JP7845355B2 - Triazine ring-containing polymer and film-forming composition containing the same - Google Patents

Description

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

In recent years, high-performance polymer materials have become increasingly required when developing electronic devices such as liquid crystal displays, organic electroluminescent (EL) elements (organic EL displays and organic EL lighting), touch panels, optoelectronic semiconductor (LED) elements, solid-state image sensors, organic thin-film solar cells, dye-sensitized solar cells, and organic thin-film transistors (light-emitting diodes (LEDs), etc.).
The specific properties that are required include: 1) heat resistance, 2) transparency, 3) high refractive index, 4) high solubility, 5) low volume shrinkage, 6) high temperature and humidity resistance, and 7) high film hardness.
In view of this, the applicant has already found that polymers containing repeating units having triazine rings and aromatic rings have a high refractive index, and that the polymer alone can achieve high heat resistance, high transparency, high refractive index, high solubility, and low volume shrinkage, making it suitable as a film-forming composition when fabricating electronic devices (Patent Document 1).
Furthermore, the applicant has already discovered that polymers containing repeating units having triazine rings and alicyclic structures have a high refractive index, and that the polymer alone can achieve high heat resistance, high transparency, high refractive index, high solubility, and low volume shrinkage, making them suitable as film-forming compositions when fabricating electronic devices (Patent Document 2).
However, there was room for improvement in terms of solvent resistance.

International Publication No. 2010/128661 International Publication No. 2012/026452

The present invention has been made in view of the above circumstances, and aims to provide a triazine ring-containing polymer that can form a cured film having high transparency and high solvent resistance.

The inventors, after diligent research to achieve the above objective, discovered that by using a triazine ring-containing polymer having at least one triazine ring terminus, and in which at least a portion of the triazine ring terminus is sealed with an amino group having a crosslinking group, it is possible to form a cured film that is highly transparent and highly solvent-resistant, thus completing the present invention.

In other words, the present invention provides the following triazine ring-containing polymers and film-forming compositions containing them.
[1] A triazine ring-containing polymer comprising a repeating unit structure represented by the following formula (1), having at least one triazine ring terminus, wherein at least a portion of this triazine ring terminus is sealed with an amino group having a crosslinking group (excluding a hydroxyl group).
(In formula (1), R and R' independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group, and Q represents a C3-C20 alkylene group having an alicyclic structure. * represents a bond.)
[2] The triazine ring-containing polymer according to [1], wherein Q in formula (1) represents at least one selected from the group shown by formulas (2) to (15).
(In formulas (2) to (15), ^R1 and ^R2 independently represent alkylene groups having 1 to 5 carbon atoms, which may have a branched structure. * represents a bond.)
[3] The triazine ring-containing polymer according to [2], wherein Q in formula (1) is represented by formula (4).
[4] The triazine ring-containing polymer according to [2], wherein ^R1 and ^R2 are methylene groups.
[5] The triazine ring-containing polymer according to any one of [1] to [4], wherein the crosslinking group is selected from the group consisting of a vinyl-containing group, an epoxy-containing group, an oxetane-containing group, a carboxy-containing group, a sulfo-containing group, a thiol-containing group, and a (meth)acryloyl-containing group.
[6] The triazine ring-containing polymer according to any one of [1] to [5], wherein the crosslinking group is a (meth)acryloyl-containing group.
[7] The triazine ring-containing polymer according to [6], wherein the crosslinking group is a (meth)acryloyloxyalkyl group or a group represented by the following formula (i).
(In formula (i), ^A1 represents an alkylene group having 1 to 10 carbon atoms, and ^A2 represents a single bond or the following formula (j)
A represents a group represented by , where ^A3 represents an (a+1) valent aliphatic hydrocarbon group which may be substituted with a hydroxyl group, ^A4 represents a hydrogen atom or a methyl group, a represents 1 or 2, and * represents a bond.
[8] The triazine ring-containing polymer according to [7], wherein the crosslinking group is selected from a (meth)acryloyloxymethyl group, a (meth)acryloyloxyethyl group, and a group represented by the following formulas (i-2) to (i-7).
(In equations (i-2) to (i-7), * represents a combination.)
[9] A film-forming composition comprising a triazine ring-containing polymer according to any one of [1] to [8].
[10] The film-forming composition according to [9], further comprising a crosslinking agent.
[11] The film-forming composition according to [10], wherein the crosslinking agent is a polyfunctional (meth)acrylic compound.
[12] A film obtained from any of the film-forming compositions described in [9] to [11].
[13] An electronic device comprising a substrate and a film described in [12] formed on the substrate.
[14] An optical member comprising a substrate and a film described in [12] formed on the substrate.

According to the present invention, a triazine ring-containing polymer can be provided that can form a cured film having high transparency and high solvent resistance.
Films produced from the film-forming composition of the present invention can exhibit properties such as solvent resistance, high heat resistance, low volume shrinkage, and solvent resistance (crack resistance), and can therefore be suitably used in the fields of electronic devices and optical materials, such as liquid crystal displays, organic EL elements (organic EL displays and organic EL lighting), touch panels, optoelectronic semiconductor elements, solid-state image sensors, organic thin-film solar cells, dye-sensitized solar cells, organic thin-film transistors, lenses, prisms, cameras, binoculars, microscopes, and semiconductor exposure equipment.
In particular, films made from the film-forming composition of the present invention have high transparency and high solvent resistance (crack resistance). Therefore, when used as a planarization layer, light scattering layer, or encapsulant for organic EL lighting, it is possible to improve the light extraction efficiency (light diffusion efficiency) and durability.

This is the ^1H -NMR spectrum of compound P-1 (polymer compound [4]) obtained in Example 1-1. This is an optical microscope image of the surface of the cured film obtained in Example 2-1. This is an optical microscope image of the surface of the cured film obtained in Comparative Example 2-1. This is an optical microscope image of the surface of the cured film in Example 3-1 after exposure to a solvent. This is an optical microscope image of the surface of the cured film in Comparative Example 3-1 after exposure to a solvent. This is an optical microscope image of the surface of the cured film obtained in Example 4-1. This is an optical microscope image of the surface of the cured film in Example 5-1 after exposure to a solvent. This is an optical microscope image of the surface of the cured film in Example 5-2 after exposure to solvent. This is an optical microscope image of the surface of the cured film in Example 5-3 after exposure to solvent.

The present invention will be described in more detail below.
(Triadine ring-containing polymer)
The triazine ring-containing polymer according to the present invention contains a repeating unit structure represented by the following formula (1).
Triazine ring-containing polymers are, for example, so-called hyperbranched polymers. Hyperbranched polymers are highly branched polymers that have an irregular branching structure. Irregularity here means that the branching structure is more irregular than that of dendrimers, which are highly branched polymers that have a regular branching structure.
For example, a hyperbranched polymer containing a triazine ring includes a structure (structure X) that is larger than the repeating unit structure represented by formula (1), in which each of the three bonds of the repeating unit structure represented by formula (1) is bonded to the repeating unit structure represented by formula (1). In a hyperbranched polymer containing a triazine ring, structure X is distributed throughout the entire triazine ring containing polymer except for the ends.
In a hyperbranched polymer containing a triazine ring, the repeating unit structure may consist solely of a repeating unit structure represented by formula (1).

<Formula (1)>
* represents a combination.

<<R, and R'>>
In the above formula, R and R' independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group, but from the viewpoint of further increasing the refractive index, it is preferable that both are hydrogen atoms.
In the present invention, the number of carbon atoms in the alkyl group is not particularly limited, but 1 to 20 is preferred, and considering the need to further improve the heat resistance of the polymer, the number of carbon atoms in the alkyl group is more preferably 1 to 10, and even more preferably 1 to 3. Furthermore, the structure of the alkyl group is not particularly limited and may be linear, branched, cyclic, or a combination of two or more of these.

Specific examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, s-butyl, t-butyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclobutyl, 1,2-dimethyl-cyclopropyl, 2,3-dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl- n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl-cyclobutyl, 2,4-dimethyl-cyclobutyl Examples include ethyl-cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-isopropyl-cyclopropyl, 2-isopropyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl, and 2-ethyl-3-methyl-cyclopropyl groups.

The number of carbon atoms in the alkoxy group is not particularly limited, but 1 to 20 is preferred. Considering the need to further enhance the heat resistance of the polymer, 1 to 10 carbon atoms are more preferred, and 1 to 3 carbon atoms are even more preferred. Furthermore, the structure of the alkyl portion is not particularly limited and may be linear, branched, cyclic, or a combination of two or more of these.

Specific examples of alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, s-butoxy, t-butoxy, n-pentoxy, 1-methyl-n-butoxy, 2-methyl-n-butoxy, 3-methyl-n-butoxy, 1,1-dimethyl-n-propoxy, 1,2-dimethyl-n-propoxy, 2,2-dimethyl-n-propoxy, 1-ethyl-n-propoxy, n-hexyloxy, 1-methyl-n-pentyloxy, 2-methyl-n-pentyloxy, and 3-methyl-n-pentyloxy. Examples include pentyloxy, 4-methyl-n-pentyloxy, 1,1-dimethyl-n-butoxy, 1,2-dimethyl-n-butoxy, 1,3-dimethyl-n-butoxy, 2,2-dimethyl-n-butoxy, 2,3-dimethyl-n-butoxy, 3,3-dimethyl-n-butoxy, 1-ethyl-n-butoxy, 2-ethyl-n-butoxy, 1,1,2-trimethyl-n-propoxy, 1,2,2-trimethyl-n-propoxy, 1-ethyl-1-methyl-n-propoxy, and 1-ethyl-2-methyl-n-propoxy groups.

