TRIAZINE RING-CONTAINING POLYMER AND FILM-FORMING COMPOSITION CONTAINING SAME

Abstract

Provided is a triazine ring-containing polymer comprising a repeat unit structure, for example, as represented by the following formula (25). (In the formula, Ra represents R102 or R103, wherein R102 represents a fluorine atom or a C1-10 fluoroalkyl group and R103 represents a crosslinking group.)

Description

[Technical field]

[0001] The present invention relates to a triazine ring-containing polymer and a film-forming composition containing the same. [Background technology]

[0002] In recent years, there has been a demand for highly functional polymer materials in the development of electronic devices such as liquid crystal displays, organic electroluminescence (EL) elements (organic EL displays and organic EL lighting), touch panels, optical semiconductor (LED) elements, solid-state imaging elements, organic thin-film solar cells, dye-sensitized solar cells, and organic thin-film transistors (TFTs). Specific properties required include 1) heat resistance, 2) transparency, 3) high refractive index, 4) high solubility, 5) low volumetric shrinkage, 6) high temperature and humidity resistance, and 7) high film hardness. In view of this, the present applicant has already discovered that a polymer containing a repeating unit having a triazine ring and an aromatic ring has a high refractive index, and can achieve high heat resistance, high transparency, high refractive index, high solubility, and low volume shrinkage by itself, and is suitable as a film-forming composition for producing electronic devices (Patent Document 1).

[0003] Incidentally, in organic EL lighting, the planarization layer, light scattering layer, and the like are generally formed into a thin film by a coating method using a composition in which a high refractive index material is dissolved in an organic solvent. However, depending on the type of transparent conductive film, there are cases in which a highly polar solvent cannot be used. In addition, after a film-forming composition containing a highly refractive polymer is applied using a coating device, a low-polarity solvent or the like may be used as a line cleaning solvent for the device, and if the polymer has low solubility in such a solvent, the line may become clogged. Furthermore, when a thin film is exposed to a solvent during the manufacture of an electronic device, cracks may occur in the thin film depending on the conditions, and further improvement in its durability is required. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2010 / 128661 Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention has been made in consideration of the above circumstances, and aims to provide a triazine ring-containing polymer that is capable of forming a thin film having a high refractive index and excellent transparency and solvent resistance (crack resistance) and has excellent solubility in various organic solvents such as low-polarity solvents, hydrophobic solvents, and low-boiling point solvents, and a film-forming composition containing the same. [Means for solving the problem]

[0006] Means for Solving the Problems The present inventors have conducted extensive research in order to achieve the above object, and as a result have found that by using a triazine ring-containing polymer having at least one triazine ring terminal, at least a portion of which is capped with a fluorine atom-containing arylamino group and an arylamino group having a crosslinking group, a thin film having a high refractive index and excellent transparency and solvent resistance can be formed, and a triazine ring-containing polymer having excellent solubility in various organic solvents can be obtained, thereby completing the present invention.

[0007] That is, the present invention provides the following triazine ring-containing polymer and film-forming composition. [1] A triazine ring-containing polymer comprising a repeating unit structure represented by the following formula (1), having at least one triazine ring terminal, at least a portion of which is blocked with a fluorine atom-containing arylamino group and an arylamino group having a crosslinking group: [ka] 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; Ar represents at least one selected from the group represented by the formulas (2) to (13). [ka] [In the formula, R 1 ~R 92 each independently represents a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms; R 93 and R 94 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, W 1 and W 2 are, independently of each other, a single bond, CR 95 R 96 (R 95 and R 96 each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms (which may be joined together to form a ring), C=O, O, S, SO, SO2, or NR 97 (R 97 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a phenyl group; X 1 and X 2 are each independently a single bond, an alkylene group having 1 to 10 carbon atoms, or a group represented by the formula (14): [ka] (In the formula, R 98 ~R 101 each independently represents a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms; Y 1 and Y 2 each independently represents a single bond or an alkylene group having 1 to 10 carbon atoms. [2]. R 1 ~R 92 and R 98 ~R101 is a hydrogen atom. [3]. A triazine ring-containing polymer represented by formula (15) [1] or [2], wherein the fluorine atom-containing arylamino group is represented by formula (15). [ka] (In the formula, R 102 represents a fluorine atom or a fluoroalkyl group having 1 to 10 carbon atoms. [4] The triazine ring-containing polymer of [3], wherein the fluorine atom-containing arylamino group is represented by formula (16) or (17). [ka] (In the formula, R 102 has the same meaning as above.) [5]. R 102 wherein the alkyl group is a perfluoroalkyl group having 1 to 10 carbon atoms. [6] A triazine ring-containing polymer having an arylamino group having a crosslinking group, the triazine ring-containing polymer being any one of [1] to [5] represented by formula (18): [ka] (In the formula, R 103 represents a bridging group. [7]. A triazine ring-containing polymer of [6], wherein the arylamino group having a crosslinking group is represented by formula (19): [ka] (In the formula, R 103 has the same meaning as above.) [8] The triazine ring-containing polymer according to any one of [1] to [7], wherein the crosslinking group is a hydroxy-containing group or a (meth)acryloyl-containing group. [9] The triazine ring-containing polymer of [8], wherein the crosslinking group is a hydroxyalkyl group, a (meth)acryloyloxyalkyl group, or a group represented by the following formula (i): [ka] (In the formula, A 1 represents an alkylene group having 1 to 10 carbon atoms; 2 is a single bond or the following formula (j) [ka] A represents a group represented by the formula: 3 represents a divalent or trivalent aliphatic hydrocarbon group which may be substituted with a hydroxy group; A 4 represents a hydrogen atom or a methyl group, a represents 1 or 2, and * represents a bond.

[10] The triazine ring-containing polymer according to [9], wherein the crosslinking group is one or more selected from a hydroxymethyl group, a 2-hydroxyethyl group, a (meth)acryloyloxymethyl group, a (meth)acryloyloxyethyl group, and groups represented by the following formulas (i-2) to (i-5): [ka] (In the formula, * represents a bond.)

[11] The triazine ring-containing polymer according to any one of [1] to

[10] , wherein Ar is represented by formula (20) or (21): [ka]

[12] A film-forming composition comprising the triazine ring-containing polymer according to any one of [1] to

[11] and an organic solvent.

[13] The film-forming composition according to

[12] , wherein the organic solvent includes at least one selected from glycol ester-based solvents, ketone-based solvents, and ester-based solvents.

[14] The film-forming composition according to

[12] or

[13] , further comprising a crosslinking agent.

[15] The film-forming composition according to

[14] , wherein the crosslinking agent is a polyfunctional (meth)acrylic compound.

[16] A thin film obtained from any one of the film-forming compositions

[12] to

[15] .

[17] . An electronic device comprising a substrate and the thin film of

[16] formed on the substrate.

[18] An optical component comprising a substrate and the thin film of

[16] formed on the substrate. Effect of the Invention

[0008] According to the present invention, it is possible to provide a triazine ring-containing polymer which can form a thin film having a high refractive index and excellent transparency and solvent resistance, and which has excellent solubility in various organic solvents such as low-polarity solvents, hydrophobic solvents, and low-boiling point solvents. It is generally known that the introduction of fluorine atoms into a compound tends to decrease the refractive index of the compound. However, the triazine ring-containing polymer of the present invention maintains a high refractive index despite the introduction of fluorine atoms. By using such a triazine ring-containing polymer of the present invention, a composition can be prepared using an organic solvent having low dissolving power, such as a low-polarity solvent or a hydrophobic solvent, so that a thin film can be formed without any problems even on a substrate that is easily eroded by a high-polarity solvent. A thin film prepared from the film-forming composition of the present invention can exhibit properties such as high heat resistance, high refractive index, 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 a part of the materials used in producing liquid crystal displays, organic EL elements (organic EL displays and organic EL lighting), touch panels, optical semiconductor (LED) elements, solid-state imaging elements, organic thin-film solar cells, dye-sensitized solar cells, organic thin-film transistors (TFTs), lenses, prisms, cameras, binoculars, microscopes, semiconductor exposure devices, etc. In particular, a thin film prepared from the film-forming composition of the present invention has high transparency, refractive index, and solvent resistance (crack resistance), and therefore, when used as a planarizing layer or light-scattering layer in an organic EL lighting device, the light extraction efficiency (light diffusion efficiency) can be improved as well as the durability. [Brief description of the drawings]

[0009] [Figure 1] FIG. 1 is a 1H-NMR spectrum of the polymer compound [5] obtained in Example 1-1. [Diagram 2] FIG. 1 is a 1H-NMR spectrum of the polymer compound [6] obtained in Example 1-2. [Diagram 3] FIG. 1 is a 1H-NMR spectrum of the polymer compound [9] obtained in Example 1-3. [Figure 4] FIG. 1 is a 1H-NMR spectrum of the polymer compound

[11] obtained in Comparative Example 1-1. [Diagram 5] 1 is an optical microscope photograph of the surface of the cured film obtained in Example 4-1 after exposure to a solvent. [Figure 6] 1 is an optical microscope photograph of the surface of the cured film obtained in Comparative Example 4-1 after exposure to a solvent. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] The present invention will be described in further detail below. The triazine ring-containing polymer according to the present invention contains a repeating unit structure represented by the following formula (1). The triazine ring-containing polymer is, for example, a so-called hyperbranched polymer. A hyperbranched polymer is a highly branched polymer having an irregular branching structure. Here, the irregularity means that the branching structure is more irregular than that of a dendrimer, which is a highly branched polymer having a regular branching structure. For example, a triazine ring-containing polymer that is a hyperbranched polymer contains a structure (structure A) that is larger than the repeating unit structure represented by formula (1) and is formed by bonding the repeating unit structure represented by formula (1) to each of three bonds of the repeating unit structure represented by formula (1). In the triazine ring-containing polymer that is a hyperbranched polymer, structure A is distributed throughout the entire triazine ring-containing polymer except for the terminals. In the triazine ring-containing polymer which is a hyperbranched polymer, the repeating unit structure may essentially consist of only the repeating unit structure represented by formula (1).

