WO2013094664A1 - Triazine ring-containing polymer and composition for film formation comprising same - Google Patents

Abstract

A triazine ring-containing hyperbranched polymer obtained by reacting a cyanuric halide and a diamine compound having an alicyclic structure under conditions in which the diamine compound has an excess of amino groups, said polymer having at least one terminal amino group derived from the diamine compound and comprising the repeating unit structure represented by formula (1). The polymer is highly transparent and highly light resistant, and can be used to provide a composition for film formation that is capable of producing a film having a thickness greater than 1,000 nm. In formula (1), R and R' each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group, and A represents an alkylene group having 3-20 alicyclic structures.

Description

Triazine ring-containing polymer and film-forming composition containing the same

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

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

In addition, a method using an inorganic metal oxide is known as the most effective method capable of achieving a higher refractive index of a polymer compound.
For example, a technique (Patent Document 1) has been reported in which a refractive index is increased by using a hybrid material obtained by mixing a siloxane polymer and a fine particle dispersed material in which zirconia or titania is dispersed.
Furthermore, a method of introducing a condensed cyclic skeleton having a high refractive index into a part of the siloxane polymer (Patent Document 2) has also been reported.

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

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

Recently, electronic devices such as liquid crystal displays, organic electroluminescence (EL) displays, optical semiconductor (LED) elements, solid-state imaging elements, organic thin film solar cells, dye-sensitized solar cells, and organic thin film transistors (TFTs) have been developed. At the same time, high-performance polymer materials have been required.
Specific characteristics required include 1) heat resistance, 2) transparency, 3) high refractive index, 4) light resistance, 5) high solubility, and 6) low volume shrinkage. In particular, optical materials are required to be improved in light resistance because deterioration due to light becomes a problem. In order to enhance light resistance, the prevention of deterioration by addition of an ultraviolet absorber or the introduction of a functional group having a stable radical has been studied, but there are few examples in which the polymer compound itself has high light resistance.

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

The inventors of the present invention can only achieve high heat resistance, high transparency, high refractive index, high solubility, and low volume shrinkage by using a hyperbranched polymer containing a repeating unit having a triazine ring and an alicyclic structure. In addition, it has also been found that it is excellent in light resistance and can be used as a film-forming composition when producing an electronic device or an optical member (PCT / JP2011 / 068937).
However, the film made of the hyperbranched polymer has several problems such as difficulty in increasing the film thickness, and further improvement is required for use as an optical material that requires a thick film.
The present invention has been made in view of such circumstances, a triazine ring-containing polymer capable of producing a film having a high transparency and a high light resistance and a thickness of 1000 nm or more, and a film formation including the same. It is an object to provide a composition for use.

In order to achieve the above object, the present inventors have conducted further studies on the hyperbranched polymer having an alicyclic structure excellent in light resistance, and as a result, cyanuric halide and a diamine containing an alicyclic structure, A hyperbranched polymer having a terminal amine obtained by reaction under an amine-excess condition can be easily combined with various crosslinking agents to form a highly transparent and light-resistant thick film. As a result, the present invention has been completed.

That is, the present invention
1. It is obtained by reacting cyanuric halide with a diamine compound having an alicyclic structure in a molar ratio in which the amino group of the diamine compound is excessive, and has at least one terminal amino group derived from the diamine compound, A triazine ring-containing hyperbranched polymer comprising 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 A represents an alkylene group having 3 to 20 alicyclic structures. )
2. 1 triazine ring-containing hyperbranched polymer obtained by reacting the cyanuric halide with the diamine compound having an alicyclic structure in a molar ratio of cyanuric halide: diamine compound = 1: 2 to 1: 6;
3. 1 or 2 triazine ring-containing hyperbranched polymer, wherein A represents at least one selected from the group represented by formulas (2) to (14),

(In the formula, R ¹ and R ² each independently represent an alkylene group which may have a branched structure having 1 to 5 carbon atoms.)
4). 3 is a triazine ring-containing hyperbranched polymer represented by formula (14),
5. 4 triazine ring-containing hyperbranched polymers in which R ¹ and R ² are both methylene groups,
6). A film-forming composition comprising the triazine ring-containing hyperbranched polymer of any one of 1 to 5 and a crosslinking agent;
7). 6. The film-forming composition according to 6, wherein the crosslinking agent is a compound having two or more blocked isocyanate groups in one molecule,
8). A film comprising any one of the triazine ring-containing hyperbranched polymers of 1 to 5,
9. A film obtained from the film forming composition of 6 or 7,
10. An optical member comprising a base material and 8 or 9 films formed on the base material is provided.