The number of carbon atoms in the aryl group is not particularly limited, but 6 to 40 is preferred, and considering the need to further improve the heat resistance of the polymer, 6 to 16 carbon atoms are more preferred, and 6 to 13 carbon atoms are even more preferred.
In the present invention, the aryl group includes aryl groups having substituents. Examples of substituents include halogen atoms, C1-C6 alkyl groups, C1-C6 alkoxy groups, nitro groups, and cyano groups.
Specific examples of aryl groups include phenyl, o-chlorophenyl, m-chlorophenyl, p-chlorophenyl, o-fluorophenyl, p-fluorophenyl, o-methoxyphenyl, p-methoxyphenyl, p-nitrophenyl, p-cyanophenyl, α-naphthyl, β-naphthyl, o-biphenylyl, m-biphenylyl, p-biphenylyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, and 9-phenanthryl groups.

The number of carbon atoms in the aralkyl group is not particularly limited, but 7 to 20 carbon atoms is preferred, and the structure of the alkyl portion is not particularly limited, and may be linear, branched, cyclic, or a combination of two or more of these.
In the present invention, the aralkyl group includes aralkyl groups having substituents. Examples of substituents include halogen atoms, C1-C6 alkyl groups, C1-C6 alkoxy groups, nitro groups, and cyano groups.
Specific examples include benzyl, p-methylphenylmethyl, m-methylphenylmethyl, o-ethylphenylmethyl, m-ethylphenylmethyl, p-ethylphenylmethyl, 2-propylphenylmethyl, 4-isopropylphenylmethyl, 4-isobutylphenylmethyl, and α-naphthylmethyl group.

<<Q>>
Q in formula (1) is not particularly limited as long as it is an alkylene group having 3 to 20 carbon atoms and an alicyclic structure. For example, the groups shown in formulas (2) to (15) below can be used. However, considering the need to further improve the heat resistance (heat resistance and transparency) of the resulting polymer, the group shown in formula (4) is particularly preferred.
Furthermore, when Q in formula (1) is an alkylene group having 3 to 20 carbon atoms and an alicyclic structure, it is expected that a cured product with a low dielectric constant and high light resistance can be obtained compared to the case where Q has an aromatic ring.

* represents a combination.

The above ^R1 and ^R2 independently represent alkylene groups having 1 to 5 carbon atoms, which may have a branched structure.
Examples of such alkylene groups include methylene, ethylene, propylene, trimethylene, tetramethylene, and pentamethylene groups. However, considering the need to increase the refractive index of the resulting polymer, alkylene groups with 1 to 3 carbon atoms are preferred, and alkylene groups with 1 to 2 carbon atoms, specifically methylene and ethylene groups, are more preferred, with the methylene group being optimal.

<Amino group with crosslinking group>
Furthermore, the triazine ring-containing polymer of the present invention has at least one triazine ring terminus, and at least a portion of this triazine ring terminus is encapsulated with an amino group having a crosslinking group (excluding a hydroxyl group).
Furthermore, "excluding hydroxyl groups" does not mean that an amino group having a crosslinking group does not have a hydroxyl group, but rather that in an amino group having a crosslinking group, the case where the only functional group contributing to crosslinking is a hydroxyl group is excluded. Therefore, an amino group having a crosslinking group may have a hydroxyl group, but in that case, it will have functional groups other than the hydroxyl group that contribute to crosslinking.
The triazine ring-containing polymer of the present invention has at least one triazine ring end, and this terminal triazine ring usually has two halogen atoms that can be substituted with the amino group having the crosslinking group. Therefore, the amino group having the crosslinking group may be bonded to the same triazine ring end, and if there are multiple triazine ring ends, each may be bonded to a different triazine ring end.

The number of crosslinking groups in the amino group having crosslinking groups is not particularly limited and can be any number, but considering the balance between solvent resistance and solubility in organic solvents, 1 to 4 groups are preferred, 1 to 2 groups are more preferred, and 1 group is even more preferred.
If an amino group having a crosslinking group has multiple crosslinking groups, the multiple crosslinking groups may have the same structure or different structures.

From the viewpoint of obtaining a cured film with low dielectric constant and high light resistance, it is preferable that the amino group having the crosslinking group does not have an aromatic ring.

An amino group having a crosslinking group can be represented, for example, by the following formula (X).
(In the formula, Z represents a group having a bridging group. * represents a bond.)
In formula (X), Z may be the bridging group itself.

Examples of crosslinking groups include vinyl-containing groups, epoxy-containing groups, oxetane-containing groups, carboxy-containing groups, sulfo-containing groups, thiol-containing groups, and (meth)acryloyl-containing groups. Considering the need to improve the heat resistance of the triazine ring-containing polymer and the solvent resistance (crack resistance) of the resulting film, (meth)acryloyl-containing groups are preferred.

Examples of (meth)acryloyl-containing groups include (meth)acryloyl groups, (meth)acryloyloxyalkyl groups, and groups represented by the following formula (i). However, (meth)acryloyloxyalkyl groups having an alkylene group with 1 to 10 carbon atoms and groups represented by the following formula (i) are preferred, and groups represented by the following formula (i) are more preferred.

(In the formula, ^A1 represents an alkylene group having 1 to 10 carbon atoms, and ^A2 represents a single bond or the following formula (j)
A represents a group represented by , where ^A3 represents an (a+1) valent aliphatic hydrocarbon group which may be substituted with a hydroxyl group, ^A4 represents a hydrogen atom or a methyl group, a represents 1 or 2, and * represents a bond.

Examples of alkylene groups included in (meth)acryloyloxyalkyl groups having an alkylene group (alkanediyl group) with 1 to 10 carbon atoms include methylene, ethylene, trimethylene, propane-1,2-diyl, tetramethylene, butane-1,3-diyl, butane-1,2-diyl, 2-methylpropane-1,3-diyl, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, and decamethylene groups. Considering the improvement of heat resistance and resistance to high temperature and high humidity, among these, those having an alkylene group with 1 to 5 carbon atoms are preferred, those having an alkylene group with 1 to 3 carbon atoms are preferred, and those having an alkylene group with 1 or 2 carbon atoms are more preferred.

Specific examples of the above (meth)acryloyloxyalkyl groups include, for example, (meth)acryloyloxymethyl group, 2-(meth)acryloyloxyethyl group, 3-(meth)acryloyloxypropyl group, and 4-(meth)acryloyloxybutyl group.

In formula (i), ^A1 is an alkylene group having 1 to 10 carbon atoms, but an alkylene group having 1 to 5 carbon atoms is preferred, and a methylene group, an ethylene group, or a propylene group is more preferred. Examples of alkylene groups having 1 to 10 carbon atoms include those similar to the alkylene groups included in the (meth)acryloyloxyalkyl groups described above.

^A2 represents a single bond or a group represented by formula (j), but the group represented by formula (j) is preferred.

^A3 is an aliphatic hydrocarbon group with an (a+1) value that may be substituted with a hydroxyl group. Specific examples include alkylene groups having 1 to 5 carbon atoms and the following formulas (k-1) to (k-3).
(In the formula, * is the same as above.)
Examples of groups represented by are shown, with alkylene groups having 1 to 5 carbon atoms being preferred, alkylene groups having 1 to 3 carbon atoms being more preferred, and methylene groups and ethylene groups being even more preferred. Examples of the alkylene group of ^A3 include alkylene groups having 1 to 5 carbon atoms from among the alkylene groups exemplified in ^A1 .

'a' represents either 1 or 2, but 1 is preferred.

A preferred embodiment of the base represented by formula (i) is the one represented by the following formula (i-1).

(In the formula, ^A1 , ^A3 , ^A4 and * are the same as above.)

More preferred embodiments of the base represented by formula (i) include those represented by the following formulas (i-2) to (i-7).

(In the formula, * is the same as above.)

Examples of vinyl-containing groups include alkenyl groups having 2 to 10 carbon atoms and having a vinyl group at one end. Specific examples include ethenyl, 1-propenyl, allyl, isopropenyl, 1-butenyl, 2-butenyl, and 2-pentenyl groups.

Examples of epoxy-containing groups include epoxy, glycidyl, and glycidyloxy groups. Specific examples include glycidylmethyl, 2-glycidylethyl, 3-glycidylpropyl, and 4-glycidylbutyl groups.

Examples of oxetane-containing groups include oxetane-3-yl, (oxetane-3-yl)methyl, 2-(oxetane-3-yl)ethyl, 3-(oxetane-3-yl)propyl, and 4-(oxetane-3-yl)butyl groups.

Examples of carboxyl-containing groups include carboxyl groups and carboxyalkyl groups having 2 to 10 carbon atoms. Among carboxyalkyl groups having 2 to 10 carbon atoms, those to which the carboxyl group is bonded to are preferably primary carbon atoms. Specific examples include carboxymethyl, 2-carboxyethyl, 3-carboxypropyl, and 4-carboxybutyl groups.

Examples of sulfo-containing groups include sulfo groups and sulfoalkyl groups having 1 to 10 carbon atoms. Among sulfoalkyl groups having 1 to 10 carbon atoms, those to which the sulfo group is bonded to are preferably primary carbon atoms. Specific examples include sulfomethyl, 2-sulfoethyl, 3-sulfopropyl, and 4-sulfobutyl groups.

