a fluorescent polymer and a solvent, such as a leveling agent, a surfactant, a crosslinking agent, and other resins. Etc. may be included.
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 parts per 100 parts by mass of the triazine ring-containing polymer that is a fluorescent polymer. More preferably, 5 parts by mass.

The crosslinking agent is not particularly limited as long as it is a compound having a substituent capable of reacting with a triazine ring-containing polymer that is a fluorescent polymer.
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 a crosslinking reaction proceeds by an addition reaction with a triazine ring-containing polymer. To do.
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 Corp.), CY175, CY177, CY179 (above, made by CIBA-GEIGY A.G), Araldite CY-182, CY-192, CY-184 (above, CIBA-GEIGY A. G), Epicron 200, 400 (above, manufactured by DIC Corporation), Epicort (currently jER) 87 872 (above, manufactured by Japan Epoxy Resin Co., Ltd.), ED-5661, ED-5862 (above, manufactured by Celanese Coating Co., Ltd.), aliphatic polyglycidyl ether, Denacol EX-611, EX- 612, EX-614, EX-622, EX-411, EX-512, EX-522, EX-522, EX-421, EX-313, EX-314, EX-321 (Nagase ChemteX) Etc.) can also be used.

The 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 a triazine ring-containing polymer is obtained. The crosslinking reaction proceeds 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.

The (meth) acrylic compound has two or more (meth) acrylic groups in one molecule and undergoes a crosslinking reaction by an addition reaction with a triazine ring-containing polymer when exposed to a high temperature during thermosetting. It is a progression.
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 part.)

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

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

The aminoplast compound has two or more methoxymethylene groups in one molecule, and when exposed to a high temperature during thermosetting, a crosslinking reaction proceeds with a triazine ring-containing polymer by a demethanol condensation reaction. Is.
Examples of the melamine-based compound include Cymel series such as hexamethoxymethylmelamine CYMEL (registered trademark) 303, tetrabutoxymethylglycoluril 1170, tetramethoxymethylbenzoguanamine 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 a dehydration condensation reaction with a triazine ring-containing polymer when exposed to a high temperature during thermosetting. It is.
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 (above, 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 that is a fluorescent polymer, but considering the solvent resistance, the lower limit is preferably 10 parts by mass. The upper limit is preferably 50 parts by mass, and more preferably 30 parts by mass in consideration of controlling the refractive index.
When the crosslinking agent and the reactive terminal substituent of the triazine ring-containing polymer react with each other, and effects such as improved film density, improved heat resistance, and improved thermal relaxation ability can be achieved There is.
In addition, the said other component can be added at the arbitrary processes at the time of preparing the composition of this invention.

The 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 allowing 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, and has fluorescence, so that it is fluorescent. It can be suitably used for a coating layer, a light emitting layer used for an organic EL device, a color / wavelength conversion film, a photoelectric conversion layer used for an organic solar cell such as an organic thin film solar cell or a dye-sensitized solar cell.

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; Polyvinyl alcohol resin; polyglycolic acid; modified starch; cellulose acetate, cellulose triacetate; chitin, chitosan; lignin and the like. Examples of thermosetting resins include phenol resin, urea resin, melamine resin, and unsaturated polyester resin. , 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, 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.