[0011] [ka]

[0012] 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, 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 is preferably 1 to 20, and in consideration of further improving 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. In addition, the structure of the alkyl group is not particularly limited, and may be, for example, any of linear, branched, cyclic, and combinations of two or more of these.

[0013] 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 Examples of such cyclopropyl ether 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.

[0014] The number of carbon atoms in the alkoxy group is not particularly limited, but is preferably 1 to 20, and in consideration of further improving the heat resistance of the polymer, the number of carbon atoms in the alkoxy group is more preferably 1 to 10, and even more preferably 1 to 3. In addition, the structure of the alkyl portion is not particularly limited, and may be, for example, any of linear, branched, cyclic, and combinations of two or more of these.

[0015] 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, 3-methyl-n-pentyloxy, and 2-methyl-n-pentyloxy. Examples of the aryloxy group 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.

[0016] The number of carbon atoms in the aryl group is not particularly limited, but is preferably 6 to 40. In consideration of further improving the heat resistance of the polymer, the number of carbon atoms in the aryl group is more preferably 6 to 16, and even more preferably 6 to 13. In the present invention, the aryl group includes an aryl group having a substituent, such as a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a nitro group, and a cyano group. Specific examples of the aryl group 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.

[0017] The number of carbon atoms in the aralkyl group is not particularly limited, but preferably is 7 to 20. The structure of the alkyl portion is not particularly limited, and may be, for example, linear, branched, cyclic, or a combination of two or more of these. In the present invention, the aralkyl group includes an aralkyl group having a substituent, for example, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, and the like. Specific examples thereof include benzyl, p-methylphenylmethyl, m-methylphenylmethyl, o-ethylphenylmethyl, m-ethylphenylmethyl, p-ethylphenylmethyl, 2-propylphenylmethyl, 4-isopropylphenylmethyl, 4-isobutylphenylmethyl, and α-naphthylmethyl groups.

[0018] The above Ar represents at least one selected from the group represented by the formulas (2) to (13).

[0019] [ka]

[0020] Above R 1 ~R 92 each independently represents a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms; R 93 and R94 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; W 1 and W 2 are, independently of each other, a single bond, CR 95 R 96 (R 95 and R 96 each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms (which may be joined together to form a ring), C=O, O, S, SO, SO2, or NR 97 (R 97 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a phenyl group.

[0021] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The alkyl group and alkoxy group include the same as the alkyl group and alkoxy group in R and R'.

[0022] The halogenated alkyl group having 1 to 10 carbon atoms is one in which at least one hydrogen atom in the above-mentioned alkyl group having 1 to 10 carbon atoms is substituted with a halogen atom. Specific examples thereof include, for example, trifluoromethyl, 2,2,2-trifluoroethyl, perfluoroethyl, 3,3,3-trifluoropropyl, 2,2,3,3,3-pentafluoropropyl, 2,2,3,3-tetrafluoropropyl, 2,2,2-trifluoro-1-(trifluoromethyl)ethyl, perfluoropropyl, 4,4,4-trifluorobutyl, 3,3 ,4,4,4-pentafluorobutyl, 2,2,3,3,4,4,4-heptafluorobutyl, perfluorobutyl, 2,2,3,3,4,4,5,5,5-nonafluoropentyl, 2,2,3,3,4,4,5,5-octafluoropentyl, perfluoropentyl, 2,2,3,3,4,4,5,5,6,6,6-undecafluorohexyl, 2,2,3,3,4,4,5,5,6,6-decafluorohexyl, 3,3,4,4,5,5,6,6,6-nonafluorohexyl, and perfluorohexyl groups.

[0023] Also, X1 and X 2 each independently represents a single bond, an alkylene group having 1 to 10 carbon atoms, or a group represented by the formula (14). The structures of these alkyl groups, halogenated alkyl groups, alkoxy groups, and alkylene groups are not particularly limited, and may be, for example, linear, branched, cyclic, or a combination of two or more of these.

[0024] [ka]

[0025] Above R 98 ~R 101 each independently represents a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms; Y 1 and Y 2 are each independently a single bond or an alkylene group having 1 to 10 carbon atoms. As the halogen atom, the alkyl group, the halogenated alkyl group, and the alkoxy group, R 1 ~R 92 Examples of the halogen atom, alkyl group, halogenated alkyl group, and alkoxy group are the same as those in the above. Examples of the alkylene group having 1 to 10 carbon atoms include methylene, ethylene, propylene, trimethylene, tetramethylene, and pentamethylene groups. The structure of the alkylene group is not particularly limited, and may be, for example, any of linear, branched, cyclic, and combinations of two or more of these.

[0026] Among these, R 1 ~R 92 and R 98 ~R 101 is preferably a hydrogen atom, a halogen atom, a sulfo group, an alkyl group having 1 to 5 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms, and more preferably a hydrogen atom.

[0027] In particular, Ar is preferably at least one of the aryl groups represented by the formulae (2), (5) to (13), and more preferably at least one of the aryl groups represented by the formulae (2), (5), (7), (8), and (11) to (13). Specific examples of the aryl groups represented by the formulae (2) to (13) include, but are not limited to, those represented by the following formulae:

[0028] [ka] "Ph" represents a phenyl group.

[0029] Among these, aryl groups represented by the following formula are more preferred because they give polymers with higher refractive indexes.

[0030] [ka] "Ph" represents a phenyl group.

[0031] In particular, in consideration of further increasing the refractive index and heat resistance of the triazine ring-containing polymer, Ar is preferably a group having a fluorene skeleton represented by formula (20) or a diphenylsulfone skeleton represented by formula (21).

[0032] [ka]

[0033] The triazine ring-containing polymer of the present invention has at least one triazine ring terminal, and at least a portion of the triazine ring terminal is blocked with a fluorine atom-containing arylamino group and an arylamino group having a crosslinking group. The triazine ring-containing polymer of the present invention has at least one triazine ring terminal, and this terminal triazine ring usually has two halogen atoms that can be substituted with the above-mentioned fluorine atom-containing arylamino group and arylamino group having a crosslinking group. Therefore, the above-mentioned fluorine atom-containing arylamino group and arylamino group having a crosslinking group may be bonded to the same triazine ring terminal, or when there are multiple triazine ring terminals, each may be bonded to a different triazine ring terminal. In other words, "at least a portion of the triazine ring terminals are terminated with a fluorine atom-containing arylamino group and an arylamino group having a crosslinking group" includes both the case where the fluorine atom-containing arylamino group and the arylamino group having a crosslinking group are bonded to the same triazine ring terminal, and the case where the fluorine atom-containing arylamino group and the arylamino group having a crosslinking group are each bonded to a different triazine ring terminal.

[0034] Examples of the aryl group of the fluorine atom-containing arylamino group and the arylamino group having a crosslinking group include the same as those mentioned above, with a phenyl group being particularly preferred. In addition, the bridging group is bonded to an aryl group. A fluorine atom-containing arylamino group is an arylamino group having a fluorine atom-containing group bonded to an aryl group. Examples of the fluorine atom-containing group include a fluorine atom and a fluorine atom-containing hydrocarbon group such as a fluoroalkyl group, with a fluorine atom and a fluoroalkyl group having 1 to 10 carbon atoms being preferred. The fluoroalkyl group having 1 to 10 carbon atoms is not particularly limited and may be, for example, any of linear, branched, and cyclic groups, and combinations of two or more thereof, such as trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, heptafluoropropyl, 2,2,3,3,3-pentafluoropropyl, 2,2,3,3-tetrafluoropropyl, 2,2,2-trifluoro-1-(trifluoromethyl)ethyl, and nonafluorobutyl. , 4,4,4-trifluorobutyl, undecafluoropentyl, 2,2,3,3,4,4,5,5,5-nonafluoropentyl, 2,2,3,3,4,4,5,5-octafluoropentyl, tridecafluorohexyl, 2,2,3,3,4,4,5,5,6,6,6-undecafluorohexyl, 2,2,3,3,4,4,5,5,6,6-decafluorohexyl, and 3,3,4,4,5,5,6,6,6-nonafluorohexyl groups.

[0035] In particular, in consideration of increasing the solubility of the triazine ring-containing polymer in low-polarity solvents and the like while maintaining the refractive index, a perfluoroalkyl group having 1 to 10 carbon atoms is preferred, and in particular, a perfluoroalkyl group having 1 to 5 carbon atoms is more preferred, with a trifluoromethyl group being the most suitable.

[0036] The number of fluorine-containing groups in the fluorine-containing arylamino group is not particularly limited and may be any number that can be substituted on the aryl group. In consideration of the balance between maintaining the refractive index and solubility in a solvent, the number is preferably 1 to 4, more preferably 1 or 2, and even more preferably 1.

[0037] Examples of the crosslinking group include a hydroxy-containing group, 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. In consideration of improving the heat resistance of the triazine ring-containing polymer and the solvent resistance (crack resistance) of the resulting thin film, the hydroxy-containing group and the (meth)acryloyl-containing group are preferred.