According to the present invention, it is possible to provide a triazine ring-containing polymer capable of producing a film having high transparency and high light resistance and a thickness of 1000 nm or more, and a film-forming composition containing the same.
The film containing the triazine ring-containing hyperbranched polymer of the present invention includes a liquid crystal display, an organic electroluminescence (EL) display, an optical semiconductor (LED) element, a solid-state imaging device, an organic thin film solar cell, a dye-sensitized solar cell, an organic thin film transistor ( It can be suitably used as a member for producing an electronic device such as a TFT. Moreover, it can utilize suitably as a member for lenses by which high refractive index is calculated | required.
In particular, since a thick film having high light resistance can be formed, application to the optical material field can be expected.

1 is a ¹ H-NMR spectrum diagram of a hyperbranched polymer [3] obtained in Example 1. FIG. 6 is a graph showing the transmittance of the coating film produced in Example 1. FIG. FIG. 3 is a diagram showing a TG-DTA measurement result of the hyperbranched polymer [3] obtained in Example 1. 6 is a graph showing the transmittance of a coating film produced in Example 2. FIG. It is a figure which shows the transmittance | permeability of the film produced in Example 3. FIG. It is a figure which shows the transmittance | permeability of the film produced in Example 4. FIG. It is a figure which shows the transmittance | permeability of the film produced in Example 5. FIG. It is a figure which shows the transmittance | permeability of the film produced in Example 6. FIG. It is a figure which shows the transmittance | permeability of the film produced in Example 7. FIG. It is a figure which shows the transmittance | permeability of the film produced in Example 8. It is a figure which shows the transmittance | permeability after 240 hours light irradiation of the film produced in Example 2. FIG. It is a figure which shows the transmittance | permeability after 240-hour light irradiation of the film produced in Example 3. FIG. It is a figure which shows the transmittance | permeability after 240-hour light irradiation of the film produced in Example 4. FIG. It is a figure which shows the transmittance | permeability after 240-hour light irradiation of the film produced in Example 5. FIG. It is a figure which shows the transmittance | permeability after 240-hour light irradiation of the film produced in Example 6. FIG. It is a figure which shows the transmittance | permeability after 240-hour light irradiation of the film produced in Example 7. FIG. It is a figure which shows the transmittance | permeability after 240-hour light irradiation of the film produced in Example 8. FIG. 3 is a ¹³ C-NMR spectrum diagram of the hyperbranched polymer [3] obtained in Example 1. FIG.

Hereinafter, the present invention will be described in more detail.
The triazine ring-containing hyperbranched polymer according to the present invention is obtained by reacting cyanuric halide with a diamine compound having an alicyclic structure at a molar ratio in which the amino group of the diamine compound is excessive, and at least one diamine compound And 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, 1-methyl group. -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, 3-methyl-cyclobutyl, 1,2-dimethyl-cyclopropyl, 2,3-dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl Ru-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, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 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 Ethyl-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-cycl And a ropropyl group and a 2-ethyl-3-methyl-cyclopropyl group.

The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably 1 to 20, and more preferably 1 to 10 carbon atoms, and even more preferably 1 to 3 carbon atoms in view of further improving the heat resistance of the polymer. . 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.

The number of carbon atoms of the aryl group is not particularly limited, but is preferably 6 to 40. In view of further improving the heat resistance of the polymer, 6 to 16 carbon atoms are more preferable, and 6 to 13 are even more preferable. .
Specific examples of the aryl group include phenyl group, o-chlorophenyl group, m-chlorophenyl group, p-chlorophenyl group, o-fluorophenyl group, p-fluorophenyl group, o-methoxyphenyl group, 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.

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

The A is not particularly limited as long as it is an alkylene group having 3 to 20 alicyclic structures, and examples thereof include groups represented by the following formulas (2) to (14). In view of further improving the light resistance of the compound, an alkylene group having a norbornane skeleton represented by the formula (14) is particularly preferable.

R ¹ and R ² independently represent an alkylene group which may have a branched structure having 1 to 5 carbon atoms.
Examples of such an alkylene group include a methylene, ethylene, propylene, trimethylene, tetramethylene, and pentamethylene group. In consideration of further increasing the refractive index of the obtained polymer, an alkylene having 1 to 3 carbon atoms. Group is preferable, an alkylene group having 1 to 2 carbon atoms, specifically, a methylene group or an ethylene group is more preferable, and a methylene group is most preferable.
In particular, in the alkylene group of the above formula (14), it is preferable that both R ¹ and R ² are methylene groups.

The weight average molecular weight of the hyperbranched polymer of the present invention is not particularly limited, but is preferably 400 to 500,000, more preferably 400 to 100,000, further improving heat resistance and reducing the shrinkage rate. Is preferably 600 or more, more preferably 50,000 or less, more preferably 30,000 or less, and even more preferably 10,000 or less from the viewpoint of further increasing the solubility and lowering the viscosity of the resulting solution. preferable.
In addition, the weight average molecular weight in this invention is an average molecular weight obtained by standard polystyrene conversion by gel permeation chromatography (henceforth GPC) analysis.