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 photo radical polymerization initiators include, for example, Ciba Japan Co., Ltd. trade names: Irgacure 184, 369, 651, 500, 819, 907, 784, 2959, CGI 1700, CGI 1750, CGI 1850, CG 24-61, Darocur 1116, 1173, manufactured by BASF Co., Ltd. Product name: Lucillin TPO, manufactured by UCB Product name: Ubekrill P36, manufactured by Fratteri Lamberti Co., Ltd. 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 a synthesis example and an 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, ¹³ C-NMR]
Device: DRX400 manufactured by BRUKER
[FT-IR]
Apparatus: JASCO Corporation FT / IR-4200 typeA
[Elemental analysis]
Device: MT-6 CHN CORDER by Yanaco Technical Science Co., Ltd.
[GPC]
Equipment: HLC-8220 GPC manufactured by Tosoh Corporation
Column: TSK-GEL (α-M) manufactured by Tosoh Corporation
Column temperature: 45 ° C
Column flow rate: 0.2 mL / min
Solvent: N-methyl-2-pyrrolidone (hereinafter referred to as NMP) (including 0.01 mol / L lithium bromide)
Detector: UV-8020 (254 nm)
Calibration curve: Standard polystyrene [fluorescence spectrum]
Apparatus: Hitachi High-Technologies Corp. Spectrofluorimeter Fluorescence Spectrometer F-7000
[Absolute quantum yield]
Apparatus: Absolute PL quantum yield measuring apparatus C9220-02G manufactured by Hamamatsu Photonics Co., Ltd.

[1] Synthesis of monomer compound [Synthesis Example 1] Synthesis of 2-anthrylamino-4,6-dichloro-1,3,5-triazine (AntDCT)

Cyanuric chloride (3.688 g, 0.02 mol) and THF (100 mL) were added to a 500 mL three-necked flask, and a stirrer, a calcium chloride tube, a dropping funnel with a side tube and a thermometer were attached, and then stirred. Thawed completely and cooled to −5 ° C. on an ice bath. A solution prepared by dissolving 2-aminoanthracene (3.865 g, 0.02 mol) in THF (150 mL) was slowly added dropwise with a dropping funnel while paying attention to an increase in the reaction temperature. After completion of dropping, the mixture was stirred at −5 ° C. for 2 hours. A solution obtained by dissolving sodium carbonate (1.060 g, 0.01 mol) in distilled water (50 mL) was slowly added dropwise with a dropping funnel while paying attention to an increase in the reaction temperature. After completion of the dropwise addition, the mixture was stirred at 0 ° C. for 1 hour and then reacted at room temperature for 12 hours to confirm that the reaction solution was neutral. In the case of acidity, a small amount of sodium carbonate was dissolved in distilled water and dropped again to adjust to neutral.
After completion of the reaction, the reaction solution was transferred to a separatory funnel and washed with THF / saturated saline. The organic layer was transferred to an Erlenmeyer flask, and sodium sulfate was added thereto for dehydration and drying. After removing sodium sulfate by filtration, it was concentrated with an evaporator to obtain a crude product. The obtained crude product was recrystallized with a mixed solvent of toluene / hexane and dried under reduced pressure at 130 ° C. for 12 hours to obtain yellow needle crystals (yield 47%). It was 216-217 degreeC (document value 219-221 degreeC) when melting | fusing point of this compound was measured. Moreover, various spectrum analysis and elemental analysis were performed about this compound. The results are shown below.

FT-IR [KBr (cm ^-1 )]
ν 3242 (NH), 2879 (CH), 1595 (bending NH), 1548 (C = C), 1508 (C = N), 1233 (CN), 835 (C-Cl).
¹ H-NMR (400 MHz, DMSO-d ₆ , ppm)
δ 7.49-7.53 (m, 2H, Ar-H), 7.68 (d, 1H, Ar-H), 8.06-8.12 (m, 3H, Ar-H), 8.35 (s, 1H, Ar-H), 8.54 (d, 2H, Ar-H), 11.4 (s, 1H, NH).
¹³ C-NMR (100 MHz, DMSO-d ₆ , ppm)
δ 117.6, 122.0, 125.6, 125.8, 126.1, 126.3, 128.0, 128.3, 129.1, 129.2, 131.1, 131.2, 132.0, 164.1, 169.0, 170.0.
Elemental analysis (C ₁₃ H ₈ Cl ₂ N ₄ )
Calcd. C, 59.84; H, 2.95; N, 16.42 (%)
Found. C, 59.86; H, 2.99; N, 16.38 (%)

[Synthesis Example 2] Synthesis of 2,4-dichloro-6- (1-pyrenylamino) -1,3,5-triazine (DCPyT)