[0038] Examples of the hydroxy-containing group include a hydroxy group and a hydroxyalkyl group, with a hydroxyalkyl group having 1 to 10 carbon atoms being preferred, a hydroxyalkyl group having 1 to 5 carbon atoms being more preferred, and a hydroxyalkyl group having 1 to 3 carbon atoms being even more preferred. Examples of the hydroxyalkyl group having 1 to 10 carbon atoms include hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 5-hydroxypentyl, 6-hydroxyhexyl, 7-hydroxyheptyl, 8-hydroxyoctyl, 9-hydroxynonyl, 10-hydroxydecyl, 2-hydroxy-1-methylethyl, 2-hydroxy-1,1-dimethylethyl, 3-hydroxy-1-methylpropyl, 3-hydroxy-2-methylpropyl, 3-hydroxy-1,1-dimethylpropyl, 3-hydroxy-1,2-dimethylpropyl, 3-hydroxy-2,2-dimethylpropyl, 4-hydroxypropyl, 5-hydroxypropyl, 6-hydroxypropyl, 7-hydroxypropyl, 8-hydroxypropyl, 9-hydroxypropyl, 10-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 4-hydroxypropyl, 5-hydroxypropyl, 6-hydroxypropyl, 7-hydroxypropyl, 8-hydroxypropyl, 9-hydroxypropyl, 10-hydroxypropyl, 2-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 3-hydroxypropyl, 4-hydroxypropyl, 5-hydroxypropyl, 6-hydroxypropyl, 7-hydroxypropyl, 8-hydroxypropyl, 9-hydroxypropyl, 10-hydroxypropyl, 1 ... -1-methylbutyl, 4-hydroxy-2-methylbutyl, 4-hydroxy-3-methylbutyl, and other groups in which the carbon atom to which a hydroxy group is bonded is a primary carbon atom; and 1-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 1-hydroxybutyl, 2-hydroxybutyl, 1-hydroxyhexyl, 2-hydroxyhexyl, 1-hydroxyoctyl, 2-hydroxyoctyl, 1-hydroxydecyl, 2-hydroxydecyl, 1-hydroxy-1-methylethyl, 2-hydroxy-2-methylpropyl, and other groups in which the carbon atom to which a hydroxy group is bonded is a secondary or tertiary carbon atom.

[0039] In particular, in consideration of improving heat resistance and resistance to high temperature and high humidity, it is preferable that the carbon atom to which the hydroxyl group is bonded is a primary carbon atom, and among these, a hydroxyalkyl group having 1 to 5 carbon atoms is more preferable, a hydroxyalkyl group having 1 to 3 carbon atoms is even more preferable, a hydroxymethyl group and a 2-hydroxyethyl group are further preferable, and a 2-hydroxyethyl group is most preferable.

[0040] Examples of the (meth)acryloyl-containing group include a (meth)acryloyl group, a (meth)acryloyloxyalkyl group, and a group represented by the following formula (i). Of these, a (meth)acryloyloxyalkyl group having an alkylene group having 1 to 10 carbon atoms and a group represented by the following formula (i) are preferred, and a group represented by the following formula (i) is more preferred.

[0041] [ka] (In the formula, A 1 represents an alkylene group having 1 to 10 carbon atoms; 2 is a single bond or the following formula (j) [ka] A represents a group represented by the formula: 3 represents a divalent or trivalent aliphatic hydrocarbon group which may be substituted with a hydroxy group; A 4 represents a hydrogen atom or a methyl group, a represents 1 or 2, and * represents a bond.

[0042] Examples of the alkylene group contained in the (meth)acryloyloxyalkyl group having an alkylene group (alkanediyl group) having 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, decimethylenemethyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl groups. In consideration of improving heat resistance and resistance to high temperature and high humidity, among these, those having an alkylene group having 1 to 5 carbon atoms are preferred, those having an alkylene group having 1 to 3 carbon atoms are preferred, and those having an alkylene group having 1 or 2 carbon atoms are more preferred.

[0043] Specific examples of the (meth)acryloyloxyalkyl group include a (meth)acryloyloxymethyl group, a 2-(meth)acryloyloxyethyl group, a 3-(meth)acryloyloxypropyl group, and a 4-(meth)acryloyloxybutyl group.

[0044] In formula (i), A 1 is an alkylene group having 1 to 10 carbon atoms, preferably an alkylene group having 1 to 5 carbon atoms, more preferably a methylene group or an ethylene group. Examples of the alkylene group having 1 to 10 carbon atoms include the same alkylene groups as those contained in the above-mentioned (meth)acryloyloxyalkyl group.

[0045] A 2 represents a single bond or a group represented by formula (j), and a group represented by formula (j) is preferred.

[0046] A 3 is a divalent or trivalent aliphatic hydrocarbon group which may be substituted with a hydroxy group, and specific examples thereof include an alkylene group having 1 to 5 carbon atoms and the following formulae (k-1) to (k-3): [ka] (In the formula, * is as defined above.) Of these, alkylene groups having 1 to 5 carbon atoms are preferred, alkylene groups having 1 to 3 carbon atoms are more preferred, and methylene and ethylene groups are even more preferred. 3 As the alkylene group of A 1 Among the alkylene groups exemplified above, alkylene groups having 1 to 5 carbon atoms can be mentioned.

[0047] a represents 1 or 2, with 1 being preferred.

[0048] A preferred embodiment of the group represented by formula (i) is one represented by the following formula (i-1).

[0049] [ka] (In the formula, A 1 , A 3 , A 4 and * are as above.)

[0050] More preferred embodiments of the group represented by formula (i) include those represented by the following formulas (i-2) to (i-5).

[0051] [ka] (In the formula, * is as defined above.)

[0052] Examples of the vinyl-containing group include alkenyl groups having 2 to 10 carbon atoms and having a vinyl group at the terminal thereof, etc. Specific examples include ethenyl, 1-propenyl, allyl, isopropenyl, 1-butenyl, 2-butenyl, and 2-pentenyl groups.

[0053] Examples of the epoxy-containing group include epoxy, glycidyl, and glycidyloxy groups. Specific examples include glycidylmethyl, 2-glycidylethyl, 3-glycidylpropyl, and 4-glycidylbutyl groups.

[0054] Examples of oxetane-containing groups include oxetan-3-yl, (oxetan-3-yl)methyl, 2-(oxetan-3-yl)ethyl, 3-(oxetan-3-yl)propyl, 4-(oxetan-3-yl)butyl groups, and the like.

[0055] Examples of the carboxy-containing group include a carboxy group and a carboxyalkyl group having 2 to 10 carbon atoms. As the carboxyalkyl group having 2 to 10 carbon atoms, the carbon atom to which the carboxy group is bonded is preferably a primary carbon atom, and specific examples include a carboxymethyl group, a 2-carboxyethyl group, a 3-carboxypropyl group, and a 4-carboxybutyl group.

[0056] Examples of the sulfo-containing group include a sulfo group and a sulfoalkyl group having 1 to 10 carbon atoms. As the sulfoalkyl group having 1 to 10 carbon atoms, the carbon atom to which the sulfo group is bonded is preferably a primary carbon atom, and specific examples include a sulfomethyl group, a 2-sulfoethyl group, a 3-sulfopropyl group, and a 4-sulfobutyl group.

[0057] Examples of the thiol-containing group include a thiol group and a mercaptoalkyl group having 1 to 10 carbon atoms. As the mercaptoalkyl group having 1 to 10 carbon atoms, the carbon atom to which the thiol group is bonded is preferably a primary carbon atom, and specific examples include mercaptomethyl, 2-mercaptoethyl, 3-mercaptopropyl, and 4-mercaptobutyl groups.

[0058] The number of crosslinking groups in the arylamino group having the above crosslinking group is not particularly limited and may be any number that can be substituted on the aryl group. In consideration of the balance between solvent resistance and solubility in a solvent, however, 1 to 4 crosslinking groups are preferred, 1 to 2 are more preferred, and 1 is even more preferred.

[0059] A suitable fluorine atom-containing arylamino group is represented by the formula (15). In particular, the formula (16) having a fluorine atom-containing group at the para-position relative to the amino group or the formula (17) having a fluorine atom-containing group at the meta-position relative to the amino group is preferred.

[0060] [ka] (In the formula, R 102 represents a fluorine atom or a fluoroalkyl group having 1 to 10 carbon atoms.

[0061] [ka] (In the formula, R 102 has the same meaning as above.)

[0062] Specific examples of fluorine atom-containing arylamino groups include those represented by the following formulae, but are not limited thereto.

[0063] [ka]

[0064] The fluorine atom-containing arylamino group can be introduced by using a corresponding fluorine atom-containing arylamino compound in the production method described below. Specific examples of the fluorine atom-containing arylamino compound include 4-fluoroaniline, 4-trifluoromethylaniline, and 4-pentafluoroethylaniline.

[0065] Suitable arylamino groups having a bridging group include those represented by formula (18), and in particular, those represented by formula (19) having a bridging group at the para position relative to the amino group are preferred.

[0066] [ka] (In the formula, R 103 represents a bridging group.

[0067] [ka] (In the formula, R 103 has the same meaning as above.)

[0068] Specific examples of the arylamino group having a crosslinking group include those represented by the following formulae, but are not limited thereto.

[0069] [ka]

[0070] An arylamino group having a hydroxyalkyl group can be introduced by using a corresponding hydroxyalkyl group-substituted arylamino compound in the production method described below. Specific examples of the hydroxyalkyl group-substituted arylamino compound include (4-aminophenyl)methanol and 2-(4-aminophenyl)ethanol.

[0071] An arylamino group having a (meth)acryloyloxyalkyl group can be introduced by a method using a corresponding (meth)acryloyloxyalkyl group-substituted arylamino compound, or by a method in which an arylamino group having a hydroxyalkyl group is introduced into a triazine ring-containing polymer and then a (meth)acrylic acid halide or glycidyl (meth)acrylate is allowed to react with the hydroxy group contained in the hydroxyalkyl group.

[0072] The arylamino group having a group represented by formula (i) can be introduced by a method using an arylamino compound having a desired crosslinking group, or by a method in which an arylamino group having a hydroxyalkyl group is introduced into a triazine ring-containing polymer, and then a (meth)acrylic acid ester compound having an isocyanate group represented by the following formula (i') is allowed to react with the hydroxy group contained in the hydroxyalkyl group.

[0073] [ka] (In the formula, A 3 , A 4 and a are as above.)

[0074] Specific examples of the (meth)acryloyloxyalkyl group-substituted arylamino compound include ester compounds obtained by reacting the hydroxy group of the above-mentioned hydroxyalkyl group-substituted arylamino compound with (meth)acrylic acid halide or glycidyl (meth)acrylate. The (meth)acrylic acid halide may include (meth)acrylic acid chloride, (meth)acrylic acid bromide, and (meth)acrylic acid iodide. Specific examples of the (meth)acrylic acid ester compound having an isocyanate group represented by the above formula (i') include 2-isocyanatoethyl acrylate, 2-isocyanatoethyl methacrylate, and 1,1-(bisacryloyloxymethyl)ethyl isocyanate.