Examples of thiol-containing groups include thiol groups and mercaptoalkyl groups having 1 to 10 carbon atoms. Among the mercaptoalkyl groups having 1 to 10 carbon atoms, those to which the thiol group is bonded are preferably secondary carbon atoms. Specific examples include mercaptomethyl, 2-mercaptoethyl, 3-mercaptopropyl, and 4-mercaptobutyl groups.

An amino group having a (meth)acryloyloxyalkyl group can be introduced by using the corresponding (meth)acryloyloxyalkylamino compound, or by introducing an amino group having a hydroxyalkyl group into a triazine ring-containing polymer, and then reacting the hydroxyl group contained in the hydroxyalkyl group with (meth)acrylate halide or (meth)acrylate glycidyl.

An amino group having the group represented by formula (i) can be introduced by using an amino compound having the desired crosslinking group, or by introducing an amino group having a hydroxyalkyl group into a triazine ring-containing polymer, and then reacting the hydroxyl group contained in the hydroxyalkyl group with an isocyanate group represented by the following formula (i') using an (meth)acrylic acid ester compound.

(In the formula, ^A3 , ^A4 , and a are the same as above.)

Specific examples of (meth)acryloyloxyalkylamino compounds include, for example, ester compounds obtained by reacting the hydroxyl group of the above-mentioned hydroxyalkylamino compound with (meth)acrylate halide or (meth)acrylate glycidyl.
Examples of (meth)acrylate halides include (meth)acrylate chloride, (meth)acrylate bromide, and (meth)acrylate iodide.
Specific examples of (meth)acrylic acid ester compounds having an isocyanate group represented by the above formula (i') include, for example, 2-isocyanatoethyl acrylate, 2-isocyanatoethyl methacrylate, and 1,1-(bisacryloyloxymethyl)ethyl isocyanate. In the present invention, 2-isocyanatoethyl acrylate is preferred from the viewpoint of a simple synthesis method.

The weight-average molecular weight of the polymer in the present invention is not particularly limited, but is preferably 500 to 500,000, more preferably 500 to 100,000, preferably 2,000 or more in terms of improving heat resistance and lowering shrinkage, preferably 50,000 or less, more preferably 30,000 or less, even more preferably 25,000 or less, and most preferably 10,000 or less in terms of increasing solubility and lowering the viscosity of the resulting composition.
In this invention, the weight-average molecular weight is the average molecular weight obtained by gel permeation chromatography (GPC) analysis on a standard polystyrene basis.

<Method for producing triazine ring-containing polymers>
The triazine ring-containing polymer (hyperbranched polymer) of the present invention can be produced according to the method disclosed in International Publication No. 2010/128661.
In other words, for example, the triazine ring-containing polymer of the present invention can be obtained by reacting a trihalogenated triazine compound and a diamino compound in an organic solvent, and then reacting them with, for example, at least one amino compound selected from an amino compound having an acryloyloxyalkyl group (acryloyl-containing group) and an amino compound having a group represented by formula (i) (acryloyl-containing group), which is a terminal encapsulant.

For example, as shown in Scheme 1 below, the triazine ring-containing polymer (24) can be obtained by reacting a triazine compound (21) and a diamino compound (22) in a suitable organic solvent, and then reacting them with an amino compound (23) having a crosslinking group (Z), which is a terminal encapsulant.

(In the formula, X independently represents halogen atoms, Q represents an alkylene group having 3 to 20 carbon atoms and an alicyclic structure, and Z represents a group having a bridging group.)

In the above scheme 1, the charging ratio of the diamino compound (22) is arbitrary as long as the desired polymer is obtained, but it is preferable to use 0.01 to 10 equivalents of the diamino compound (22) per 1 equivalent of the triazine compound (21), and more preferably 0.7 to 5 equivalents.
The diamino compound (22) may be added neat or as a solution dissolved in an organic solvent, but the latter method is preferred considering the ease of handling and the ease of controlling the reaction.
The reaction temperature can be set appropriately within the range from the melting point to the boiling point of the solvent used, but -30 to 150°C is preferred, and -10 to 100°C is more preferred.

Another embodiment is the method shown in Scheme 2 below. In this method, the triazine ring-containing polymer (36) is obtained by reacting a triazine compound (31) and a diamino compound (32) in a suitable organic solvent, and then reacting them with an amino compound (33) having a hydroxyalkyl group ( ^A1 ') as a terminal encapsulant to obtain a triazine ring-containing polymer (34) (first step), and then further reacting the hydroxyl group of the hydroxyalkyl group contained in the triazine ring-containing polymer (34) with an isocyanate group (meth)acrylic acid ester compound (35) (second step).

(In the formula, X independently represents a halogen atom, Q represents a C3-C20 alkylene group having an alicyclic structure, ^A1 ' represents a C1-C10 hydroxyalkyl group, ^A3 represents an (a+1) valent aliphatic hydrocarbon group which may be substituted with a hydroxyl group, ^A4 represents a hydrogen atom or a methyl group, and ^A1 represents a C1-C10 alkylene group.)

In Scheme 2 described above, the charging ratio and method of adding the diamino compound (32) in the first step, and the reaction temperature in the reaction until obtaining the triazine ring-containing polymer (34) can be the same as those described in Scheme 1.
Furthermore, in the second stage, the charging ratio of the (meth)acrylic acid ester compound (35) having an isocyanate group to the triazine ring-containing polymer (34) can be arbitrarily set according to the ratio of the hydroxyalkyl group ( ^A1 ') to the isocyanate group, preferably 0.1 to 10 equivalents, more preferably 0.5 to 5 equivalents, even more preferably 0.7 to 3 equivalents, and still more preferably 0.9 to 1.5 equivalents per equivalent of the amino compound (33) having a hydroxyalkyl group used. For example, if all the hydroxyalkyl groups ( ^A1 ') contained in the triazine ring-containing polymer (34) are groups represented by formula (i), the charging ratio is preferably 1.0 to 10 equivalents, more preferably 1.0 to 5 equivalents, even more preferably 1.0 to 3 equivalents, and still more preferably 1.0 to 1.5 equivalents of the (meth)acrylic acid ester compound (35) per equivalent of the amino compound (33) having a hydroxyalkyl group used.
The reaction temperature in this reaction is the same as the reaction temperature in the reaction to obtain the triazine ring-containing polymer (34), but considering that the (meth)acryloyl group does not undergo polymerization during the reaction, 30 to 80°C is preferred, 40 to 70°C is more preferred, and 50 to 60°C is even more preferred.

In the second step of Scheme 2, the reaction may be carried out in the presence of a polymerization inhibitor to prevent polymerization of the (meth)acryloyl group during the reaction.
Examples of polymerization inhibitors include N-methyl-N-nitrosoaniline, N-nitrosophenylhydroxyamine or its salts, benzoquinones, phenolic polymerization inhibitors, and phenothiazines. Among these, N-nitrosophenylhydroxyamine or its salts are preferred due to their excellent polymerization inhibitory effect.
Examples of N-nitrosophenylhydroxyamine salts include N-nitrosophenylhydroxyamine ammonium salt and N-nitrosophenylhydroxyamine aluminum salt.
Examples of benzoquinones include p-benzoquinone and 2-methyl-1,4-benzoquinone.
Examples of phenolic polymerization inhibitors include hydroquinone, p-methoxyphenol, 4-t-butylcatechol, 2-t-butylhydroquinone, and 2,6-di-t-butyl-4-methylphenol.
The amount of polymerization inhibitor used is not particularly limited, but for example, it may be 1 to 200 ppm or 10 to 100 ppm by mass ratio with respect to the (meth)acrylic acid ester compound having an isocyanate group represented by formula (i').
By using a polymerization inhibitor, the polymerization of (meth)acryloyl groups can be suppressed and the second-step reaction can be carried out even when the reaction temperature is raised to around 60-80°C.

As organic solvents, various solvents commonly used in this type of reaction can be used, such as tetrahydrofuran (THF), dioxane, dimethyl sulfoxide; amide solvents such as N,N-dimethylformamide, N-methyl-2-pyrrolidone, tetramethylurea, hexamethylphosphoramide, N,N-dimethylacetamide, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, N-methyl-2-piperidone, N,N'-dimethylethyleneurea, N,N,N',N'-tetramethylmalonamide, N-methylcaprolactam, N-acetylpyrrolidine, N,N-diethylacetamide, N-ethyl-2-pyrrolidone, N,N-dimethylpropionic acid amide, N,N-dimethylisobutylamide, N-methylformamide, N,N'-dimethylpropyleneurea, and mixtures thereof.
Among these, N,N-dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, and mixtures thereof are preferred, and in particular, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 3-methoxy-N,N-dimethylpropanamide, and 3-butoxy-N,N-dimethylpropanamide are preferred.

Furthermore, in the reaction of Scheme 1 or the first step of Scheme 2, various bases commonly used during 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, 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, n-propylamine, trimethylamine, triethylamine, diisopropylamine, diisopropylethylamine, N-methylpiperidine, 2,2,6,6-tetramethyl-N-methylpiperidine, pyridine, 4-dimethylaminopyridine, N-methylmorpholine, 2-aminoethanol, ethyldiethanolamine, and diethylaminoethanol.
The amount of base added is preferably 1 to 100 equivalents, and more preferably 1 to 10 equivalents, per equivalent of the triazine compound. These bases may also be used in aqueous solution.
Preferably, the resulting polymer does not contain any residual raw material components, but some raw materials may remain as long as the effects of the present invention are not impaired.
After the reaction is complete, the product can be easily purified by methods such as reprecipitation.