Cyanuric chloride (3.688 g, 0.02 mol) and THF (100 mL) were added to a 500 mL three-necked flask, and a stirrer, a calcium chloride tube, a dropping funnel with a side tube and a thermometer were attached, and then stirred. Thawed completely and cooled to −5 ° C. on an ice bath. A solution prepared by dissolving 1-aminopyrene (4.325 g, 0.02 mol) in THF (50 mL) was slowly dropped with a dropping funnel while paying attention to an increase in reaction temperature, and stirred at −5 ° C. for 2 hours after completion of the dropping. . A solution prepared by dissolving sodium carbonate (1.060 g, 0.01 mol) in distilled water (50 mL) was slowly dropped with a dropping funnel while paying attention to an increase in reaction temperature. After completion of the dropwise addition, the mixture was stirred at 0 ° C. for 1 hour, and then The reaction was carried out at room temperature for 3 hours, and the reaction solution was confirmed to be neutral. In the case of acidity, a small amount of sodium carbonate was dissolved in distilled water and dropped again to adjust to neutral.
After completion of the reaction, the reaction solution was transferred to a separatory funnel and washed with THF / saturated saline. The organic layer was transferred to an Erlenmeyer flask, and sodium sulfate was added thereto for dehydration and drying. After removing sodium sulfate by filtration, it was concentrated with an evaporator to obtain a crude product. The obtained crude product was recrystallized with a mixed solvent of 1,4-dioxane / hexane and dried under reduced pressure at 150 ° C. for 12 hours to obtain white powder crystals (yield 63%). When the melting point of this compound was measured, it was 228 to 230 ° C. (literature value 219 to 221 ° C.). Moreover, various spectrum analysis and elemental analysis were performed about this compound. The results are shown below.

FT-IR [KBr (cm ^-1 )]
ν 3223 (NH), 3090 (CH), 1603 (bending NH), 1548 (C = C), 1508 (C = N), 1232 (CN), 848 (C-Cl).
¹ H-NMR (400 MHz, DMSO-d ₆ , ppm)
δ 8.06-8.34 (m, 9H, Ar-H), 11.561 (s, 1H, -NH).
¹³ C-NMR (100 MHz, DMSO-d ₆ , ppm)
δ 122.4, 123.7, 124.4, 124.9, 125.1, 125.6, 125.7, 126.7, 127.2, 127.6, 128.0, 129.7, 129.8, 130.5, 130.7, 166.0, 169.3, 169.9.
Elemental analysis (C ₁₃ H ₈ Cl ₂ N ₄ )
Calcd. C, 62.48; H, 2.76; N, 15.34 (%)
Found. C, 62.71; H, 2.88; N, 15.29 (%)

[2] Synthesis of fluorescent polymer [Example 1-1] Synthesis of polymer compound [3]

Cesium fluoride (0.332 g, 2.2 mmol) was added to a 30 mL two-necked flask joined with a septum cap, a stirrer, a three-way cock, a nitrogen inlet tube, and a Dimroth condenser, and heated with a heat gun for 10 minutes under a nitrogen stream. After the heating, it was naturally cooled to room temperature. Thereafter, 9,9-bis (4-aminophenyl) fluorene [2] (1.0 mmol, manufactured by Aldrich) was added thereto, and dissolved in dehydrated NMP (2 mL). After stirring for about 10 minutes, AntDCT [1] (1.0 mmol) obtained in Synthesis Example 1 was added, and the mixture was further stirred for about 10 minutes, and then heated to 150 to 200 ° C. and stirred for 6 hours to be reacted. It was.
After completion of the reaction, the reaction solution was cooled to room temperature and diluted with NMP. This polymer solution was poured into methanol (300 mL / 3 mL) containing ammonia water to recover the polymer. The obtained polymer was dried under reduced pressure at room temperature for 6 hours. The dried polymer is dissolved in NMP and re-precipitated by adding it through methanol through a filter paper. The re-precipitate is dried under reduced pressure at 180 ° C. for 12 hours, and the target polymer [3] (Poly (βAntDCT-BAFL)) (Yield 95%). The obtained polymer [3] had a weight average molecular weight Mw measured in terms of polystyrene by GPC of 125,800 and a polydispersity Mw / Mn of 7.4.