[0075] In the present invention, particularly preferred triazine ring-containing polymers include those containing repeating units represented by formulae (22) to (25) and formulae (26) to (29).

[0076] [ka] (In the formula, R a is R 102 or R 103 R, R', R 69 ~R 76 , R 98 ~R 101 , R 102 and R 103 has the same meaning as above.)

[0077] [ka] (In the formula, R a , R 69 ~R 76 , R 98 ~R 101 has the same meaning as above.)

[0078] [ka] (In the formula, R a has the same meaning as above.)

[0079] [ka] (In the formula, R a has the same meaning as above.)

[0080] [ka] (In the formula, R a , R 16 ~R 23 , R and R' have the same meanings as above.)

[0081] [ka] (In the formula, R a , R 16 ~R 23 has the same meaning as above.)

[0082] [ka] (In the formula, R a has the same meaning as above.)

[0083] [ka] (In the formula, R 102 and R 103 has the same meaning as above.)

[0084] 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. From the viewpoints of further improving heat resistance and reducing shrinkage, it is preferably 2,000 or more. From the viewpoints of further increasing solubility and reducing the viscosity of the obtained solution, it is preferably 50,000 or less, more preferably 30,000 or less, and even more preferably 10,000 or less. The weight average molecular weight in the present invention is an average molecular weight obtained by gel permeation chromatography (hereinafter, referred to as GPC) analysis in terms of standard polystyrene.

[0085] The triazine ring-containing polymer (hyperbranched polymer) of the present invention can be produced in accordance with the method disclosed in the above-mentioned WO 2010 / 128661. That is, a trihalogenated triazine compound is reacted with an aryldiamino compound in an organic solvent, and then the resulting mixture is reacted with, for example, a fluorine atom-containing arylamino compound, which is an end-capping agent, and at least one arylamino compound selected from an arylamino compound having a hydroxyalkyl group (hydroxy-containing group), an arylamino compound having an acryloyloxyalkyl group (acryloyl-containing group), and an arylamino compound having a group represented by formula (i) (acryloyl-containing group), to obtain the triazine ring-containing polymer of the present invention.

[0086] For example, as shown in the following scheme 1, the triazine ring-containing polymer (24) can be obtained by reacting a triazine compound (30) with an aryldiamino compound (31) in a suitable organic solvent, followed by reaction with a terminal-capping agent, that is, a fluorine atom-containing aniline compound, and at least one arylamino compound (32) selected from arylamino compounds having a hydroxyalkyl group and arylamino compounds having a group represented by formula (i).

[0087] [ka] (In the formula, X's each independently represent a halogen atom; R b represents a fluorine atom-containing group, a hydroxyalkyl group, or a group represented by formula (i).

[0088] In the above reaction, the charging ratio of the aryldiamino compound (31) is arbitrary as long as the target polymer is obtained, but the charging ratio is preferably 0.01 to 10 equivalents, more preferably 0.7 to 5 equivalents, of the aryldiamino compound (31) relative to 1 equivalent of the triazine compound (30). The aryldiamino compound (31) may be added neat or in the form of a solution dissolved in an organic solvent. In view of ease of operation and control of the reaction, the latter method is preferred. The reaction temperature may be appropriately set within the range from the melting point of the solvent used to the boiling point of the solvent, and is preferably about -30 to 150°C, more preferably -10 to 100°C.

[0089] Another embodiment is the method shown in the following scheme 2. In this method, the triazine ring-containing polymer (24) can be obtained by reacting a triazine compound (30) with an aryldiamino compound (31) in a suitable organic solvent, and then reacting the resulting mixture with a fluorine atom-containing aniline compound and an arylamino compound (32') having a hydroxyalkyl group, which are end-capping agents, to obtain a triazine ring-containing polymer (24') (first step), and then reacting a (meth)acrylic acid ester compound having an isocyanate group represented by formula (i') with the hydroxy group of the hydroxyalkyl group contained in the triazine ring-containing polymer (24') (second step). When the triazine ring-containing polymer (24') is the target product, the reaction may be completed in the first stage without carrying out the second stage reaction.

[0090] [ka] (In the formula, R c represents a fluorine atom-containing group or a hydroxyalkyl group; X, A 3 , A 4 , R b and a have the same meaning as above.)

[0091] In the above reaction, the charge ratio and addition method of the aryldiamino compound (31) in the first step, and the reaction temperature in the reaction until the triazine ring-containing polymer (24′) is obtained can be the same as those explained in Scheme 1. In the second step, the ratio of the (meth)acrylic acid ester compound having an isocyanate group represented by the above formula (i') to the triazine ring-containing polymer (24') can be arbitrarily set according to the ratio of the hydroxyalkyl group to the group represented by formula (i), and is preferably 0.1 to 10 equivalents, more preferably 0.5 to 5 equivalents, even more preferably 0.7 to 3 equivalents, and even more preferably 0.9 to 1.5 equivalents relative to 1 equivalent of the arylamino compound having a hydroxyalkyl group used. For example, when all of the hydroxyalkyl groups contained in the triazine ring-containing polymer (24') are groups represented by formula (i), the ratio of the (meth)acrylic acid ester compound is preferably 1.0 to 10 equivalents, more preferably 1.0 to 5 equivalents, even more preferably 1.0 to 3 equivalents, and even more preferably 1.0 to 1.5 equivalents relative to 1 equivalent of the arylamino compound having a hydroxyalkyl group used. The reaction temperature in this reaction is the same as that in the reaction to obtain the triazine ring-containing polymer (24'), but in consideration of preventing polymerization of the (meth)acryloyl group during the reaction, the reaction temperature is preferably 30 to 80°C, more preferably 40 to 70°C, and even more preferably 50 to 60°C.

[0092] As yet another embodiment, there is a method shown in the following scheme 3. In this method, the triazine ring-containing polymer (28) can be obtained by reacting a triazine compound (30) with an aryldiamino compound (33) in a suitable organic solvent, and then reacting the resulting mixture with a terminal-capping agent, that is, a fluorine atom-containing aniline compound, and at least one arylamino compound (32) selected from arylamino compounds having a hydroxyalkyl group and arylamino compounds having a group represented by formula (i).

[0093] [ka] (Wherein, X and R b has the same meaning as above.)

[0094] In the above reaction, the charging ratio of the aryldiamino compound (33) is arbitrary as long as the target polymer is obtained, but the charging ratio is preferably 0.01 to 10 equivalents, more preferably 0.7 to 5 equivalents, of the aryldiamino compound (33) relative to 1 equivalent of the triazine compound (30). The aryldiamino compound (33) may be added neat or in the form of a solution dissolved in an organic solvent. In view of ease of operation and control of the reaction, the latter method is preferred. The reaction temperature may be appropriately set within the range from the melting point of the solvent used to the boiling point of the solvent, and is preferably about -30 to 150°C, more preferably -10 to 100°C.

[0095] As the organic solvent, various solvents commonly used in this type of reaction can be used, for example, tetrahydrofuran (THF), dioxane, dimethyl sulfoxide; amide solvents such as N,N-dimethylformamide, N-methyl-2-pyrrolidone, tetramethylurea, hexamethylphosphoramide, N,N-dimethylacetamide, N-methyl-2-piperidone, N,N-dimethylethyleneurea, N,N,N',N'-tetramethylmalonamide, N-methylcaprolactam, N-acetylpyrrolidine, N,N-diethylacetamide, N-ethyl-2-pyrrolidone, N,N-dimethylpropionic acid amide, N,N-dimethylisobutyramide, N-methylformamide, and N,N'-dimethylpropyleneurea, and mixed solvents thereof. Among these, N,N-dimethylformamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, and mixtures thereof are preferred, and N,N-dimethylacetamide and N-methyl-2-pyrrolidone are particularly suitable.

[0096] In the first step reaction of the above scheme 1, various bases that are commonly used may be added during or after the polymerization. Specific examples of the 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, and the like. The amount of the base to be added is preferably 1 to 100 equivalents relative to 1 equivalent of the triazine compound (30), and more preferably 1 to 10 equivalents. These bases may be used in the form of an aqueous solution. It is preferred that no raw material components remain in the resulting polymer, but some raw materials may remain as long as the effects of the present invention are not impaired. After completion of the reaction, the product can be easily purified by a method such as reprecipitation.

[0097] As a method for terminal blocking using a fluorine atom-containing aniline compound and an arylamino compound having a crosslinking group, a known method may be adopted. In this case, the total amount of the end-capping 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 the halogen atom derived from the excess triazine compound not used in the polymerization reaction. The reaction solvent and reaction temperature may be the same as those described in the first step of the above scheme 1, and the end-capping agent may be charged simultaneously with the aryldiamino compound (33). An arylamino compound having no substituent may be used and end-capping may be performed with three or more types of groups. The aryl groups of this arylamino compound having no substituent may be the same as those mentioned above.

[0098] From the viewpoint of achieving a good balance between solubility in organic solvents and solvent resistance (crack resistance), the ratio of the fluorine atom-containing aniline compound to the arylamino compound having a crosslinking group is preferably 0.5 to 1.5 mol, more preferably 0.8 to 1.2 mol, even more preferably 0.9 to 1.1 mol, and still more preferably 0.95 to 1.05 mol, of the arylamino compound having a crosslinking group per 1 mol of the fluorine atom-containing aniline compound.

[0099] The above-mentioned triazine ring-containing polymer of the present invention can be suitably used as a film-forming composition, and in this case, a crosslinking agent may be added. The crosslinking agent is not particularly limited as long as it is a compound having a substituent capable of reacting with the crosslinking group of the above-mentioned triazine ring-containing polymer. Examples of such compounds include melamine-based compounds having a crosslinking substituent such as a methylol group or a methoxymethyl group (e.g., a phenoplast compound, an aminoplast compound, etc.), a substituted urea-based compound, a compound containing a crosslinking substituent such as an epoxy group or an oxetane group (e.g., a polyfunctional epoxy compound, a polyfunctional oxetane compound, etc.), a compound containing a blocked isocyanate group, a compound having an acid anhydride group, a compound having a (meth)acrylic group, etc., from the viewpoint of heat resistance and storage stability, a compound containing an epoxy group, a blocked isocyanate group, or a (meth)acrylic group is preferred, and in particular, a compound having a blocked isocyanate group, or a polyfunctional epoxy compound and / or a polyfunctional (meth)acrylic compound that gives a composition that can be photocured without using an initiator is preferred. In addition, when these compounds are used for terminal treatment of a polymer, they are required to have at least one cross-linking substituent, but when they are used for cross-linking treatment between polymers, they are required to have at least two cross-linking substituents.