An example is given and demonstrated about the manufacturing method of the triazine ring containing hyperbranched polymer used by this invention.
For example, as shown in Scheme 1 below, the hyperbranched polymer (17) has a cyanuric halide (15) and a norbornanediamine (16) in which the amino group of the norbornanediamine (16) is a halogenated cyanuric (15) halogen. It can be obtained by reacting in an appropriate organic solvent at an excess molar ratio with respect to the atoms.
Thus, by making it react on amine excess conditions, the hyperbranched polymer (17) which has the amino group derived from the raw material diamine in the at least 1 (triazine ring) terminal is obtained.

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

The charging amount of each raw material is arbitrary as long as it is a ratio that causes an excess of amino groups so as to obtain the desired hyperbranched polymer, but diamine (1) (mol) with respect to 1 equivalent (mol) of cyanuric halide (15). 16) 2 to 6 equivalents (mol) are preferred, 2.5 to 6 equivalents (mol) are more preferred, and 3 to 5 equivalents (mol) are even more preferred.

As the organic solvent, various solvents usually used in this kind of reaction can be used, for example, tetrahydrofuran (THF), 1,4-dioxane, dimethyl sulfoxide; N, N-dimethylformamide, N-methyl- 2-pyrrolidone, tetramethylurea, hexamethylphosphoramide, N, N-dimethylacetamide, N-methyl-2-piperidone, N, N-dimethylethyleneurea, N, N, N ′, N′-tetramethylmalon Acid amide, N-methylcaprolactam, N-acetylpyrrolidine, N, N-diethylacetamide, N-ethyl-2-pyrrolidone, N, N-dimethylpropionic acid amide, N, N-dimethylisobutyramide, N-methylformamide, Amide solvents such as N, N′-dimethylpropyleneurea, and the like Mixed solvents thereof.
Of these, THF, 1,4-dioxane, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide and a mixed solvent thereof are preferable.

The reaction temperature may be appropriately set within 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 150 ° C, more preferably 60 to 100 ° C.
In particular, the reaction temperature is preferably 60 to 150 ° C., preferably 80 to 150 ° C., and preferably 80 to 120 ° C. from the viewpoint of suppressing linearity and increasing the degree of branching.

The mixing order of each component is arbitrary, but a solution containing cyanuric halide (15) or diamine (16) and an organic solvent is heated to 60 to 150 ° C., preferably 80 to 150 ° C., and at this temperature, the solution The method in which diamine (16) or cyanuric halide (15) is added is optimal.
In this case, either a component previously dissolved in a solvent or a component added later may be used, but a method of adding cyanuric halide (15) to a heated solution of diamine (16) is preferable.
Components added later may be added neat or in a solution dissolved in an organic solvent as described above, but the latter method is preferred in view of ease of operation and ease of reaction control. It is.
The addition may be gradually added by dropping or the like, or may be added all at once.
In Scheme 1, after mixing both compounds in a heated state, the target triazine ring-containing hyperbranch can be obtained without gelation even when reacted in one step (without increasing the temperature stepwise). A polymer can be obtained.

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 hydrogen carbonate, sodium ethoxide, sodium acetate, lithium carbonate, lithium hydroxide, lithium oxide, potassium acetate, magnesium oxide, oxidized Calcium, barium hydroxide, trilithium phosphate, trisodium phosphate, tripotassium phosphate, cesium fluoride, aluminum oxide, ammonia, trimethylamine, triethylamine, diisopropylmethylamine, diisopropylethylamine, N-methylpiperidine, 2,2, Examples include 6,6-tetramethyl-N-methylpiperidine, pyridine, 4-dimethylaminopyridine, N-methylmorpholine and the like.
The amount of base added is preferably 1 to 100 equivalents, more preferably 1 to 10 equivalents, per 1 equivalent of cyanuric halide (15). These bases may be used as an aqueous solution.
In the polymer obtained, it is preferable that no raw material components remain, but some raw materials may remain as long as the effects of the present invention are not impaired.
In any of the scheme methods, after completion of the reaction, the product can be easily purified by a reprecipitation method or the like.

In the production of the triazine ring-containing hyperbranched polymer of the present invention, after reacting cyanuric halide and the diamine compound, alkanolamine is added and further heated and stirred, but the reason is not clear. The coloring of the hyperbranched polymer obtained can be reduced, and the transparency of the film obtained therefrom can be improved.
Specific examples of the alkanolamine include methanolamine, ethanolamine, propanolamine, 1-amino-2-propanol, 1-amino-2-butanol, 1-amino-3-butanol, 4-amino-1-butanol and the like. Can be mentioned.