For end-capturing methods using amino compounds having crosslinking groups, known methods can be employed.
In this case, the amount of end-capturing agent used is preferably about 0.05 to 10 equivalents, more preferably 0.1 to 5 equivalents, and even more preferably 0.5 to 2 equivalents, per equivalent of excess halogen atoms derived from the triazine compound that were not used in the polymerization reaction.
The reaction solvent and reaction temperature may be the same conditions as those described in the reaction of Scheme 1 or the first step of Scheme 2, and the end-capturing agent may be charged at the same time as the diamino compound (22) or (32).
Alternatively, an unsubstituted amino compound without a crosslinking group may be used, and end capping may be performed using two or more types of groups.

The specific unsubstituted amino group is not particularly limited.
Furthermore, unsubstituted amino groups can be introduced using the corresponding unsubstituted amino compounds.

Furthermore, when introducing unsubstituted amino groups, the ratio of the amino compound having a crosslinking group to the unsubstituted amino compound is preferably 0.1 to 1.0 moles, more preferably 0.1 to 0.5 moles, and even more preferably 0.1 to 0.3 moles, of the unsubstituted amino compound per mole of the amino compound having a crosslinking group, from the viewpoint of exhibiting a good balance between solubility in organic solvents and resistance to yellowing.

In addition to end encapsulation using an amino compound having a crosslinking group, end encapsulation may also be performed using an arylamino compound having a specific heteroatom-containing substituent. End encapsulation with an arylamino group having a specific heteroatom-containing substituent can increase the refractive index of the resulting film.
Examples of specific heteroatom-containing substituents include cyano groups, alkylamino groups, arylamino groups, nitro groups, alkylmercapto groups, arylmercapto groups, alkoxycarbonyl groups, and alkoxycarbonyloxy groups.
Examples of arylamino groups having specific heteroatom-containing substituents include those represented by the following formula (41).

In the formula, Y is a "specific heteroatom-containing substituent" and represents a cyano group, alkylamino group, arylamino group, nitro group, alkylmercapto group, arylmercapto group, alkoxycarbonyl group, or alkoxycarbonyloxy group. m represents an integer from 1 to 5. If m is 2 or greater, Y may be the same or different. * represents a bond.

Among these, Y is preferably a cyano group or a nitro group. m is preferably 1. When m is 1, Y is preferably substituted at the para or meta position.

Furthermore, when introducing an arylamino group having a specific heteroatom-containing substituent, the ratio of the amino compound having a crosslinking group to the arylamino compound having the specific heteroatom-containing substituent is preferably 0.1 to 1.0 moles, more preferably 0.1 to 0.5 moles, and even more preferably 0.1 to 0.3 moles, of the arylamino compound having the specific heteroatom-containing substituent per mole of the amino compound having a crosslinking group, from the viewpoint of achieving a good balance between solvent resistance and high refractive index.

(Film forming composition)
The film-forming composition of the present invention contains at least the triazine ring-containing polymer of the present invention, and optionally further contains a crosslinking agent or the like.
One embodiment of the film-forming composition of the present invention is a solvent-free composition. The solvent-free composition does not contain organic solvents.
Here, "contains no organic solvents" means that it is substantially free of organic solvents, specifically indicating that the organic solvent content is 10% by mass or less.

The content of the triazine ring-containing polymer in the film-forming composition is not particularly limited, but is preferably 0.1 to 50% by mass, and more preferably 1 to 30% by mass, relative to the film components. In this invention, film components refer to components other than the solvent contained in the composition.

<Crosslinking agent>
The crosslinking agent is not particularly limited as long as it is a compound having two or more substituents that can react with the crosslinking group of the triazine ring-containing polymer described above.
Examples of such compounds include melamine compounds having crosslinking substituents such as methylol groups and methoxymethyl groups (e.g., phenoplast compounds, aminoplast compounds, etc.), substituted urea compounds, compounds containing crosslinking substituents such as epoxy groups or oxetane groups (e.g., polyfunctional epoxy compounds, polyfunctional oxetane compounds, etc.), compounds containing blocked isocyanate groups, compounds having acid anhydride groups, and compounds having (meth)acrylic groups. From the viewpoint of heat resistance and storage stability, compounds containing epoxy groups, blocked isocyanate groups, and (meth)acrylic groups are preferred, and in particular, compounds having blocked isocyanate groups and polyfunctional epoxy compounds and/or polyfunctional (meth)acrylic compounds that give a photocurable composition without the use of an initiator are preferred.
.

The polyfunctional epoxy compound is not particularly limited as long as it has two or more epoxy groups in a single molecule.
Specific examples 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, pentaerythritol polyglycidyl ether, and the like.

Furthermore, commercially available epoxy resins include YH-434 and YH434L (manufactured by Nippon Steel Chemical & Material Co., Ltd.), which have at least two epoxy groups; Epolid GT-401, GT-403, GT-301, GT-302, Celoxide 2021, and GT-3000 (manufactured by Daicel Corporation), which have a cyclohexene oxide structure; JER1001, 1002, 1003, 1004, 1007, 1009, 1010, and 828 (all manufactured by Mitsubishi Chemical Corporation), which are bisphenol A type epoxy resins; and bisphenol F type epoxy resins. jER807 (manufactured by Mitsubishi Chemical Corporation), jER152, jER154 (both manufactured by Mitsubishi Chemical Corporation), EPPN201, EPPN202 (both manufactured by Nippon Kayaku Co., Ltd.), cresol novolac type epoxy resins EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, EOCN-1027 (all manufactured by Nippon Kayaku Co., Ltd.), jER180S75 (manufactured by Mitsubishi Chemical Corporation), alicyclic epoxy resins Denacol EX-252 (manufactured by Nagase ChemteX Corporation), CY175, CY177, CY179 (all manufactured by CIBA-GEIGY Other products that can be used include: Araldite CY-182, CY-192, CY-184 (all manufactured by CIBA-GEIGY A.G.), Epiclon 200, 400 (both manufactured by DIC Corporation), JER871, 872 (both manufactured by Mitsubishi Chemical Corporation), ED-5661, ED-5662 (both manufactured by Celanese Coatings Co., Ltd.), and aliphatic polyglycidyl ethers such as Denacol EX-611, EX-612, EX-614, EX-622, EX-411, EX-512, EX-522, EX-421, EX-313, EX-314, EX-321 (manufactured by Nagase ChemteX Corporation).

The polyfunctional (meth)acrylic compound is not particularly limited as long as it has two or more (meth)acrylic groups in one molecule.
Specific examples include ethylene glycol diacrylate, ethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, ethoxylated bisphenol A diacrylate, ethoxylated bisphenol A dimethacrylate, ethoxylated trimethylolpropane triacrylate, ethoxylated trimethylolpropane trimethacrylate, ethoxylated glycerin triacrylate, ethoxylated glycerin trimethacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetramethacrylate, ethoxylated dipentaerythritol hexaacrylate, and polyglycerin monoethylene oxide Examples include polyacrylates, polyglycerin polyethylene glycol polyacrylates, dipentaerythritol hexaacrylates, dipentaerythritol hexamethacrylates, neopentyl glycol diacrylates, neopentyl glycol dimethacrylates, pentaerythritol triacrylates, pentaerythritol trimethacrylates, trimethylolpropane triacrylates, trimethylolpropane trimethacrylates, tricyclodecane dimethanol diacrylates, tricyclodecane dimethanol dimethacrylates, 1,6-hexanediol diacrylates, 1,6-hexanediol dimethacrylates, and polybasic acid-modified acrylic oligomers.

Furthermore, polyfunctional (meth)acrylic compounds are available commercially, and specific examples include NK ester A-200, A-400, A-600, A-1000, A-9300 (tris(2-acryloyloxyethyl) isocyanurate), A-9300-1CL, A-TMPT, UA-53H, 1G, 2G, 3G, 4G, 9G, 14G, 23G, ABE-300, A-BPE-4, A-BPE-6, A-BPE-10, A-BPE-20, A-BPE-30, BPE-80N, BPE-100N, BPE-200, BPE-500, and BPE- 900, BPE-1300N, A-GLY-3E, A-GLY-9E, A-GLY-20E, A-TMPT-3EO, A-TMPT-9EO, AT-20E, ATM-4E, ATM-35E, APG-100, APG-200 (all manufactured by Shin Nakamura Chemical Industry Co., Ltd.), KAYARAD® DPEA-12, PEG400DA, THE-330, RP-1040 (all manufactured by Nippon Kayaku Co., Ltd.), Aronics M-210, M-350 (both manufactured by Toagosei Co., Ltd.), KAYARAD® DPHA, NPGDA, PET30 (all manufactured by Nippon Kayaku Co., Ltd.), NK Ester Examples include A-DPH, A-TMPT, A-DCP, A-HD-N, TMPT, DCP, NPG, and HD-N (all manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), NK Oligo U-15HA (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), NK Polymer Banaresin GH-1203 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), and DN-0075 (manufactured by Nippon Kayaku Co., Ltd.).
The above-mentioned polybasic acid-modified acrylic oligomers are also available commercially, with specific examples including Aronics M-510 and 520 (both manufactured by Toagosei Co., Ltd.).