[0100] The polyfunctional epoxy compound is not particularly limited as long as it has two or more epoxy groups in one molecule. Specific examples thereof 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, and pentaerythritol polyglycidyl ether.

[0101] Commercially available products include epoxy resins having at least two epoxy groups, YH-434 and YH434L (manufactured by Nippon Steel Chemical & Material Co., Ltd.); epoxy resins having a cyclohexene oxide structure, Epolead GT-401, GT-403, GT-301, GT-302, Celloxide 2021, and 3000 (manufactured by Daicel Corporation); bisphenol A type epoxy resins, jER1001, 1002, 1003, 1004, 1007, 1009, 1010, and 828 (all manufactured by Mitsubishi Chemical Co., Ltd.); and bisphenol F type epoxy resins. jER807 (manufactured by Mitsubishi Chemical Corporation), phenol novolac type epoxy resins jER152 and jER154 (both manufactured by Mitsubishi Chemical Corporation), EPPN201 and EPPN202 (both manufactured by Nippon Kayaku Co., Ltd.), cresol novolac type epoxy resins EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, and EOCN-1027 (both 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, and CY179 (all manufactured by CIBA-GEIGY Co., Ltd.), AG), Araldite CY-182, CY-192, and CY-184 (all manufactured by CIBA-GEIGY AG), Epiclon 200 and 400 (all manufactured by DIC Corporation), jER871 and jER872 (all manufactured by Mitsubishi Chemical Corporation), ED-5661 and ED-5662 (all 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, and EX-321 (manufactured by Nagase ChemteX Corporation) can also be used.

[0102] 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 thereof 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, polyglycerin monoethylene oxide, and the like. Examples of the polyacrylate include side polyacrylate, polyglycerin polyethylene glycol polyacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tricyclodecane dimethanol diacrylate, tricyclodecane dimethanol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, and polybasic acid-modified acrylic oligomers.

[0103] In addition, the polyfunctional (meth)acrylic compound is commercially available. Specific examples thereof 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, and BPE-5. 00, 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 (manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD (registered trademark) )DPEA-12, PEG400DA, THE-330, RP-1040 (manufactured by Nippon Kayaku Co., Ltd.), Aronix M-210, M-350 (manufactured by Toagosei Co., Ltd.), KAYARAD (registered trademark) DPHA, NPGDA, PET30 (manufactured by Nippon Kayaku Co., Ltd.), NK ester Examples of such compounds include A-DPH, A-TMPT, A-DCP, A-HD-N, TMPT, DCP, NPG, and HD-N (all manufactured by Shin-Nakamura Chemical Co., Ltd.), NK Oligo U-15HA (manufactured by Shin-Nakamura Chemical Co., Ltd.), NK Polymer Vanaresin GH-1203 (manufactured by Shin-Nakamura Chemical Co., Ltd.), and DN-0075 (manufactured by Nippon Kayaku Co., Ltd.). The polybasic acid-modified acrylic oligomer is also available as a commercial product, and specific examples thereof include Aronix M-510 and 520 (both manufactured by Toagosei Co., Ltd.).

[0104] The compound having an acid anhydride group is not particularly limited as long as it is a carboxylic acid anhydride obtained by dehydration condensation of two molecules of carboxylic acid, and specific examples thereof include compounds having one acid anhydride group in the molecule, such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, maleic anhydride, succinic anhydride, octyl succinic anhydride, and dodecenyl succinic anhydride; 1,2,3,4-cyclobutanetetracarboxylic dianhydride, pyromellitic anhydride, and 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene. Examples of the dianhydride include succinic dianhydride, bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic dianhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 1,2,3,4-butanetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, and 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, which have two acid anhydride groups in the molecule.

[0105] The compound containing a blocked isocyanate group is not particularly limited as long as it has two or more blocked isocyanate groups in one molecule, in which the isocyanate group (-NCO) is blocked with an appropriate protecting group, and when exposed to high temperatures during thermal curing, the protecting group (blocking moiety) is thermally dissociated and removed, and the resulting isocyanate group undergoes a crosslinking reaction with a crosslinking group (e.g., a hydroxy-containing group) of the triazine ring-containing polymer of the present invention. For example, a compound having two or more groups represented by the following formula in one molecule (note that these groups may be the same or different from each other) may be mentioned.

[0106] [ka] (In the formula, R b represents an organic group in the block portion.)

[0107] Such a compound 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 one molecule include polyisocyanates such as isophorone diisocyanate, 1,6-hexamethylene diisocyanate, methylene bis(4-cyclohexyl isocyanate), and trimethylhexamethylene diisocyanate, as well as dimers and trimers thereof, 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.

[0108] Compounds containing a blocked isocyanate group are also available as commercially available products. Specific examples thereof include Takenate (registered trademark) B-830, B-815N, B-842N, B-870N, B-874N, B-882N, B-7005, B-7030, B-7075, and B-5010 (all manufactured by Mitsui Chemicals, Inc.), Duranate (registered trademark) 17B-60PX, TPA-B80E, MF-B60X, MF-K60X, and E402-B80T (all manufactured by Asahi Kasei Corporation), Karenz MOI-BM (registered trademark) (all manufactured by Showa Denko K.K.), and TRIXENE (registered trademark). Examples include BI-7950, BI-7951, BI-7960, BI-7961, BI-7963, BI-7982, BI-7991, and BI-7992 (manufactured by Baxenden Chemicals LTD).

[0109] The aminoplast compound is not particularly limited as long as it has two or more methoxymethyl groups in one molecule, and examples thereof include melamine compounds such as the Cymel series, such as hexamethoxymethylmelamine CYMEL (registered trademark) 303, tetrabutoxymethylglycoluril 1170, and tetramethoxymethylbenzoguanamine 1123 (all manufactured by Nihon Cytec Industries Co., Ltd.), and the Nikalac series, such as methylated melamine resins Nikalac (registered trademark) MW-30HM, MW-390, MW-100LM, and MX-750LM, and methylated urea resins MX-270, MX-280, and MX-290 (all manufactured by Sanwa Chemical Co., Ltd.). The polyfunctional oxetane compound is not particularly limited as long as it has two or more oxetanyl groups in one molecule, and examples thereof include OXT-221, OX-SQ-H, and OX-SC (all manufactured by Toagosei Co., Ltd.), which contain oxetanyl groups.

[0110] The phenoplast compound has two or more hydroxymethyl groups in one molecule, and when exposed to high temperatures during heat curing, a crosslinking reaction proceeds through a dehydration condensation reaction between the phenoplast compound and the crosslinking groups of the triazine ring-containing polymer of the present invention. 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 as commercially available products, 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.).

[0111] Among these, polyfunctional (meth)acrylic compounds are preferred because they can suppress the decrease in refractive index caused by the incorporation of a crosslinking agent and because the curing reaction proceeds quickly. Among these, polyfunctional (meth)acrylic compounds having an isocyanuric acid skeleton as shown below are more preferred because they have excellent compatibility with the triazine ring-containing polymer. Examples of polyfunctional (meth)acrylic compounds having such a skeleton include NK Ester A-9300 and NK Ester A-9300-1CL (both manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0112] [ka] (In the formula, R 111 ~R 113 are each independently a monovalent organic group having at least one (meth)acrylic group at its terminal.

[0113] From the viewpoints of further improving the curing rate and enhancing the solvent resistance, acid resistance, and alkali resistance of the obtained cured film, it is preferable to use a polyfunctional (meth)acrylic compound 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 (hereinafter referred to as "low-viscosity crosslinking agent"), either alone or in combination of two or more kinds, or in combination with the above-mentioned polyfunctional (meth)acrylic compound having an isocyanuric acid skeleton. Such low-viscosity crosslinking agents are also commercially available. Examples of such crosslinking agents include those having a relatively long chain length between (meth)acrylic groups, such as 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 Co., Ltd.), among the above-mentioned polyfunctional (meth)acrylic compounds.

[0114] Furthermore, in order to improve 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 Co., Ltd.) and NK Ester ATM-35E (manufactured by Shin-Nakamura Chemical Co., Ltd.) in combination with the polyfunctional (meth)acrylic compound having an isocyanuric acid skeleton.

[0115] In addition, when a thin film made of the triazine ring-containing polymer of the present invention is laminated on a protective film such as a PET or polyolefin film and light is irradiated through the protective film, the thin film laminated film can also obtain good curability without being inhibited by oxygen. 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 gives a thin film with good peelability.

[0116] The crosslinking agent may be used alone or in combination of two or more. The amount of the crosslinking agent is preferably 1 to 100 parts by mass relative to 100 parts by mass of the triazine ring-containing polymer, but considering the solvent resistance, the lower limit is preferably 2 parts by mass, more preferably 5 parts by mass, and further, considering the control of the refractive index, the upper limit is preferably 20 parts by mass, more preferably 15 parts by mass.

[0117] The composition of the present invention can also contain an initiator according to each crosslinking agent. As described above, when a polyfunctional epoxy compound and / or a polyfunctional (meth)acrylic compound is used as a crosslinking agent, photocuring proceeds without the use of an initiator to give a cured film, but in this case, an initiator may be used.