In this case, the amount of alkanolamine used is not particularly limited, but is preferably 0.05 to 500 equivalents, more preferably 0.05 to 120 equivalents, relative to 1 equivalent of cyanuric halide. 0.05 to 50 equivalents are even more preferable.
In this case, the treatment temperature is preferably 60 to 150 ° C., more preferably 80 to 150 ° C., and preferably 80 to 120 ° C.

The film-forming composition of the present invention contains the hyperbranched polymer described above, and can be suitably used, for example, as a composition in which the hyperbranched polymer is dissolved in various solvents.
The solvent used for polymer dissolution 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 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, dipropylene glycol mono Tyl ether, diethylene glycol monomethyl ether, dipropylene glycol monoethyl ether, diethylene glycol monoethyl ether, triethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, γ-butyrolactone, acetone, methyl ethyl ketone, methyl isopropyl ketone, diethyl ketone, methyl isobutyl ketone, methyl normal Butyl ketone, cyclohexanone, ethyl acetate, isopropyl ketone, normal propyl acetate, isobutyl acetate, normal butyl acetate, ethyl lactate, methanol, ethanol, normal propanol, isopropanol, normal butanol, isobutanol, tert-butanol, 1-pentanol, 2-methyl-2-butanol, 2- Methyl-1-butanol, 1-hexanol, cyclohexanol, 2-methyl-1-pentanol, 1-heptanol, 1-octanol, 2-ethylhexanol, 1-methoxy-2-butanol, diacetone alcohol, allyl alcohol, Ethylene glycol, propylene glycol, hexylene glycol, trimethylene glycol, furfuryl alcohol, tetrahydrofurfuryl alcohol, benzyl alcohol, diethylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, isopropyl Ether, tetrahydrofuran, 1,4-dioxane, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, di Til sulfoxide, N-cyclohexyl-2-pyrrolidinone, and the like. From the viewpoint of solubility and storage stability of the polymer, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene are more preferable. Examples include glycol monobutyl ether and cyclohexanone.

At this time, the solid content concentration in the film-forming composition is not particularly limited as long as it does not affect the storage stability, and may be appropriately set according to the target film thickness. Specifically, from the viewpoint of solubility and storage stability, the solid content concentration is preferably 0.1 to 50% by mass, and considering the formation of a thicker film, 1 to 30% by mass is preferable.

The film-forming composition of the present invention may contain other components, for example, a leveling agent, a surfactant, a crosslinking agent, etc., as long as the effects of the present invention are not impaired. In particular, it is preferable that a crosslinking agent is contained for the purpose of increasing the light resistance and strength of the thin film obtained from the composition.
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 Electronics Kasei Co., Ltd. (formerly Gemco Co., Ltd.)), trade names MegaFuck F171, F173, F554, R-08, R-30 (DIC Corporation), Florard FC430, Fluorosurfactants such as FC431 (manufactured by Sumitomo 3M Limited), trade names Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (produced by Asahi Glass Co., Ltd.), Organoshiroki 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 (BIC 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 still more preferably 0.01 to 0.5 parts by mass with respect to 100 parts by mass of the hyperbranched polymer. preferable.

The crosslinking agent is not particularly limited as long as it is a compound having a substituent capable of reacting with the hyperbranched polymer of the present invention.
Examples of such compounds include melamine compounds having a crosslinkable substituent such as a methylol group and a methoxymethyl group, substituted urea compounds, compounds containing a crosslinkable substituent such as an epoxy group or an oxetane group, and isocyanate groups. A compound having a blocked isocyanate group, a compound having an acid anhydride, a compound having a (meth) acryl group, a phenoplast compound, etc., from the viewpoint of heat resistance and storage stability, an epoxy group, A compound containing a blocked isocyanate group or a (meth) acryl group is preferred.
Further, the blocked isocyanate group is preferable from the viewpoint that the refractive index does not decrease because it is crosslinked by a urea bond and has a carbonyl group, and low temperature curability and thick film formation.
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 is caused by an addition reaction with the hyperbranched polymer of the present invention. It is a progression.
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, Celoxide 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.) A phenol novolac epoxy resin Coat (currently jER) 152, 154 (above, Japan Epoxy Resin Co., Ltd.), EPPN 201, 202 (above, Nippon Kayaku Co., Ltd.), cresol novolac type epoxy resin, EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, EOCN-1027 (manufactured by Nippon Kayaku Co., Ltd.), Epicort (currently jER) 180S75 (manufactured by Japan Epoxy Resin Co., Ltd.), Alicyclic Denacol EX-252 (manufactured by Nagase ChemteX Corp.), CY175, CY177, CY179 (above, CIBA-GEIGY AG), Araldite CY-182, CY-192, CY- 184 (above, manufactured by CIBA-GEIGY AG), Epicron 200, 4 0 (above, manufactured by DIC Corporation), Epicoat (currently, jER) 871, 872 (above, manufactured by Japan Epoxy Resin Co., Ltd.), ED-5661, ED-5661 (above, manufactured by Celanese Coating Co., Ltd.) ), An aliphatic polyglycidyl ether, Denacol EX-611, EX-612, EX-614, EX-622, EX-411, EX-512, EX-522, EX-421, The same EX-313, EX-314, EX-321 (manufactured by Nagase ChemteX Corporation) and the like can also be used.