Compounds containing an acid anhydride group are not particularly limited as long as they are carboxylic acid anhydrides obtained by dehydrating and condensing two molecules of carboxylic acid. Specific examples include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, maleic anhydride, succinic anhydride, octyl succinic anhydride, dodecenyl succinic anhydride, etc., which have one acid anhydride group in their molecule; 1,2,3,4-cyclobutanetetracarboxylic dianhydride, pyromellitic anhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene Examples include succinic acid 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 acid anhydride, 1,2,3,4-butanetetracarboxylic acid dianhydride, 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, and 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, which have two acid anhydride groups in their molecule.

Compounds containing blocked isocyanate groups are not particularly limited as long as they have two or more blocked isocyanate groups in one molecule, in which the isocyanate group (-NCO) is blocked by an appropriate protecting group, and when exposed to high temperatures during thermal curing, the protecting group (blocking portion) thermally dissociates and detaches, and the resulting isocyanate group undergoes a crosslinking reaction with the crosslinking group (e.g., hydroxyl group) of the triazine ring-containing polymer of the present invention. For example, compounds having two or more groups represented by the following formula in one molecule (these groups may be the same or different) are examples.

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

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

Compounds containing blocked isocyanate groups are available commercially. Specific examples include Takenate® B-830, B-815N, B-842N, B-870N, B-874N, B-882N, B-7005, B-7030, B-7075, B-5010 (all manufactured by Mitsui Chemicals, Inc.), Duranate® 17B-60PX, TPA-B80E, MF-B60X, MF-K60X, E402-B80T (all manufactured by Asahi Kasei Corporation), Karens MOI-BM® (all manufactured by Showa Denko K.K.), and TRIXENE®. Examples include BI-7950, BI-7951, BI-7960, BI-7961, BI-7963, BI-7982, BI-7991, and BI-7992 (manufactured by Baxenden Chemicals LTD).

The aminoplast compound is not particularly limited as long as it has two or more methoxymethylene groups in one molecule. Examples include the Cymel series such as hexamethoxymethylmelamine CYMEL® 303, tetrabutoxymethylglycoluryl CYMEL® 1170, and tetramethoxymethylbenzoguanamine CYMEL® 1123 (all manufactured by Japan Cytec Industries Co., Ltd.), as well as the Nikalac series such as the methylated melamine resins Nikalac® MW-30HM, MW-390, MW-100LM, and MX-750LM, and the methylated urea resins Nikalac® MX-270, MX-280, and MX-290 (all manufactured by Sanwa Chemical Co., Ltd.).
The oxetane compound is not particularly limited as long as it has two or more oxetanyl groups in one molecule. Examples include OXT-221, OX-SQ-H, and OX-SC (all manufactured by Toagosei Co., Ltd.), which contain oxetanyl groups.

The phenoplast compound has two or more hydroxymethylene groups in one molecule, and when exposed to high temperatures during thermal curing, a crosslinking reaction proceeds with the crosslinking groups of the triazine ring-containing polymer of the present invention via a dehydration condensation reaction.
Examples of phenoplast compounds 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, and α,α-bis(4-hydroxy-2,5-dimethylphenyl)-4-formyltoluene.
Phenoplast compounds are also available commercially, and specific examples include 26DMPC, 46DMOC, DM-BIPC-F, DM-BIOC-F, TM-BIP-A, BISA-F, BI25X-DF, and BI25X-TPA (all manufactured by Asahi Organic Chemicals Co., Ltd.).

Among these, polyfunctional (meth)acrylic compounds are preferred because they can suppress the reduction in refractive index due to the addition of crosslinking agents and the curing reaction proceeds rapidly. Among these, polyfunctional (meth)acrylic compounds having the isocyanuric acid skeleton described below are more preferred because they have excellent compatibility with triazine ring-containing polymers.
Examples of polyfunctional (meth)acrylic compounds having such a skeleton include NK Ester A-9300 and A-9300-1CL (both manufactured by Shin Nakamura Chemical Industry Co., Ltd.).

(In the formula, R ¹¹¹ to R ¹¹³ are monovalent organic groups that independently have at least one (meth)acrylic group at their terminal end.)

Furthermore, from the viewpoint of further improving the curing speed and enhancing the solvent resistance, acid resistance, and alkali resistance of the resulting cured film, it is preferable to use a polyfunctional (meth)acrylic compound (hereinafter referred to as a low-viscosity crosslinking agent) that is liquid at 25°C and has a viscosity of 5,000 mPa·s or less, preferably 1 to 3,000 mPa·s, more preferably 1 to 1,000 mPa·s, and even more preferably 1 to 500 mPa·s, either alone or in combination of two or more, or in combination with the polyfunctional (meth)acrylic compound having the isocyanuric acid skeleton.
Such low-viscosity crosslinking agents are also available commercially. For example, among the polyfunctional (meth)acrylic compounds mentioned above, examples include NK ester A-GLY-3E (85 mPa·s, 25°C), A-GLY-9E (95 mPa·s, 25°C), A-GLY-20E (200 mPa·s, 25°C), A-TMPT-3EO (60 mPa·s, 25°C), A-TMPT-9EO, ATM-4E (150 mPa·s, 25°C), and ATM-35E (350 mPa·s, 25°C) (all manufactured by Shin Nakamura Chemical Industry Co., Ltd.), which are crosslinking agents with relatively long chain lengths between (meth)acrylic groups.

Furthermore, considering the improvement of the alkali resistance of the resulting cured film, it is preferable to use at least one of NK ester A-GLY-20E (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) and ATM-35E (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) in combination with the polyfunctional (meth)acrylic compound having the isocyanuric acid skeleton.

Furthermore, when a film made of the triazine ring-containing polymer of the present invention is laminated onto a protective film such as PET or polyolefin film, and light irradiation is performed through the protective film, good curability can be obtained in the laminated film without oxygen inhibition. In this case, since the protective film needs to be peeled off after curing, it is preferable to use a polybasic acid-modified acrylic oligomer that provides a film with good peelability.

The crosslinking agents mentioned above may be used individually or in combination of two or more types.
The crosslinking agent content in the film-forming composition is preferably 1 to 500 parts by mass per 100 parts by mass of the triazine ring-containing polymer, but considering the control of the refractive index, it is preferably 10 to 300 parts by mass, and more preferably 30 to 200 parts by mass.

<Reactive Diluent>
The film-forming composition of the present invention may contain a reactive diluent.
In particular, if the film-forming composition of the present invention is a solvent-free composition, it is preferable to include a reactive diluent.
Reactive diluents are low-molecular-weight compounds having one reactive group that reacts with at least one of the crosslinking groups of a triazine ring-containing polymer and the crosslinking agent. Those that are liquid at room temperature and have low viscosity also have viscosity-adjusting properties and can therefore be used as a substitute for organic solvents.

Commonly used reactive diluents include compounds having one radical polymerizable group, or compounds having one cationic polymerizable group such as an epoxy group, oxetanyl group, or vinyl ether group.

The molecular weight of the reactive diluent is not particularly limited; for example, it may be 200 or less.

As a reactive diluent, a compound having one radical polymerizable group is preferred, and at least one of the compounds of the following formulas (A) and (B) is more preferred in terms of excellent solubility of triazine ring-containing polymers.

In formula (A), R ²⁰¹ and R ²⁰³ independently represent a hydrogen atom, a C1-C10 alkyl group, or a polymerizable carbon-carbon double bond-containing group, and R ²⁰² represents a hydrogen atom or a C1-C10 alkyl group. However, either R ²⁰¹ or R ²⁰³ is a polymerizable carbon-carbon double bond-containing group, and both R ²⁰¹ and R ²⁰³ cannot be polymerizable carbon-carbon double bond-containing groups at the same time. Furthermore, when R ²⁰¹ is a polymerizable carbon-carbon double bond-containing group, R ²⁰² and R ²⁰³ may form a ring structure together with N.
The structure of the alkyl group described above is not particularly limited and may be linear, branched, cyclic, or any combination of two or more of these.
In formula (B), R ²⁰⁴ represents a hydrogen atom or a methyl group. n represents an integer between 1 and 2.

Specific examples of alkyl groups having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1 Examples include 1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, and n-decyl groups.
Preferably, it is an alkyl group having 1 to 5 carbon atoms.

The polymerizable carbon-carbon double bond-containing group is not particularly limited, but carbon-carbon double bond-containing hydrocarbon groups (alkenyl groups) having 2 to 10 carbon atoms, preferably 2 to 5 carbon atoms, are preferred. For example, ethenyl (vinyl), n-1-propenyl, n-2-propenyl (aryl group), 1-methylethenyl, n-1-butenyl, n-2-butenyl, n-3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylethenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, n-1-pentenyl, n-2-pentenyl, n-3-pentenyl, n-4-pentenyl, 1-n-propylethenyl, Examples include 1-methyl-1-butenyl, 1-methyl-2-butenyl, 1-methyl-3-butenyl, 2-ethyl-2-propenyl, 2-methyl-1-butenyl, 2-methyl-2-butenyl, 2-methyl-3-butenyl, 3-methyl-1-butenyl, 3-methyl-2-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1-i-propylethenyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, n-1-hexenyl, n-2-hexenyl, n-3-hexenyl, n-4-hexenyl, n-5-hexenyl, n-heptenyl, n-octenyl, n-nonenyl, and n-decenyl groups.