[0118] When a polyfunctional epoxy compound is used as a crosslinking agent, a photoacid generator or a photobase generator can be used. The photoacid generator may be appropriately selected from known ones and used. For example, onium salt derivatives such as diazonium salts, sulfonium salts and iodonium salts can be used. Specific examples thereof include aryl diazonium salts such as phenyl diazonium hexafluorophosphate, 4-methoxyphenyl diazonium hexafluoroantimonate, and 4-methylphenyl diazonium hexafluorophosphate; diaryliodonium salts such as diphenyl iodonium hexafluoroantimonate, di(4-methylphenyl)iodonium hexafluorophosphate, and di(4-tert-butylphenyl)iodonium hexafluorophosphate; triphenylsulfonium hexafluoroantimonate, tris(4-methoxyphenyl)sulfonium hexafluorophosphate, diphenyl-4-thiophenoxyphenylsulfonium hexafluoroantimonate, and diphenyl-4-thiophenoxyphenylsulfonium hexafluorophosphate. triarylsulfonium salts such as 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-di(4-fluorophenyl)sulfonium hexafluorophosphate.

[0119] These onium salts may be commercially available products, and specific examples thereof include San-Aid SI-60, SI-80, SI-100, SI-60L, SI-80L, SI-100L, SI-L145, SI-L150, SI-L160, SI-L110, and SI-L147 (all manufactured by Sanshin Chemical Industry Co., Ltd.), UVI-6950, UVI-6970, UVI-6974, UVI-6990, and UVI-6992 (all manufactured by Union Carbide Corporation), CPI-100P, CPI-100A, CPI-200K, and CPI-200S (all manufactured by San-Apro Co., Ltd.), Adeka Optomer SP-150, SP-151, SP-170, and SP-171 (all manufactured by Asahi Denka Kogyo Co., Ltd.), and 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 Sartomer), 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 of such binders 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.), and the like.

[0120] On the other hand, the photobase generator may be appropriately selected from known ones, and for example, Co-amine complex-based, oxime carboxylate-based, carbamate-based, and quaternary ammonium salt-based photobase generators may be used. Specific examples thereof include 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-carbamoylhydroxylamide, O-carbamoyloxime, [[(2,6-dinitrobenzyl)oxy]carbonyl]cyclohexylamine, bis[[(2-nitrobenzyl)oxy]carbonyl]hexane 1,6-diamine, 4-(methylthiobenzoyl)-1-methyl-1-morpholinoethane, (4-morpholinobenzoyl)-1-benzyl-1-dimethyla amminecobalt(III) tris(triphenylmethylborate), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2,6-dimethyl-3,5-diacetyl-4-(2'-nitrophenyl)-1,4-dihydropyridine, 2,6-dimethyl-3,5-diacetyl-4-(2',4'-dinitrophenyl)-1,4-dihydropyridine, and the like. Moreover, the photobase generator may be a commercially available product, specific examples of which include TPS-OH, NBC-101, and ANC-101 (all product names, manufactured by Midori Kagaku Co., Ltd.).

[0121] When a photoacid or base generator is used, it is preferably used in the range of 0.1 to 15 parts by mass, more preferably 1 to 10 parts by mass, per 100 parts by mass of the polyfunctional epoxy compound. If necessary, an epoxy resin curing agent may be added in an amount of 1 to 100 parts by mass based on 100 parts by mass of the polyfunctional epoxy compound.

[0122] On the other hand, when a polyfunctional (meth)acrylic compound is used, a photoradical polymerization initiator can be used. The photoradical polymerization initiator may be appropriately selected from known initiators, and examples thereof include acetophenones, benzophenones, Michler's benzoyl benzoate, 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: Takasuki Kazuhiro, publisher: Technical Information Association Co., Ltd., published in 1991). Examples of commercially available photoradical polymerization initiators include those manufactured by BASF under the trade names Irgacure 127, 184, 369, 379, 379EG, 651, 500, 754, 819, 903, 907, 784, 2959, CGI1700, CGI1750, CGI1850, CG24-61, OXE01, OXE02, Darocur 1116, 1173, MBF, those manufactured by BASF under the trade name Lucirin TPO, those manufactured by UCB under the trade name Ubecryl P36, and those manufactured by Fratelli Lamberti under the trade name Ezacure KIP150, KIP65LT, KIP100F, KT37, KT55, KTO46, KIP75 / B. When a photoradical polymerization initiator is used, it is preferably used in the range of 0.1 to 200 parts by mass, and more preferably 1 to 150 parts by mass, per 100 parts by mass of the polyfunctional (meth)acrylate compound.

[0123] Furthermore, a polyfunctional thiol compound having two or more mercapto groups in the molecule may be added to the composition of the present invention for the purpose of promoting the reaction between the triazine ring-containing polymer and the crosslinking agent. Specifically, a polyfunctional thiol compound represented by the following formula is preferred.

[0124] [ka]

[0125] The above L represents a divalent to tetravalent organic group, preferably a divalent to tetravalent aliphatic group having 2 to 12 carbon atoms or a divalent to tetravalent heterocycle-containing group, and more preferably 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: The above n represents an integer of 2 to 4 corresponding to the valence of L.

[0126] [ka] (In the formula, "." represents a bond to an oxygen atom.)

[0127] Specific 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), trimethylolpropane tris(3-mercaptobutyrate), trimethylolethane tris(3-mercaptobutyrate), and the like. These polyfunctional thiol compounds are also available as commercial products, and examples thereof include KarenzMT-BD1, KarenzMT NR1, KarenzMT PE1, TPMB, and TEMB (all manufactured by Showa Denko KK). These polyfunctional thiol compounds may be used alone or in combination of two or more.

[0128] When a polyfunctional thiol compound is used, the amount added is not particularly limited as long as it does not adversely affect the thin film obtained, but in the present invention, the amount is preferably 0.01 to 10 mass %, and more preferably 0.03 to 6 mass %, based on 100 mass % of the solid content.

[0129] It is preferable to add various solvents to the composition of the present invention to dissolve the triazine ring-containing polymer before use. Examples of the solvent include water, toluene, p-xylene, o-xylene, m-xylene, ethylbenzene, styrene, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol methyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, diethylene glycol diethyl ether, 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, cyclohexanol, diacetone alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, propylene glycol, benzyl alcohol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, γ-butyrolactone, acetone, methyl ethyl ketone, methyl isopropyl ketone, diethyl ketone, methyl isobutyl ketone, methyl normal butyl ketone, cyclopentanone, cyclohexanone, ethyl acetate, isopropyl acetate, normal propyl acetate propyl, isobutyl acetate, normal butyl acetate, ethyl lactate, methanol, ethanol, isopropanol, tert-butanol, allyl alcohol, normal propanol, 2-methyl-2-butanol, isobutanol, normal butanol, 2-methyl-1-butanol, 1-pentanol, 2-methyl-1-pentanol, 2-ethylhexanol, 1-methoxy-2-propanol, tetrahydrofuran, 1,4-dioxane, N,N-dimethylformamide, N,N-dimethylacetamide (DMAc), N-methylpyrrolidone, 1,Examples of the dimethyl ether include 3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, and N-cyclohexyl-2-pyrrolidinone. These may be used alone or in combination of two or more.

[0130] As described above, 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, normal propyl acetate, isopropyl acetate, methyl lactate, ethyl lactate, and butyl lactate, and is particularly suitable for forming a thin film in a portion where these solvents are required.

[0131] In this case, the solid content concentration in the composition is not particularly limited as long as it is within a range that does not affect storage stability, and may be appropriately set according to the intended thickness of the film. Specifically, from the viewpoints of solubility and storage stability, the solid content concentration is preferably 0.1 to 50 mass%, more preferably 0.1 to 40 mass%.

[0132] The composition of the present invention may contain other components other than the triazine ring-containing polymer, crosslinking agent and solvent, such as additives such as a leveling agent, a surfactant and a silane coupling agent, as long as the effects of the present invention are not impaired. Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkyl aryl 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 such as restearate, trade names: F-TOP EF301, EF303, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd. (formerly JEMCO Co., Ltd.)), trade names: Megafac F171, F173, R-08, R-30, R-40, F-553, F-554, RS-75, RS-72-K (manufactured by DIC Corporation), Fluorad FC430, FC431 (manufactured by Sumitomo 3M Limited), trade name: Asahi Fluorine-based surfactants such as Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, and SC106 (manufactured by AGC Corporation), 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 BYK Japan KK), etc.

[0133] 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 even more preferably 0.01 to 0.5 parts by mass, based on 100 parts by mass of the triazine ring-containing polymer.

[0134] The film-forming composition of the present invention can be applied to a substrate, and then heated, if necessary, to evaporate the solvent, and then heated or irradiated with light to form a desired cured film. The composition may be applied by any method, and examples of the method that can be used include spin coating, dipping, flow coating, inkjet coating, jet dispenser coating, spraying, bar coating, gravure coating, slit coating, roll coating, transfer printing, brush coating, blade coating, and air knife coating.

[0135] Examples of the substrate include substrates made of silicon, glass coated with indium tin oxide (ITO), glass coated with indium zinc oxide (IZO), metal nanowires, polyethylene terephthalate (PET), plastic, glass, quartz, ceramics, etc., and flexible substrates having flexibility can also be used. The baking temperature is not particularly limited as long as it is for the purpose of evaporating the solvent, and the baking can be performed at, for example, 110 to 400°C. The baking method is not particularly limited, and may be, for example, evaporation using a hot plate or oven in a suitable atmosphere such as air, an inert gas such as nitrogen, or a vacuum. The baking temperature and baking time may be selected according to the process steps of the target electronic device, and baking conditions may be selected such that the physical properties of the resulting film meet the required characteristics of the electronic device. The conditions for light irradiation are not particularly limited, and appropriate irradiation energy and time may be selected depending on the triazine ring-containing polymer and crosslinking agent used.

[0136] The thin film or cured film of the present invention obtained as described above can achieve high heat resistance, high refractive index, and low volume shrinkage, and can therefore be suitably used in the fields of electronic devices and optical materials, such as as a part of the materials used in producing liquid crystal displays, organic EL elements (organic EL displays and organic EL lighting), touch panels, optical semiconductor (LED) elements, solid-state imaging elements, organic thin-film solar cells, dye-sensitized solar cells, organic thin-film transistors (TFTs), lenses, prism cameras, binoculars, microscopes, semiconductor exposure devices, etc. In particular, thin films and cured films prepared from the composition of the present invention have high transparency and a high refractive index, and therefore when used as a planarizing film or light-scattering layer in organic EL lighting, the light extraction efficiency (light diffusion efficiency) can be improved as well as the durability.