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

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

The compound having the (meth) acryl group is available as a commercial product, and specific examples thereof include NK ester A-200, A-400, A-600, A-1000, A-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.), KAYARAD (registered trademark) DPEA-12, PEG400DA, THE- 30, RP-1040 (above, Nippon Kayaku Co., Ltd.), M-210, M-350 (above, Toagosei Co., Ltd.), KAYARAD (registered trademark) DPHA, NPGDA, PET30 (above , Nippon Kayaku Co., Ltd.), NK Esters A-DPH, A-TMPT, A-DCP, A-HD-N, TMPT, DCP, NPG, HD-N Nakamura Chemical Co., Ltd.).

As a compound containing a blocked isocyanate group, when the isocyanate group (—NCO) has two or more blocked isocyanate groups blocked by an appropriate protective group in one molecule, it is exposed to a high temperature during thermosetting. , The protecting group (block part) is dissociated by thermal dissociation, and the resulting isocyanate group causes a crosslinking reaction with the hyperbranched polymer of the present invention. Examples thereof include compounds having at least one group (these groups may be the same or different from each other).

(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, cyclohexanol; phenol, 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.

The compound containing a blocked isocyanate group 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 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.

Examples of the compound having an isocyanate group include the above-described compounds having two or more isocyanate groups in one molecule, and isocyanurate type polyfunctional isocyanate compounds are particularly suitable. Such a compound is also available as a commercial product. For example, Duranate (registered trademark) 24A-100, 22A-75P, 21S-75E, TPA-100, TKA-100, MFA-75B, MHG-80B, TLA-100, TSE-100, TSA-100, TSS-100, TSE-100, P301-75E, E402-80B, E405-70B, AE700-100, D101, D201, A201H 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 the hyperbranched polymer of the present invention by a demethanol condensation reaction. To do.
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 when exposed to a high temperature during thermosetting, a crosslinking reaction proceeds with the hyperbranched polymer of the present invention by an addition reaction. .
Examples of the compound having an oxetane group include OX-221-containing oxetane group, OX-SQ-H, and OX-SC (manufactured by Toagosei Co., Ltd.).

The phenoplast compound has two or more hydroxymethylene groups in one molecule, and when exposed to a high temperature during thermosetting, a crosslinking reaction proceeds with the hyperbranched polymer of the present invention by a dehydration condensation reaction. 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 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, BI25X-DF. BI25X-TPA (above, manufactured by Asahi Organic Materials Co., Ltd.).

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 hyperbranched polymer, but considering the solvent resistance, the lower limit is preferably 10 parts by mass, more preferably 20 parts by mass. Furthermore, in consideration of controlling the refractive index, the upper limit is preferably 50 parts by mass, more preferably 30 parts by mass.
By using the cross-linking agent, the cross-linking agent and the reactive terminal amino group of the hyperbranched polymer react to exhibit effects such as improvement in film density, heat resistance, and heat relaxation ability.
In addition, the said other component can be added at the arbitrary processes at the time of preparing the composition of this invention.

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

As the base material, silicon, glass with indium tin oxide (ITO) formed, glass with indium zinc oxide (IZO) formed, polyethylene terephthalate (PET), plastic, glass, quartz, ceramics A flexible substrate having flexibility can be used.
The firing temperature is not particularly limited for the purpose of evaporating the solvent, and can be carried out, for example, at 40 to 400 ° C. However, when the above-mentioned crosslinking agent having a blocked isocyanate group is used, a low temperature heating of about 40 to 200 ° C. is sufficient. It is. 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 thickness of the film made of the composition of the present invention thus obtained is not particularly limited, but in the present invention, it is one of the features that a thick film can be formed, It can be 1000 nm or more, and can also be 1500 nm or more.
Since the film of the present invention can achieve high heat resistance, high transparency, high refractive index, high solubility, low volume shrinkage and high light resistance, it can be used for liquid crystal displays, organic electroluminescence (EL) displays, optical semiconductors (LEDs). ) It can be suitably used as one member or an optical member for producing an electronic device such as an element, a solid-state imaging device, an organic thin film solar cell, a dye-sensitized solar cell, or an organic thin film transistor (TFT).