Specific examples of the compound represented by formula (A) include N-vinylformamide, N-vinylacetamide, N-arylformamide, N-arylacetamide, 4-acryloylmorpholine, (meth)acrylamide, N-methyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-ethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, and N,N-diisopropyl(meth)acrylamide, but N-vinylformamide, 4-acryloylmorpholine, N,N-dimethylacrylamide, and N,N-diethyl(meth)acrylamide are preferred.
Specific examples of the compound represented by formula (B) include tetrahydrofuran-2-ylmethyl acrylate, tetrahydrofuran-2-ylmethyl methacrylate, tetrahydrofuran-2-ylethyl acrylate, and tetrahydrofuran-2-ylethyl methacrylate.
The reactive diluents mentioned above may be used individually or in combination of two or more.

The content of the reactive diluent in the film-forming composition is not particularly limited, but is preferably 1 to 2000 parts by mass per 100 parts by mass of the triazine ring-containing polymer. However, considering the degree of improvement in refractive index of the resulting film, solvent resistance, and viscosity, it is preferably 100 to 1500 parts by mass, and more preferably 200 to 1000 parts by mass.

<Soluble Organic Solvents>
The film-forming composition of the present invention may contain an organic solvent.
Examples of organic 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 monomethyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, diethylene glycol diethyl ether, dipropylene glycol 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, cyclohex Butanol, 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 ketone, diethyl ketone, methyl isobutyl ketone, methyl n-butyl ketone, cyclopentanone, cyclohexanone, ethyl acetate, isopropyl acetate, n-propyl acetate, isobutyl acetate, n-butyl acetate, ethyl lactate, methanol, ethanol, isopropanol, tert-butanol, Examples include allyl alcohol, n-propanol, 2-methyl-2-butanol, isobutanol, n-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 (DMAc), N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, N-cyclohexyl-2-pyrrolidinone, etc. These may be used individually or in combination of two or more.

The triazine ring-containing polymer of the present invention has excellent solubility in organic solvents, and therefore dissolves well in glycol ester solvents such as ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol monobutyl ether acetate, and diethylene glycol monoethyl ether acetate; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, and diacetone alcohol; and ester solvents such as ethyl acetate, methyl acetate, butyl acetate, methoxybutyl acetate, cellosolve acetate, amyl acetate, n-propyl acetate, isopropyl acetate, methyl lactate, ethyl lactate, and butyl lactate. Therefore, it is particularly suitable for forming films in areas where these solvents are required.

In this case, the solid content concentration in the composition is not particularly limited as long as it does not affect storage stability, and can be set appropriately according to the desired film thickness. Specifically, from the viewpoint of solubility and storage stability, a solid content concentration of 0.1 to 50% by mass is preferred, and more preferably 0.1 to 40% by mass.

The film-forming compositions of the present invention may also contain initiators corresponding to each crosslinking agent and reactive diluent. As mentioned above, when a polyfunctional epoxy compound and/or a polyfunctional (meth)acrylic compound is used as the crosslinking agent, photocuring proceeds and a cured film is formed even without the use of an initiator; however, an initiator may be used in such cases.

When using polyfunctional epoxy compounds as crosslinking agents, photoacid generators and photobase generators can be used.
As the photoacid generator, any known one can be appropriately selected and used. For example, onium salt derivatives such as diazonium salts, sulfonium salts, and iodonium salts can be used.
Specific examples include aryldiazonium salts such as phenyldiazonium hexafluorophosphate, 4-methoxyphenyldiazonium hexafluoroantimonate, and 4-methylphenyldiazonium hexafluorophosphate; diaryliodonium salts such as diphenyliodonium hexafluoroantimonate, bis(4-methylphenyl)iodonium hexafluorophosphate, and bis(4-tert-butylphenyl)iodonium hexafluorophosphate; triphenylsulfonium hexafluoroantimonate, tris(4-methoxyphenyl)sulfonium hexafluorophosphate, diphenyl-4-thiophenoxyphenylsulfonium hexafluoroantimonate, and diphenyl-4-thiophenoxyphenylsulfonium hexafluorophosphate. Examples of triarylsulfonium salts include phosphate, 4,4'-bis(diphenylsulfonio)phenylsulfide-bishexafluoroantimonate, 4,4'-bis(diphenylsulfonio)phenylsulfide-bishexafluorophosphate, 4,4'-bis[di(β-hydroxyethoxy)phenylsulfonio]phenylsulfide-bishexafluoroantimonate, 4,4'-bis[di(β-hydroxyethoxy)phenylsulfonio]phenylsulfide-bis-hexafluorophosphate, 4-[4'-(benzoyl)phenylthio]phenyl-di(4-fluorophenyl)sulfonium hexafluoroantimonate, and 4-[4'-(benzoyl)phenylthio]phenyl-bis(4-fluorophenyl)sulfonium hexafluorophosphate.

These onium salts may be commercially available products, specifically: San-Aid SI-60, SI-80, SI-100, SI-60L, SI-80L, SI-100L, SI-L145, SI-L150, SI-L160, SI-L110, SI-L147 (all manufactured by Sanshin Chemical Industry Co., Ltd.), UVI-6950, UVI-6970. UVI-6974, UVI-6990, UVI-6992 (all manufactured by Union Carbide), CPI-100P, CPI-100A, CPI-200K, CPI-200S (all manufactured by Sunapro Co., Ltd.), Adeka Optomer SP-150, SP-151, SP-170, SP-171 (all manufactured by Asahi Denka Kogyo Co., Ltd.), Irgacure 261 (BASF), CI-2481, CI-2624, CI-2639, CI-2064 (all manufactured by Nippon Soda Co., Ltd.), CD-1010, CD-1011, CD-1012 (all manufactured by Sartmar), DS-100, DS-101, DAM-101, DAM-102, DAM-105, DAM-201, DSM-301, NAI-100, NAI-101, NAI-105, NAI-106, SI-100, SI-101, SI-105, SI-106, PI-105, NDI-105, BENZOIN Examples include TOSYLATE, MBZ-101, MBZ-301, PYR-100, PYR-200, DNB-101, NB-101, NB-201, BBI-101, BBI-102, BBI-103, BBI-109 (all manufactured by Midori Chemical Co., Ltd.), PCI-061T, PCI-062T, PCI-020T, PCI-022T (all manufactured by Nippon Kayaku Co., Ltd.), IBPF, IBCF (manufactured by Sanwa Chemical Co., Ltd.), etc.

On the other hand, the photobase generator can be appropriately selected from known types, such as Co-amine complex-based, oxime carboxylic acid ester-based, carbamic acid ester-based, and quaternary ammonium salt-based photobase generators.
Specific examples include 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-carbamoylhydroxylamide, O-carbamoyloxime, [[(2,6-dinitrobenzyl)oxy]carbonyl]cyclohexylamine, bis[[(2-nitrobenzyl)oxy]carbonyl]hexane1,6-diamine, 4-(methylthiobenzoyl)-1-methyl-1-morpholinoethane, (4-morpholinobenzoyl)-1-benzyl-1-dimethylamine Examples include minopropane, N-(2-nitrobenzyloxycarbonyl)pyrrolidine, hexaamminecobalt(III)tris(triphenylmethylborate), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2,6-dimethyl-3,5-diacetyl-4-(2'-nitrophenyl)-1,4-dihydropyridine, and 2,6-dimethyl-3,5-diacetyl-4-(2',4'-dinitrophenyl)-1,4-dihydropyridine.
Furthermore, commercially available photobase generators may be used, and specific examples include TPS-OH, NBC-101, and ANC-101 (all product names, manufactured by Midori Chemical Co., Ltd.).

When using a photoacid or base generator, it is preferable to use it in the range of 0.1 to 15 parts by mass, and more preferably in the range of 1 to 10 parts by mass, per 100 parts by mass of the polyfunctional epoxy compound.
Furthermore, if necessary, an epoxy resin curing agent may be added in an amount of 1 to 100 parts by mass per 100 parts by mass of the polyfunctional epoxy compound.

On the other hand, when using polyfunctional (meth)acrylic compounds, photoradical polymerization initiators can be used.
As a photoradical polymerization initiator, any known ones may be appropriately selected and used, for example, acetophenones, benzophenones, Michler's benzoylbenzoate, amyloxime esters, oxime esters, tetramethylthiuram monosulfide, and thioxanthones.
In particular, photocleavage-type photoradical polymerization initiators are preferred. Photocleavage-type photoradical polymerization initiators are described in "Latest UV Curing Technology" (page 159, publisher: Kazuhiro Takasuki, publisher: Technical Information Association Co., Ltd., published in 1991).
Examples of commercially available photoradical polymerization initiators include BASF products such as Irgacure 127, 184, 369, 379, 379EG, 651, 500, 754, 819, 903, 907, 784, 2959, CGI1700, CGI1750, CGI1850, CG24-61, OXE01, OXE02, Darocure 1116, 1173, MBF, BASF product name: Lucilin TPO, UCB product name: Ebecryl P36, and Fratezuri-Lamberti product names: Ezacure KIP150, KIP65LT, KIP100F, KT37, KT55, KTO46, KIP75/B.
When using a photoradical polymerization initiator, it is preferable to use it in the range of 0.1 to 200 parts by mass, and more preferably in the range of 1 to 150 parts by mass, per 100 parts by mass of the polyfunctional (meth)acrylate compound.

Furthermore, the film-forming composition of the present invention may contain a polyfunctional thiol compound having two or more mercapto groups in its molecule, for purposes such as promoting the reaction between the triazine ring-containing polymer and the crosslinking agent.
Specifically, polyfunctional thiol compounds represented by the following formula are preferred.