[0137] When the composition of the present invention is used in the light scattering layer of an organic EL lighting device, the light diffusing agent may be a known light diffusing agent, and is not particularly limited. These may be used alone, or two or more of the same type may be used in combination, or two or more of different types may be used in combination.

[0138] The light diffusing agent may be, for example, an organic light diffusing agent. Examples of organic light diffusing agents include crosslinked polymethyl methacrylate (PMMA) particles, crosslinked polymethyl acrylate particles, crosslinked polystyrene particles, crosslinked 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 be surface-treated with an appropriate surface modifier. EXAMPLES

[0139] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples. The measuring devices used in the examples are as follows. [ 1 H-NMR] Equipment: Bruker NMR System AVANCE III HD 500(500MHz) Measurement solvent: DMSO-d6 Reference material: tetramethylsilane (TMS) (δ 0.0 ppm) [GPC] Apparatus: Tosoh Corporation HLC-8200 GPC Column: Tosoh TSKgel α-3000 + Tosoh TSKgel α-4000 Column temperature: 40℃ Solvent: Dimethylformamide (DMF) Detector: UV (271 nm) Calibration curve: Standard polystyrene [Ellipsometer] Equipment: J.A. Woollam Japan Multi-angle Spectroscopic Ellipsometer VASE [Spectrophotometer] Equipment: Konica Minolta CM-3700A [Optical microscope] Equipment: OLYMPUS BX51 manufactured by Olympus Optical Co., Ltd.

[0140] [1] Synthesis of triazine ring-containing polymers [Example 1-1] Synthesis of polymer compound [5] [ka]

[0141] In a 3,000 mL four-neck flask, 9,9-bis(4-aminophenyl)fluorene [2] (264.53 g, 0.759 mol, JFE Chemical Co., Ltd.) and 2,022.64 g of dimethylacetamide (DMAc, Kanto Chemical Co., Ltd.) were added, and the atmosphere was replaced with nitrogen. The mixture was then stirred to dissolve 9,9-bis(4-aminophenyl)fluorene [2] in DMAc. The mixture was then cooled to -10°C in an ethanol-dry ice bath, and 2,4,6-trichloro-1,3,5-triazine [1] (140.00 g, 0.759 mol, Tokyo Chemical Industry Co., Ltd.) was added while making sure that the internal temperature did not rise above 0°C. After stirring for 30 minutes, the reaction solution was added with 2,022.64 g of DMAc in advance, and after nitrogen replacement, the oil bath was set to 90-100 ° C., and the internal temperature was dropped into a 5,000 mL four-neck flask so that it was 70 ° C. ± 5 ° C. After stirring at an internal temperature of 70 ° C. for 1 hour, 4-trifluoromethylaniline [3] (122.32 g, 0.759 mol, Tianjin Jiahan Chemical Co., Ltd.) and 2-(4-aminophenyl)ethanol [4] (104.14 g, 0.759 mol, Sugai Chemical Industry Co., Ltd.) were dissolved in 208.29 g of DMAc in advance and dropped, and stirred for 3 hours. After that, the temperature was lowered to room temperature, n-propylamine (134.63 g, Tokyo Chemical Industry Co., Ltd.) was dropped, and after stirring for 30 minutes, the stirring was stopped. The reaction solution was dropped into ion-exchanged water (7,027 g) containing 501.9 g of ammonium acetate to cause reprecipitation. The precipitate was filtered off and redissolved in THF (3,585 g), and ammonium acetate (209 g) and ion-exchanged water (149 g) were added to the solution and stirred for 30 minutes. After stirring was stopped, 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 dropped into a mixture of methanol (2,008 g) and ion-exchanged water (5,019 g) to cause reprecipitation again. The obtained precipitate was filtered off and dried in a vacuum dryer at 120°C for 8 hours to obtain 424.3 g of the desired polymer compound [5] (hereinafter referred to as P-1). The amount of compound P-1 was 1.0 g. 1 The results of H-NMR spectrum measurement are shown in FIG. The weight average molecular weight Mw of compound P-1 measured by GPC in terms of polystyrene was 7,700, and the polydispersity Mw / Mn was 2.7.

[0142] [Example 1-2] Synthesis of polymer compound [6] [ka]

[0143] In a 150 mL four-neck flask, 20.0 g of P-1 synthesized in Example 1-1, 100.0 g of tetrahydrofuran (THF, manufactured by Junsei Chemical Co., Ltd.), and 2.58 g of pure water were added, and the mixture was replaced with nitrogen, and then stirred to dissolve P-1 in THF. The temperature was then raised to 60° C., and 3.38 g of 2-isocyanatoethyl acrylate (Karenz AOI, manufactured by Showa Denko K.K.) was added and stirred for 3 hours. The temperature was then lowered to room temperature, and the reaction solution was dropped into a mixture of methanol (189 g) and ion-exchanged water (113 g) to cause reprecipitation. The resulting precipitate was filtered and dried in a vacuum dryer at 80° C. for 3 hours, to obtain 17.9 g of the target polymer compound [6] (hereinafter referred to as P-2). The amount of compound P-2 was 1.0 g. 1 The results of H-NMR spectrum measurement are shown in FIG. The weight average molecular weight Mw of compound P-2 measured by GPC in terms of polystyrene was 6,140, ​​and the polydispersity Mw / Mn was 2.4.

[0144] [Example 1-3] Synthesis of polymer compound [9] [ka]

[0145] In a 1,000 mL four-neck flask, 4,4'-diphenylaminosulfone [7] (53.86 g, 0.217 mol, Mitsui Fine Chemicals Co., Ltd.) and 525.61 g of dimethylacetamide (DMAc, Kanto Chemical Co., Ltd.) were added, and after nitrogen replacement, 4,4'-diphenylaminosulfone [7] was dissolved in DMAc by stirring. Then, it was cooled to -10 ° C in an ethanol-dry ice bath, and 2,4,6-trichloro-1,3,5-triazine [1] (40.00 g, 0.217 mol, Tokyo Chemical Industry Co., Ltd.) was added while making sure that the internal temperature did not exceed 0 ° C. After stirring for 30 minutes, the reaction vessel was transferred to an oil bath set at 90-100 ° C, and the reaction solution was heated until the internal temperature reached 85 ± 5 ° C. After stirring for 1 hour, 2-(4-aminophenyl)ethanol [4] (44.63 g, 0.325 mol, Oakwood Chemical) and 3-trifluoromethylaniline [8] (17.47 g, 0.108 mol, Tokyo Chemical Industry Co., Ltd.) dissolved in 98.55 g of dimethylacetamide were added dropwise and stirred for 3 hours. Then, 2-aminoethanol (39.75 g, Tokyo Chemical Industry Co., Ltd.) was added dropwise, cooled to room temperature, stirred for 30 minutes, and then the stirring was stopped. THF (426 g), ammonium acetate (298 g) and ion-exchanged water (298 g) were added to the reaction solution and stirred for 30 minutes. After stirring was stopped, the solution was transferred to a separatory funnel, separated into an organic layer and an aqueous layer, and the organic layer was collected. The collected organic layer was added dropwise to a mixture of methanol (426 g) and ion-exchanged water (853 g) to cause reprecipitation. The resulting precipitate was filtered and dried in a vacuum dryer at 120°C for 8 hours to obtain 103.6 g of the target polymer compound [9] (hereinafter referred to as P-3). 1 The results of H-NMR spectrum measurement are shown in FIG. The weight average molecular weight Mw of compound P-3 measured by GPC in terms of polystyrene was 11,070, and the polydispersity Mw / Mn was 3.2.

[0146] [Comparative Example 1-1] Synthesis of polymer compound

[11] [ka]

[0147] In a 1,000mL four-neck flask, 9,9-bis(4-aminophenyl)fluorene [2] (45.35g, 0.130mol, JFE Chemical Co., Ltd.) and 346.74g of dimethylacetamide (DMAc, Kanto Chemical Co., Ltd.) were added, and after replacing with nitrogen, the flask was stirred to dissolve 9,9-bis(4-aminophenyl)fluorene [2] in DMAc. The flask was then cooled to -10°C in an ethanol-dry ice bath, and 2,4,6-trichloro-1,3,5-triazine [1] (24.00g, 0.130mol, Tokyo Chemical Industry Co., Ltd.) was added while making sure that the internal temperature did not rise above 0°C. After stirring for 30 minutes, the reaction solution was added to 346.74 g of DMAc in advance, and after replacing with nitrogen, the oil bath was set to 90-100 ° C., and the internal temperature was dropped into a 1,000 mL four-neck flask so that it was 85 ° C. ± 5 ° C. After stirring for 1 hour at an internal temperature of 85 ° C., aniline

[10] (36.36 g, 0.390 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) was dropped and stirred for 3 hours. Then, the temperature was lowered to room temperature, n-propylamine (23.08 g, manufactured by Tokyo Chemical Industry Co., Ltd.) was dropped, and after stirring for 30 minutes, the stirring was stopped. The reaction solution was dropped into ion-exchanged water (2,056 g) to which 28.8 g of ammonium acetate had been added to cause reprecipitation. The precipitate was filtered off and redissolved in THF (556 g). To the solution, 25% aqueous ammonia (92.6 g), ammonium acetate (46.3 g) and ion-exchanged water (138.9 g) were added and stirred for 30 minutes. After stirring was stopped, the solution was transferred to a separatory funnel and separated into an organic layer and an aqueous layer, and the organic layer was collected. The collected organic layer was dropped into a mixture of methanol (740 g) and ion-exchanged water (1,702 g) to cause reprecipitation again. The obtained precipitate was filtered off and dried in a vacuum dryer at 120°C for 8 hours to obtain 47.4 g of the target polymer compound

[11] (hereinafter referred to as P-4). The amount of compound P-4 was 1.0 g. 1 The results of H-NMR spectrum measurement are shown in FIG. The weight average molecular weight Mw of compound P-4 measured by GPC in terms of polystyrene was 6,050, and the polydispersity Mw / Mn was 2.6.