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); cyclic olefin resin; Polystyrene resins such as PS (polystyrene), HIPS (high impact polystyrene), AS (acrylonitrile-styrene copolymer), ABS (acrylonitrile-butadiene-styrene copolymer), MS (methyl methacrylate-styrene copolymer) Polycarbonate resin; polyamide resin; polyimide resin; (meth) acrylic resin such as PMMA (polymethyl methacrylate); PET (polyethylene terephthalate), polybutylene terephthalate, polyethylene naphthalate, poly Polyester resins such as tylene naphthalate, PLA (polylactic acid), poly-3-hydroxybutyric acid, polycaprolactone, polybutylene succinate, polyethylene succinate / adipate; polyphenylene ether resin; modified polyphenylene ether resin; polyacetal resin; Polyphenylene sulfide 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, Examples include unsaturated polyester resins, polyurethane resins, and epoxy resins.
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 weight, more preferably 100 parts by weight of the hyperbranched polymer. 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, 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) Chlorate, 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 polymerization initiator or a heat radical polymerization 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).
Commercially available radical photopolymerization initiators include, for example, BASF Corporation trade names: Irgacure 184, 369, 651, 500, 819, 907, 784, 2959, trade names: CGI 1700, CGI 1750, CGI 1850, CG 24-61, trade names : Darocur 1116, 1173, trade name: Lucyrin TPO, manufactured by UCB trade name: Ubekrill P36, manufactured by Fratteri Lamberti trade name: Ezacure KIP150, KIP65LT, KIP100F, KT37, KT55, KTO46, KIP75 / B, etc. .

The radical photopolymerization initiator is preferably used in the range of 0.1 to 15 parts by mass, more preferably in the range of 1 to 10 parts by mass with respect to 100 parts by mass of the (meth) acrylate compound.
Examples of the solvent used for the polymerization include the same solvents as those exemplified above for the film-forming composition.

EXAMPLES Hereinafter, although an Example is 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]
Equipment: JEOL-ECX300 (300 MHz)
Measuring solvent: DMSO-d6
Reference substance: Tetramethylsilane (TMS) (δ0.0ppm)
[ ¹³ C-NMR]
Equipment: JEOL-ECA700 (700MHz)
Measuring solvent: DMSO-d6
Reference substance: DMSO (δ 39.5 ppm)
Measurement temperature: Room temperature [GPC]
Equipment: HLC-8320 GPC manufactured by Tosoh Corporation
Column: Shodex KF-802.5 + KF-803L
Column temperature: 40 ° C
Solvent: Tetrahydroamine-added tetrahydrofuran with 20 mM Detector: UV (254 nm)
Calibration curve: Standard polystyrene [UV-visible spectrophotometer]
Apparatus: SHIMADSU UV-3600 manufactured by Shimadzu Corporation
[Ellipsometer]
Apparatus: Multi-angle-of-incidence spectroscopic ellipsometer VASE manufactured by JA Woollam Japan
[Differential thermal balance (TG-DTA)]
Equipment: TG-8120, manufactured by Rigaku Corporation
Temperature increase rate: 15 ° C / min Measurement temperature: 25 ° C-750 ° C
[Light resistance test]
Device: Q-Sun Xe-1 manufactured by Q-Lab Corporation
Illuminance: 0.55 W / cm ² (@ 340 nm)
Black panel temperature: 80 ° C
[Film thickness measurement]
Ellipsometer

[1] Synthesis of triazine ring-containing hyperbranched polymer [Example 1]

Under nitrogen, 189.6 g of N, N-dimethylacetamide was placed in a 1000 mL four-necked flask, and 138.81 g of norbornanediamine [2] (0.9 mol, manufactured by Mitsui Chemicals Fine Co., Ltd.) was added to the flask. Heated to. Thereto, 55.18 g of 2,4,6-trichloro-1,3,5-triazine [1] (0.3 mol, manufactured by Evonik Degussa) was dissolved in 352.1 g of dimethylacetamide and maintained at −10 ° C. The solution was added dropwise to initiate polymerization. One hour after the completion of dropping, 59.50 g of cyclohexylamine (0.6 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) and 90.13 g of DL-1-amino-2-propanol (1.2 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) ) And the mixture was stirred for 60 minutes. The reaction system was returned to room temperature, and the reaction solution was added to 2500 g of ion-exchanged water for reprecipitation. The precipitate was filtered, the filtrate was redissolved in 864 g of THF, and 200 g of 28% aqueous ammonia solution was added. This solution was dropped into 4000 g of ion-exchanged water for reprecipitation, and the precipitate was filtered. The obtained solid was dried under reduced pressure at 150 ° C. for 8 hours to obtain 56.6 g of the desired hyperbranched polymer [3] (hereinafter abbreviated as TNB-C).
The measurement result of ¹ H-NMR spectrum of TNB-C is shown in FIG. 1, and the measurement result of ¹³ C-NMR spectrum is shown in FIG. The obtained TNB-C is a compound having a structural unit represented by the formula (1). Further, ¹³ C-NMR measurement revealed that no characteristic aminopropanol-derived signal was observed at 21 ppm, 48 ppm, or 65 ppm, and thus aminopropanol was not introduced into the obtained compound.
The weight average molecular weight Mw measured by GPC of TNB-C in terms of polystyrene was 5300, and the polydispersity Mw / Mn was 8.70.