The above L represents a divalent to tetravalent organic group, but a divalent to tetravalent aliphatic group having 2 to 12 carbon atoms or a divalent to tetravalent heterocycle-containing group is preferred, and a divalent to tetravalent aliphatic group having 2 to 8 carbon atoms or a trivalent group having an isocyanuric acid skeleton (1,3,5-triazine-2,4,6(1H,3H,5H)-trione ring) represented by the following formula is more preferred.
The above n represents an integer between 2 and 4, corresponding to the valence of L.

(In the formula, "•" indicates a bond with an oxygen atom.)

Specific examples of compounds include 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, pentaerythritol tetrakis(3-mercaptobutyrate), trimethylolpropanetris(3-mercaptobutyrate), and trimethylolethanetris(3-mercaptobutyrate).
These polyfunctional thiol compounds are also available commercially, such as Karenz MT-BD1, Karenz MT NR1, Karenz MT PE1, TPMB, and TEMB (all manufactured by Showa Denko Corporation).
These polyfunctional thiol compounds may be used individually or in combination of two or more.

When using a polyfunctional thiol compound, the amount added is not particularly limited as long as it does not adversely affect the resulting film. However, in this invention, 0.01 to 10% by mass, and more preferably 0.03 to 6% by mass, is preferred, based on 100% by mass of solid content.

The film-forming composition of the present invention may contain additives other than the triazine ring-containing polymer and crosslinking agent, such as leveling agents, surfactants, and silane coupling agents, as long as the effects of the present invention are not impaired.
Examples of surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkylaryl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether; polyoxyethylene-polyoxypropylene block copolymers; sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate; polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters including tristearate, product names F-Top EF301, EF303, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd. (formerly Gemco Co., Ltd.)), product names Megafac F171, F173, R-08, R-30, R-40, F-553, F-554, RS-75, RS-72-K (manufactured by DIC Corporation), Florard FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), product name Asa Examples include fluorine-based surfactants such as Higard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, and SC106 (manufactured by AGC Inc.), and organosiloxane 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, and BYK-378 (manufactured by Bic Chemie Japan Co., Ltd.).

These surfactants may be used individually or in combination of two or more. The amount of surfactant used is preferably 0.0001 to 5 parts by mass, more preferably 0.001 to 1 part by mass, and even more preferably 0.01 to 0.5 parts by mass, per 100 parts by mass of the triazine ring-containing polymer.

The film-forming composition of the present invention can be applied to a substrate, then heated as needed to evaporate the solvent, and finally heated or irradiated with light to form a desired cured film.
The method of applying the film-forming composition is arbitrary, and methods such as spin coating, dip coating, flow coating, inkjet coating, jet dispenser coating, spray coating, bar coating, gravure coating, slit coating, roll coating, transfer printing, brush coating, blade coating, and air knife coating can be used.

Furthermore, suitable substrates include silicon, glass coated with indium tin oxide (ITO), glass coated with indium zinc oxide (IZO), metal nanowires, polyethylene terephthalate (PET), plastics, glass, quartz, ceramics, and other materials. Flexible substrates with flexibility can also be used.
The firing temperature is not particularly limited for the purpose of evaporating the solvent, and can be, for example, 110 to 400°C.
The firing method is not particularly limited; for example, it can be evaporated using a hot plate or oven under appropriate conditions such as air, an inert gas such as nitrogen, or a vacuum.
The firing temperature and firing time should be selected to match the process steps of the target electronic device, and the firing conditions should be chosen so that the physical properties of the resulting film match the required characteristics of the electronic device.
The conditions for light irradiation are not particularly limited; appropriate irradiation energy and time can be adopted depending on the triazine ring-containing polymer and crosslinking agent used.

The films and cured films of the present invention obtained as described above can achieve high heat resistance and low volume shrinkage, and are therefore suitable for use in the fields of electronic devices and optical materials, such as liquid crystal displays, organic EL elements (organic EL displays and organic EL lighting), touch panels, optoelectronic semiconductor (LED) elements, solid-state image sensors, organic thin-film solar cells, dye-sensitized solar cells, organic thin-film transistors (TFTs), lenses, prism cameras, binoculars, microscopes, and semiconductor exposure equipment.
In particular, films and cured films made from the film-forming composition of the present invention have high transparency, and when used as planarization films, light scattering layers, or encapsulants for organic EL lighting, they can improve the light extraction efficiency (light diffusion efficiency) and durability.

Furthermore, when the film-forming composition of the present invention is used as a light scattering layer for organic EL lighting, known light diffusing agents can be used, and are not particularly limited. These may be used individually, in combination of two or more of the same type, or in combination of two or more of different types.

Examples of light diffusing agents include organic diffusing agents.
Examples of organic light diffusing agents include cross-linked polymethyl methacrylate (PMMA) particles, cross-linked polymethyl acrylate particles, cross-linked polystyrene particles, cross-linked styrene-acrylic copolymer particles, melamine-formaldehyde particles, silicone resin particles, silica-acrylic composite particles, nylon particles, benzoguanamine-formaldehyde particles, benzoguanamine-melamine-formaldehyde particles, fluororesin particles, epoxy resin particles, polyphenylene sulfide resin particles, polyethersulfone resin particles, polyacrylonitrile particles, and polyurethane particles.
These light diffusing agents may also be used after being surface-treated with an appropriate surface modifier.

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples. The measuring devices used in the examples are as follows.

[ ^1H -NMR]
Equipment: Bruker NMR System AVANCE III HD 500 (500MHz)
Measurement solvent: Deuterated dimethyl sulfoxide (DMSO- _d6 )
Reference substance: Tetramethylsilane (TMS) (δ 0.0 ppm)
[GPC]
Equipment: Tosoh Corporation HLC-8200 GPC
Column: Tosoh TSKgel α-3000 + Tosoh TSKgel α-4000
Column temperature: 40°C
Solvent: Dimethylformamide (DMF)
Detector: RI
Calibration curve: Standard polystyrene [ellipsometer]
Equipment: J.A. Woolam Japan Multi-incidence angle ellipsometer VASE
[Spectrophotometer]
Equipment: Konica Minolta CM-3700A
[Optical Microscope]
Device: OLYMPUS BX51, manufactured by Olympus Optical Co., Ltd.
[exposure]
Equipment: UV irradiation device manufactured by iGraphics Co., Ltd. Equipment: Compact ultraviolet LED irradiator manufactured by Nitride Semiconductor Co., Ltd. NS395-CLT-100W3020

[1] Synthesis of triazine ring-containing polymers [Synthesis example 1] Synthesis of polymer compounds [4]

In a 3,000 mL four-necked flask, 4,4'-methylenebis-2-methylcyclohexylamine [2] (51.72 g, 0.217 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) and 513.61 g of N,N-dimethylacetamide (DMAc, manufactured by Kanto Chemical Co., Ltd.) were added. After purging with nitrogen, the mixture was stirred to dissolve 4,4'-methylenebis-2-methylcyclohexylamine [2] in DMAc. The mixture was then cooled to -5°C using an ethanol-dry ice bath, and 2,4,6-trichloro-1,3,5-triazine [1] (40.00 g, 0.217 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) was added while ensuring that the internal temperature did not exceed 5°C. Finally, the mixture was washed with 32.10 g of DMAc. After stirring for 30 minutes, the reaction solution was heated until the internal temperature reached 85°C ± 5°C. After stirring for 1 hour, 3-amino-1-propanol[3] (19.55 g, 0.260 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise, washed with DMAc 96.30 g, and stirred for 3 hours. Then, 3-amino-1-propanol[3] (48.88 g, 0.651 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise, stirred for 30 minutes, and then the stirring was stopped. Tetrahydrofuran (THF, 481 g, manufactured by Junsei Chemical Co., Ltd.), ammonium acetate (280.8 g), and deionized water (280.8 g) were added to the reaction solution and stirred for 30 minutes. After stopping the stirring, the solution was transferred to a separatory funnel and separated into an organic layer and an aqueous layer, and the organic layer was recovered. The recovered organic layer was returned to a 3,000 mL four-necked flask, ammonium acetate (280.8 g) and deionized water (280.8 g) were added again, and the mixture was stirred for 30 minutes. After stopping the stirring, the solution was transferred to a separatory funnel and separated into an organic layer and an aqueous layer, and the organic layer was recovered again. The recovered organic layer was dried in a vacuum dryer at 50°C for 8 hours to obtain 45.2 g of the target polymer compound [4] (hereinafter referred to as P-1).
The weight-average molecular weight Mw of compound P-1, measured in polystyrene equivalent by GPC, was 3,191, and the polydispersity Mw/Mn was 5.3. Figure 1 shows the results of the ^1H -NMR spectrum measurement of compound P-1.

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

In a 100 mL four-necked flask, 12.70 g of P-1[4] obtained in Synthesis Example 1 and 42.55 g of cyclopentanone (CPN, manufactured by ZEON Corporation) were added, and after purging with nitrogen, the mixture was stirred to dissolve. The solution was then heated to an internal temperature of 65°C, and 0.0045 g of N-nitrosophenylhydroxyamine aluminum salt (Q-1301, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 19.69 g of 2-isocyanatoethyl acrylate (AOI-VM, manufactured by Showa Denko Corporation) were added dropwise. The mixture was kept at an internal temperature of 65°C and stirred for 3 hours to obtain a 30% by mass CPN solution (hereinafter referred to as P-1-1 solution).