[0148] [2] Confirmation of solubility [Example 2-1] When P-1 (2.5 g) obtained in Example 1-1 was dissolved in propylene glycol monomethyl ether (hereinafter abbreviated as PGME) (10.0 g), propylene glycol monomethyl ether acetate (hereinafter abbreviated as PGMEA) (10.0 g), and cyclopentanone (hereinafter abbreviated as CPN) (10.0 g), it was dissolved in each solvent, and a uniform varnish was obtained.

[0149] [Comparative Example 2-1] When P-4 (2.5 g) obtained in Comparative Example 1-1 was dissolved in PGME (10.0 g), PGMEA (10.0 g), and CPN (10.0 g), it dissolved only in CPN and did not dissolve in PGME or PGMEA.

[0150] [3] Preparation of film-forming composition and production of coating [Example 3-1] P-1 (2.5 g) obtained in Example 1-1 was dissolved in CPN (2.5 g) to prepare a uniform and transparent varnish (hereinafter referred to as P-1 solution). The obtained P-1 solution was spin-coated onto a 50 mm × 50 mm × 0.7 t alkali-free glass substrate using a spin coater aiming for 500 nm, pre-baked on a hot plate at 100°C for 1 minute, and then baked at 250°C for 5 minutes to obtain a coating (hereinafter referred to as P-1 film).

[0151] [Comparative Example 3-1] A coating (hereinafter referred to as P-2 coating) was obtained in the same manner as in Example 3-1, except that P-4 was used instead of P-1.

[0152] The refractive index and thickness of the coatings prepared in Example 3-1 and Comparative Example 3-1 are shown in Table 1.

[0153] [Table 1]

[0154] From Example 2-1, Comparative Example 2-1, and Table 1, it can be seen that the thin film prepared from the polymer compound obtained in Example 1-1 has a refractive index exceeding 1.71 while improving the solubility in organic solvents.

[0155] [4] Preparation of film-forming composition with added crosslinking agent and production of cured film [Example 4-1] To the PGMEA solution (12.49 g) of P-1 prepared in Example 2-1, 0.71 g of a 70 mass% PGME solution of blocked isocyanate (BI7992, 1,500 mPa s, manufactured by BAXENDEN) as a crosslinking agent, 0.12 g of a 1 mass% PGMEA solution of Megafac F-563 (manufactured by DIC Corporation) as a surfactant, 4.97 g of PGMEA, and 1.70 g of THFA were added, and dissolution was confirmed visually to prepare a varnish with a solid content of 15 mass% (hereinafter referred to as SP-1 solution). This SP-1 solution was spin-coated onto a 50 mm x 50 mm x 0.7 t alkali-free glass substrate using a spin coater at 200 rpm for 5 seconds and at 1,000 rpm for 30 seconds, pre-dried using a hot plate at 100°C for 1 minute, and then baked at 250°C for 5 minutes to obtain a cured film (hereinafter referred to as SP-1 film).

[0156] [Comparative Example 4-1] To the CPN solution (12.49 g) of P-4 prepared in Comparative Example 2-1, 0.71 g of a 70 mass% PGME solution of blocked isocyanate (BI7992, 1,500 mPa s, manufactured by BAXENDEN) as a crosslinking agent, 0.12 g of a 1 mass% PGMEA solution of Megafac R-40 (manufactured by DIC Corporation) as a surfactant, and 6.67 g of CPN were added, and dissolution was confirmed visually to prepare a varnish with a solid content of 15 mass% (hereinafter referred to as SP-2 solution). This SP-2 solution was spin-coated onto a 50 mm x 50 mm x 0.7 t alkali-free glass substrate using a spin coater at 200 rpm for 5 seconds and at 1,000 rpm for 30 seconds, pre-dried using a hot plate at 100°C for 1 minute, and then baked at 250°C for 5 minutes to obtain a cured film (hereinafter referred to as SP-2 film).

[0157] The refractive index, thickness and b * Furthermore, the yellowing resistance and solvent resistance of the cured film were confirmed by the following procedure.

[0158] [Yellowing resistance] The yellowing resistance was evaluated by annealing the obtained cured film at 250°C for 180 minutes, and then measuring the refractive index, film thickness and b * The yellowing resistance was measured by comparing the results before and after annealing. * The smaller the increase in this value, the higher the yellowing resistance can be evaluated. The results are shown in Table 2.

[0159] [Table 2]

[0160] From Table 2, it can be seen that the cured film of Example 4-1 (SP-1 film) has excellent heat yellowing resistance while maintaining a high refractive index.

[0161] [Solvent resistance (crack resistance)] The substrate with the cured film prepared above was set on a spin coater and 1 ml of CPN was applied. Next, the substrate was rotated at 50 rpm for 60 seconds to expose the cured film to the solvent so that the liquid would not splash from the substrate. Then, the substrate was rotated at 1,000 rpm for 30 seconds to remove the solvent from the substrate. Finally, the substrate was dried at 120°C for 10 seconds using a hot plate, after which the refractive index and film thickness were measured, the remaining film rate was calculated, and the film surface was observed using an optical microscope. The remaining film rate was calculated by the following formula. Remaining film rate (%) = (film thickness after exposure to solvent) ÷ (film thickness before exposure to solvent) × 100 The results of the refractive index, film thickness measurement and film remaining rate are shown in Table 3, a micrograph of the cured film surface of Example 4-1 is shown in FIG. 5, and a micrograph of the cured film surface of Comparative Example 4-1 is shown in FIG.

[0162] [Table 3]

[0163] From Table 3, it can be seen that the cured film (SP-1 film) of Example 4-1 had a high film remaining rate, and from FIG. 5, it can be seen that no film roughness or cracks occurred, and thus it is understood that it has excellent solvent resistance (crack resistance). On the other hand, the cured film of Comparative Example 4-1 (SP-2 film) showed film roughness and cracks when it was dried at 120°C for 10 seconds using a hot plate after exposure to the solvent (see Figure 6), and the refractive index and film thickness were not in a condition to be measured. These results show that the cured film prepared from the polymer compound obtained in Example 1-1 maintains a high refractive index and also has excellent solvent resistance (crack resistance).

Claims

1. A triazine ring-containing polymer comprising a repeating unit structure represented by the following formula (1), having at least one triazine ring terminal, at least a portion of which is terminated with an arylamino group having a fluorine atom-containing arylamino group and a crosslinking group, and the crosslinking group is a hydroxyalkyl group or a (meth)acryloyl-containing group: 【Chemistry 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; Ar represents at least one selected from the group represented by formulas (2) to (13). 【Chemistry 2】 [In the formula, R １ ~R ９２ each independently represents a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms; R ９３ and R ９４ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, W １ and W. ２ are each independently a single bond, CR ９５ R ９６ (R ９５ and R ９６ each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms (which may be joined together to form a ring). ), C=O, O, S, SO, SO ２ , or N.R. ９７ (R ９７ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a phenyl group; X １ and X ２ are each independently a single bond, an alkylene group having 1 to 10 carbon atoms, or a group represented by the formula (14): 【Chemistry 3】 (In the formula, R ９８ ~R １０１ each independently represents a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms; Y １ and Y ２ each independently represents a single bond or an alkylene group having 1 to 10 carbon atoms.

2. The R １ ~R ９２ and R ９８ ~R １０１ 2. The triazine ring-containing polymer according to claim 1, wherein is a hydrogen atom.

3. 3. The triazine ring-containing polymer according to claim 1, wherein the fluorine atom-containing arylamino group is represented by formula (15): 【Chemistry 4】 (In the formula, R １０２ represents a fluorine atom or a fluoroalkyl group having 1 to 10 carbon atoms.

4. 4. The triazine ring-containing polymer according to claim 3, wherein the fluorine atom-containing arylamino group is represented by formula (16) or (17). 【Chemistry 5】 (In the formula, R １０２ has the same meaning as above.)

5. The R １０２ 5. The triazine ring-containing polymer according to claim 3, wherein R is a perfluoroalkyl group having 1 to 10 carbon atoms.

6. The triazine ring-containing polymer according to any one of claims 1 to 5, wherein the arylamino group having a crosslinking group is represented by formula (18): 【Chemistry 6】 (In the formula, R １０３ represents a bridging group.)

7. The triazine ring-containing polymer according to claim 6, wherein the arylamino group having a crosslinking group is represented by formula (19): 【Chemistry 7】 (In the formula, R １０３ has the same meaning as above.)

8. 2. 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): 【Chemistry 8】 (In the formula, A １ represents an alkylene group having 1 to 10 carbon atoms; ２ represents a single bond or the following formula (j): 【Chemistry 9】 A represents a group represented by the formula: ３ represents a divalent or trivalent aliphatic hydrocarbon group which may be substituted with a hydroxy group; A ４ represents a hydrogen atom or a methyl group, a represents 1 or 2, and * represents a bond.

9. The triazine ring-containing polymer according to claim 1, wherein the crosslinking group is at least one selected from a hydroxymethyl group, a 2-hydroxyethyl group, a (meth)acryloyloxymethyl group, a (meth)acryloyloxyethyl group, and groups represented by the following formulas (i-2) to (i-5): 【Chemistry 10】 (In the formula, * represents a bond.)

10. The triazine ring-containing polymer according to any one of claims 1 to 9, wherein Ar is represented by formula (20) or (21). 【Chemistry 11】

11. A film-forming composition comprising the triazine ring-containing polymer according to any one of claims 1 to 10 and an organic solvent.

12. 12. The film forming composition according to claim 11, wherein the organic solvent comprises at least one selected from the group consisting of glycol ester solvents, ketone solvents, and ester solvents.

13. The film forming composition according to claim 11 or 12, further comprising a crosslinking agent.

14. The film forming composition according to claim 13, wherein the crosslinking agent is a polyfunctional (meth)acrylic compound.

15. A thin film obtained from the film forming composition according to any one of claims 11 to 14.

16. An electronic device comprising a substrate and the thin film according to claim 15 formed on the substrate.

17. An optical member comprising a substrate and the thin film according to claim 15 formed on the substrate.

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