<Refractive index and transmittance measurement>
0.1 g of TNB-C obtained in Example 1 was dissolved in 0.9 g of propylene glycol monomethyl ether to obtain a colorless transparent solution. The obtained solution was spin-coated on a glass substrate with a spin coater at 100 rpm for 5 seconds and at 800 rpm for 30 seconds, baked at 100 ° C. for 1 minute and 250 ° C. for 5 minutes to remove the solvent, and the film (thickness 3517 nm) ) When the refractive index of the obtained film was measured, the refractive index at 550 nm was 1.5997.
Further, the transmittance of the film obtained above was measured at 400 to 800 nm. The results are shown in FIG.

<Heat resistance test>
When 4.970 mg of TNB-C obtained in Example 1 was added to a platinum pan and measured with TG-DTA at a heating rate of 15 ° C./min, the 5% weight loss was 433 ° C. The result is shown in FIG.

[2] Preparation of film-forming composition (thermosetting composition) and film [Example 2]
1.0 g of TNB-C, 0.2 g of Cymel 303 (manufactured by MT Aqua Polymer Co., Ltd.), 0.0005 g of MegaFace F-554 (manufactured by DIC Co., Ltd.) were dissolved in 4.80 g of PGME and 0.17 g of cyclohexanone to obtain a solid content. A 20 mass% solution (hereinafter abbreviated as TNB-CC2) was prepared.
The obtained TNB-CC2 was used to spin-coat with a film thickness of 2000 nm, fired at 100 ° C. for 2 minutes, and then fired at 150 ° C. for 10 minutes to produce a coating (hereinafter abbreviated as TNB-CC2F).

[Example 3]
1.0 g of TNB-C, 0.3 g of Cymel 303 (manufactured by MT Aqua Polymer Co., Ltd.), 0.0005 g of Megafac F-554 (manufactured by DIC Co., Ltd.) were dissolved in 5.20 g of PGME and 0.19 g of cyclohexanone to obtain a solid content. A 20 mass% solution (hereinafter abbreviated as TNB-CC3) was prepared.
Using the obtained TNB-CC3, spin coating was performed with a spin coating method aiming at a film thickness of 2000 nm, baked at 100 ° C. for 2 minutes, and then baked at 150 ° C. for 10 minutes. Was made.

[Example 4]
1.0 g of TNB-C, 0.4 g of Cymel 303 (manufactured by MT Aqua Polymer Co., Ltd.), and 0.0005 g of MegaFac F-554 (manufactured by DIC Co., Ltd.) were dissolved in 5.60 g of PGME and 0.20 g of cyclohexanone to obtain a solid. A 20% by weight concentration solution (hereinafter abbreviated as TNB-CC4) was prepared.
Using the obtained TNB-CC4, spin coating was performed aiming at a film thickness of 2000 nm, baking was performed at 100 ° C. for 2 minutes, and then baking was performed at 150 ° C. for 10 minutes to form a coating (hereinafter abbreviated as TNB-CC4F).

[Example 5]
1.0 g of TNB-C, 0.058 g of B-882N (Mitsui Chemicals Co., Ltd.), and 0.0005 g of Megafac F-554 (manufactured by DIC Co., Ltd.) were dissolved in 4.40 g of PGME and 0.10 g of cyclohexanone, and the solid was dissolved. A 20% by weight concentration solution (hereinafter abbreviated as TNB-CB1) was prepared.
Using the obtained TNB-CB1, spin-coated with a thickness of 2000 nm, fired at 100 ° C. for 2 minutes, and then fired at 150 ° C. for 10 minutes to produce a coating (hereinafter abbreviated as TNB-CB1F).

[Example 6]
1.0 g of TNB-C, 0.116 g of B-882N (Mitsui Chemicals Co., Ltd.), and 0.0005 g of MegaFac F-554 (manufactured by DIC Co., Ltd.) were dissolved in 4.80 g of PGME and 0.17 g of cyclohexanone to obtain a solid. A 20% by weight concentration solution (hereinafter abbreviated as TNB-CB2) was prepared.
Using the obtained TNB-CB2, spin-coated with a thickness of 2000 nm, fired at 100 ° C. for 2 minutes, and then fired at 150 ° C. for 10 minutes to form a coating (hereinafter abbreviated as TNB-CB2F).