[Example 1-2] Synthesis of polymer compound [5] and preparation of polymer compound [5]-containing solution 45.20 g of P-1 [4] obtained in Synthesis Example 1 and 151.41 g of tetrahydrofuran (THF, manufactured by Junsei Chemical Co., Ltd.) were added to a 500 mL four-necked flask, and after purging with nitrogen, the mixture was stirred to dissolve. The solution was then heated to an internal temperature of 65°C, and 0.0045 g of N-nitrosophenylhydroxyamine aluminum salt (Q-1301, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 19.69 g of 2-isocyanatoethyl acrylate (AOI-VM, manufactured by Showa Denko K.K.) were added dropwise, and the mixture was stirred for 1 hour while maintaining an internal temperature of 65°C. After stirring for 1 hour, 151.41 g of tetrahydrofurfuryl acrylate (THFA, manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the THF was completely removed by evaporation using an evaporator to obtain a 30% by mass THFA solution (hereinafter referred to as solution P-1-2).

[2] Preparation of film-forming composition and production of cured film [Example 2-1]
To the P-1-1 solution (6.337 g) synthesized in Example 1-1, 0.095 g of Irgacure 2959 (BASF) as a UV radical generator, 0.038 g of Megafac F-477 (DIC Corporation), a 10% CPN solution, as a surfactant, and 13.530 g of CPN as an additional solvent were added, and the solution was prepared by visual confirmation that all components were dissolved (hereinafter referred to as SP-1 solution).
The SP-1 solution was spin-coated onto a 50 mm x 50 mm x 0.7 mm alkali-free glass substrate using a spin coater at 200 rpm for 5 seconds and then at 500 rpm for 30 seconds. After pre-curing on a 100°C hot plate for 2 minutes, a cured film was obtained by irradiating it with a UV irradiation device at an exposure dose of 200 mJ/ ^cm² (hereinafter referred to as the SP-1 film).

[Comparative Example 2-1]
P-1[4] (8.0 g) synthesized in Synthesis Example 1 and CPN (18.67 g) were added and dissolved to obtain a 30% by mass CPN solution (hereinafter referred to as P-1-3 solution).
The SP-2 solution was prepared in the same manner as in Example 2-1, except that the polymer solution was changed to the P-1-3 solution, and the SP-2 film was obtained.

For the cured films obtained as described above, the refractive index, film thickness, b ^* , transmittance from 400 to 800 nm, and haze were measured. The results are shown in Table 1, Figure 2, and Figure 3. For transmittance, the average transmittance from 400 to 800 nm was calculated and is shown in Table 1.

[Solvent resistance (crack resistance)]
[Example 3-1]
The SP-1 film obtained in Example 2-1 was set in a spin coater, and 1 mL of propylene glycol monomethyl ether (PGME) was applied. Next, the cured film was exposed to the solvent by rotating at 50 rpm for 60 seconds, taking care not to cause the liquid to splash from the substrate. After that, the solvent was removed from the substrate by rotating at 1,000 rpm for 30 seconds, and the refractive index and film thickness were measured, the residual film percentage was calculated, and the film surface was observed using an optical microscope.
The residual film percentage was calculated using the following formula.
Residual film percentage (%) = [(Film thickness after solvent exposure) ÷ (Film thickness before solvent exposure)] × 100

[Example 3-2]
Except for changing the solvent used for coating to cyclopentanone (CPN), the cured film was prepared and solvent resistance testing was performed in the same manner as in Example 2-1.

[Comparative Example 3-1]
Using the SP-2 film obtained in Comparative Example 2-1, a cured film was prepared and a solvent resistance test was performed in the same manner as in Example 2-1, except that the solvent used for coating was changed to PGME.

[Comparative Example 3-2]
Using the SP-2 film obtained in Comparative Example 2-1, a cured film was prepared and a solvent resistance test was performed in the same manner as in Example 2-1, except that the solvent used for coating was changed to CPN.

The results of the film thickness measurements and residual film percentages for Examples 3-1 to 3-2 and Comparative Examples 3-1 to 3-2 are shown in Table 1, and micrographs of the cured film surface are shown in Figures 4 and 5, respectively.

These results show that the cured film obtained in Example 2-1 has excellent effects, maintaining high refractive index and high transmittance while maintaining high solvent resistance and low b* and haze.

[4] Preparation of film-forming composition and production of cured film [Example 4-1]
To the P-1 solution (19.977 g) synthesized in Example 1-2, 3.596 g of DN-0075 (manufactured by Nippon Kayaku Co., Ltd.) as a crosslinking agent, 0.599 g of pentaerythritol tetrakis (3-mercaptobutyrate) (Karenz MT PE1, manufactured by Showa Denko K.K.) as a UV radical curing aid, 0.300 g of OXE-02 (manufactured by BASF) as a UV radical generator, 0.120 g of Megafac F-477 (manufactured by DIC Corporation) as a 10% by mass THFA solution as a surfactant, and 5.408 g of 4-acroylmorpholine (manufactured by KJ Chemicals) as an additional diluent monomer were added, and the solution was confirmed to be dissolved visually to prepare a solvent-free solution (hereinafter referred to as NP-1 solution).
This NP-1 solution was spin-coated onto a 50 mm x 50 mm x 0.7 mm alkali-free glass substrate using a spin coater at 200 rpm for 5 seconds and then at 770 rpm for 30 seconds. A cured film was obtained by irradiating the substrate with 395 nm wavelength light under nitrogen at an exposure dose of 900 mJ/ ^cm² using a UV-LED irradiation device (hereinafter referred to as the NP-1 film).

For the cured films obtained as described above, the refractive index, film thickness, b ^* , transmittance from 400 to 800 nm, and haze were measured. The results are shown in Table 2 and Figure 6. For transmittance, the average transmittance from 400 to 800 nm was calculated and is shown in Table 2.

[Solvent resistance (crack resistance)]
[Example 5-1]
The NP-1 film (cured film) obtained in Example 4-1 was set in a spin coater, and 1 mL of propylene glycol monomethyl ether (PGME) was applied. Next, the cured film was exposed to the solvent by rotating at 50 rpm for 60 seconds, taking care not to cause the liquid to splash from the substrate. After that, the solvent was removed from the substrate by rotating at 1,000 rpm for 30 seconds, and the refractive index and film thickness were measured, the residual film percentage was calculated, and the film surface was observed using an optical microscope.
The residual film percentage was calculated using the following formula.
Residual film percentage (%) = [(Film thickness after solvent exposure) ÷ (Film thickness before solvent exposure)] × 100

[Example 5-2]
A solvent resistance test was conducted in the same manner as in Example 5-1, except that the solvent to be applied was changed to propylene glycol monomethyl ether acetate (PGMEA).

[Example 5-3]
The solvent resistance test was performed in the same manner as in Example 5-1, except that the solvent to be applied was changed to cyclopentanone (CPN).

The results of the film thickness measurements and residual film percentages for Examples 5-1 to 5-3 are shown in Table 3, and micrographs of the cured film surface after the solvent resistance test are shown in Figures 7 to 9, respectively.

These results demonstrate that the cured film obtained from the NP-1 solution exhibits excellent properties, maintaining high solvent resistance even at thicker film thicknesses, while simultaneously maintaining high transmittance and low haze.

Claims (12)

A triazine ring-containing polymer comprising a repeating unit structure represented by the following formula (1), having at least one triazine ring terminus, wherein at least a portion of this triazine ring terminus is sealed with an amino group having a crosslinking group , and the crosslinking group is a (meth)acryloyl-containing group.
(In formula (1), R and R' independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group, and Q represents a C3-C30 alkylene group having an alicyclic structure. * represents a bond.) The triazine ring-containing polymer according to claim 1, wherein Q in formula (1) represents at least one selected from the group shown by formulas (2) to (15).
(In formulas (2) to (15), ^R1 and ^R2 independently represent alkylene groups having 1 to 5 carbon atoms, which may have a branched structure. * represents a bond.) The triazine ring-containing polymer according to claim 2, wherein Q in formula (1) is represented by formula (4). The triazine ring-containing polymer according to claim 2, wherein ^R1 and ^R2 are methylene groups. The triazine ring-containing polymer according to claim 1 , wherein the crosslinking group is a (meth)acryloyloxyalkyl group or a group represented by the following formula (i).
(In formula (i), ^A1 represents an alkylene group having 1 to 10 carbon atoms, and ^A2 represents a single bond or the following formula (j)
A represents a group represented by , where ^A3 represents an (a+1) valent aliphatic hydrocarbon group which may be substituted with a hydroxyl group, ^A4 represents a hydrogen atom or a methyl group, a represents 1 or 2, and * represents a bond. The triazine ring-containing polymer according to claim 5 , wherein the crosslinking group is selected from a (meth)acryloyloxymethyl group, a (meth)acryloyloxyethyl group, and a group represented by the following formulas (i-2) to (i-7).
(In equations (i-2) to (i-7), * represents a combination.) A film-forming composition comprising a triazine ring-containing polymer according to any one of claims 1 to 6 . The film-forming composition according to claim 7 , further comprising a crosslinking agent. The film-forming composition according to claim 8 , wherein the crosslinking agent is a polyfunctional (meth)acrylic compound. A film obtained from the film-forming composition described in claim 7 . An electronic device comprising a substrate and a film according to claim 10 formed on the substrate. An optical member comprising a substrate and a film according to claim 10 formed on the substrate.