[Example 1-2] Synthesis of polymer compound [5]

In the same manner as in Example 1 except that AntDCT [1] (1.0 mmol) obtained in Synthesis Example 1 was replaced with DCPyT [4] (1.0 mmol) obtained in Synthesis Example 2, the target polymer [ 5] (Poly (αDCPyT-BAFL)) was obtained (yield 75%). The obtained polymer [5] had a weight average molecular weight Mw measured in terms of polystyrene by GPC of 111,360 and a polydispersity Mw / Mn of 3.2. ¹ H-NMR spectrum analysis was performed on this compound. The results are shown below.

The βAntDCT, Poly (βAntDCT-BAFL), α-DCPyT, and Poly (αDCPyT-BAFL) obtained in Synthesis Examples 1 and 2 and Examples 1-1 and 1-2 were adjusted to a concentration of 10 ⁻⁶ M. The product was dissolved in NMP, and the fluorescence spectrum and absolute quantum yield were measured.
FIG. 1 shows the obtained fluorescence spectrum, and Table 1 shows values of excitation wavelength (λex), fluorescence wavelength (λem), and absolute quantum yield (Φem).

  As shown in FIG. 1 and Table 1, Poly (βAntDCT-BAFL) and Poly (αDCPyT-BAFL) obtained in Examples 1-1 and 1-2 were 36.5% and 59.5%, respectively. The quantum yield was confirmed and it was confirmed to be a fluorescent polymer.

Claims (10)

A fluorescent polymer comprising a triazine ring-containing polymer containing a repeating unit structure represented by the following formula (1).

{Wherein, R and R 'each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group,
Ar ¹ represents a naphthyl group, anthryl group, or pyrenyl group that may be substituted with Z;
Ar ² represents the formula (2) or (3).

[Wherein, R ^{1 to} R ¹² are each independently a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group which may have a branched structure having 1 to 10 carbon atoms, or 1 carbon atom. Represents an alkoxy group optionally having 10 to 10 branched structures,
W ¹ is a single bond, CR ¹³ R ¹⁴ (R ¹³ and R ¹⁴ are each independently a hydrogen atom or an alkyl group optionally having a branched structure of 1 to 10 carbon atoms (however, these are the same) And may form a ring.), C═O, O, S, SO, SO ₂ , or NR ¹⁵ (R ¹⁵ is a hydrogen atom or a branched structure having 1 to 10 carbon atoms). Represents an alkyl group which may have
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 (4).

(In the formula, R ^{16 to} R ¹⁹ are each independently a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group which may have a branched structure of 1 to 10 carbon atoms, or 1 carbon atom. Represents an alkoxy group optionally having 10 to 10 branched structures,
Y ¹ and Y ² each independently represent an alkylene group which may have a single bond or a branched structure having 1 to 10 carbon atoms. )]} The fluorescent polymer according to claim 1, wherein Ar ¹ represents an anthryl group or a pyrenyl group. The fluorescent polymer according to claim 1 or 2, wherein Ar ² is represented by formula (3). The fluorescent polymer according to claim 3, wherein Ar ² is represented by Formula (5).

  The composition for fluorescent coating film formation containing the fluorescent polymer of any one of Claims 1-4.   The luminescent material containing the fluorescent polymer of any one of Claims 1-4.   The pigment | dye containing the fluorescent polymer of any one of Claims 1-4.   A color / wavelength conversion material comprising the fluorescent polymer according to claim 1.   The organic solar cell containing the fluorescent polymer of any one of Claims 1-4.   An organic electroluminescence device comprising a light emitting layer containing the light emitting material according to claim 6.

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