[Example 7]
1.0 g of TNB-C, 0.175 g of B-882N (Mitsui Chemicals Co., Ltd.), and 0.0005 g of Megafac F-554 (manufactured by DIC Co., Ltd.) were dissolved in 5.20 g of PGME and 0.19 g of cyclohexanone to obtain a solid. A 20% by weight partial concentration solution (hereinafter abbreviated as TNB-CB3) was prepared.
Using the obtained TNB-CB3, spin coating was performed aiming at a film thickness of 2000 nm, followed by baking at 100 ° C. for 2 minutes, and then baking at 150 ° C. for 10 minutes to form a coating (hereinafter abbreviated as TNB-CB3F).

[Example 8]
1.0 g of TNB-C, 0.233 g of B-882N (Mitsui Chemicals Co., Ltd.), and 0.0005 g of Megafac F-554 (manufactured by DIC Co., Ltd.) were dissolved in 5.60 g of PGME and 0.20 g of cyclohexanone to obtain a solid. A 20% by weight concentration solution (hereinafter abbreviated as TNB-CB4) was prepared.
Using the obtained TNB-CB4, spin coating was performed aiming at a film thickness of 2000 nm, followed by baking at 100 ° C. for 2 minutes, and then baking at 150 ° C. for 10 minutes to form a coating (hereinafter abbreviated as TNB-CB4F).

<Refractive index, transmittance and film thickness measurement>
With respect to the coating films prepared in Examples 2 to 8, the transmittance, refractive index, and film thickness were measured.
The transmittances of the films obtained in Examples 2 to 8 are shown in FIGS. 4 to 10, respectively, and the refractive index and film thickness are shown in Table 1.
<Solvent resistance test>
The films prepared in Examples 2 to 8 were immersed in PGME for 5 minutes, and the film thickness after removing PGME by spray drying was measured to evaluate the solvent resistance. The results of the remaining film rate are also shown in Table 1.

As shown in Table 1, by using the terminal functional group of the hyperbranched polymer and combining with various crosslinking agents, a curable coating film having a relatively thick thickness of 1700 nm or more and good solvent resistance can be obtained. I understand that.
The obtained cured film has high transparency from the visible light region to the near ultraviolet region, as shown in FIGS.
Polyolefin, PMMA, and cycloolefin polymers have a refractive index of about 1.49 to 1.55, but as shown in Table 1, hyperbranched polymers composed of alicyclic structures and triazine rings It was found that the refractive index was higher than that.

<Light resistance test>
The films prepared in Examples 2 to 8 were subjected to a light resistance test by irradiation with light for 240 hours. Further, the refractive index after the light resistance test was measured.
The transmittances after the light resistance test of the coatings obtained in Examples 2 to 8 are shown in FIGS. 11 to 17, respectively, and the refractive index is shown in Table 2.

As shown in FIGS. 11 to 17 and Table 2, as a result of a light resistance test using a xenon lamp, it was found that the refractive index and transmittance did not change and the material was highly light resistant. It is expected to be applied to the field of optical materials because of its high light resistance.

Claims (10)

1. It is obtained by reacting cyanuric halide with a diamine compound having an alicyclic structure in a molar ratio in which the amino group of the diamine compound is excessive, and has at least one terminal amino group derived from the diamine compound, A triazine ring-containing hyperbranched polymer comprising 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 A represents an alkylene group having 3 to 20 alicyclic structures. )
2. 2. The triazine ring-containing hyperbranched polymer according to claim 1, obtained by reacting the cyanuric halide with the diamine compound having an alicyclic structure in a molar ratio of cyanuric halide: diamine compound = 1: 2 to 1: 6. .
3. The triazine ring-containing hyperbranched polymer according to claim 1 or 2, wherein A represents at least one selected from the group represented by formulas (2) to (14).
   

   

   (In the formula, R ¹ and R ² each independently represent an alkylene group which may have a branched structure having 1 to 5 carbon atoms.)
4. The triazine ring-containing hyperbranched polymer according to claim 3, wherein A is represented by formula (14).
5. The triazine ring-containing hyperbranched polymer according to claim 4, wherein both R ¹ and R ² are methylene groups.
6. A film-forming composition comprising the triazine ring-containing hyperbranched polymer according to any one of claims 1 to 5 and a crosslinking agent.
7. The film-forming composition according to claim 6, wherein the crosslinking agent is a compound having two or more blocked isocyanate groups in one molecule.
8. A film containing the triazine ring-containing hyperbranched polymer according to any one of claims 1 to 5.
9. A film obtained from the film-forming composition according to claim 6 or 7.
10. An optical member comprising a base material and the film according to claim 8 or 9 formed on the base material.

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