阅读说明：本技术 含三嗪环的聚合物、树脂组合物、固化膜及固体摄像元件 (Triazine ring-containing polymer, resin composition, cured film, and solid-state imaging element ) 是由 日比野利保 的羽良典 诹访充史 于 2019-03-18 设计创作，主要内容包括：本发明的目的在于提供即使不添加金属氧化物也能单独利用聚合物达成高耐热性、高折射率并且对热、湿度的长期稳定性优异的含三嗪环的聚合物以及包含该聚合物的膜形成用组合物。本发明为含三嗪环的聚合物,其特征在于,包含下述式(1)所示的重复单元结构。<Image he="299" wi="531" file="DDA0002692802240000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The purpose of the present invention is to provide a triazine ring-containing polymer that can achieve high heat resistance and high refractive index by using the polymer alone without adding a metal oxide, and that has excellent long-term stability against heat and humidity, and a film-forming composition containing the polymer. The present invention is a triazine ring-containing polymer characterized by containing a repeating unit structure represented by the following formula (1).)

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

[ chemical formula 1]

In which X and Y are-S-or-NR¹-，R¹Is a hydrogen atom or an organic group; n is an integer of 1 or more; z¹Represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, an acetyl group, a combination of 1 or more of these groups, or a single bond, -S-, -O-, -NR²A combination of at least 1 of- (CO) -NH-, - (CO) -O-and- (CO) -; z¹May further have a substituent R²Is a hydrogen atom or an organic group; z²Represents an aliphatic hydrocarbon group, an aryl group, a heterocyclic group, or a combination of 1 or more of them, or comprises a combination of these groups and one or more of-S-, -SO-, -C-O-groups₂-、-O-、-NR³A combination of 1 or more of-, - (CO) -NH-, - (CO) -O-, - (CO) -and-NH- (CO) -NH-; z²May further have a substituent R³Is a hydrogen atom or an organic group.

2. The triazine ring-containing polymer according to claim 1, wherein Z is²Represents at least 1 selected from the group represented by the following general formulae (2) to (10),

[ chemical formula 2]

Wherein, represents a bond directly bonded to Y; w¹～W³Is a single bond, -CR⁶⁸R⁶⁹-, -O-or-S-, R⁶⁸And R⁶⁹Is a hydrogen atom, an aryl group, a heterocyclic group or a hydrocarbon group having 1 to 10 carbon atoms; r⁴～R⁶⁷Independently of one another, represent an organic group; w⁴Represents a single bond, -S-, -SO₂-、-O-、-NR³-, - (CO) -NH-, -NH- (CO) -, - (CO) -O-, - (CO) -, -O- (CO) -and-NH- (CO) -NH-, W⁵And W⁶Independently of one another, represents a single bond, -CR⁷⁰R⁷¹-(R⁷⁰And R⁷¹Independently of each other, a hydrogen atom or an organic group), - (CO) -, -O-, -S-, - (SO) -, -SO₂-；W⁷～W⁹Is a single bond, -O-, -S-or-NR⁷²-，R⁷²Is a hydrogen atom or an organic group; w¹⁰Is N or a group represented by the following general formula (11),

[ chemical formula 3]

R⁷³Represents a hydrogen atom or an organic group.

3. The triazine ring-containing polymer according to claim 2, wherein Z is²Represented by any one of (12), (13) or (14),

[ chemical formula 4]

4. The triazine ring-containing polymer according to any one of claims 1 to 3, which has a partial structure represented by the following general formulae (15) to (17),

[ chemical formula 5]

In the formula, R⁷⁴Is a substituent having 1 or more of arbitrary alkoxysilyl group, hydroxysilyl group and hydrosilyl group, and is a linking group directly linked to Y in the formula (1).

5. A resin composition comprising the triazine ring-containing polymer according to any one of claims 1 to 4.

6. A cured film obtained from the resin composition according to claim 5.

7. A solid-state imaging element comprising the cured film according to claim 6.

Technical Field

The present invention relates to a resin composition containing a triazine ring-containing polymer, a cured film of the resin composition, a method for producing the cured film, and a substrate and a solid-state imaging element provided with the cured film.

Background

In recent years, with the rapid progress of digital cameras, mobile phones with cameras, and the like, there has been a demand for a solid-state imaging device having a smaller size and higher pixel density. Since the reduction in the size of the solid-state imaging element causes a decrease in sensitivity, studies have been made to prevent the decrease in sensitivity by improving the light collection efficiency. Specifically, a method of disposing a microlens for condensing light on the color filter is adopted.

As a general method for manufacturing a microlens, a method of processing a resin film by dry etching is generally used. As the material of the resin film, organic materials such as polystyrene and acrylic are often used, and the refractive index thereof is 1.5 to 1.6, and in order to further improve the light condensing performance, it is required to increase the refractive index of the lens.

In order to increase the refractive index of the lens material, various attempts have been made to increase the refractive index of the polymer compound, and the introduction of metal oxide particles, aromatic groups, halogen atoms, and hetero atoms has been studied. For example, a method of mixing a siloxane polymer with metal oxide particles of titanium oxide, zirconium oxide, or the like is known as the most effective method for increasing the refractive index (patent document 1).

On the other hand, it is also known that the flexibility and crack resistance of the cured film may be impaired by the introduction of a metal oxide, and that a triazine ring polymer having a high refractive index can be obtained without introducing a metal oxide (patent document 2). Such polymers do not contain metal oxides and exhibit high refractive indices using the polymers alone. Therefore, even when a dry process such as etching or ashing is performed, the etching rate is constant, a coating film having a uniform thickness can be obtained, and the process margin in the device fabrication is increased.

Although having such advantages, the triazine ring polymer is poor in heat resistance, and a decrease in transmittance due to coloring is observed in a microlens formation step and subsequent steps, and thus it is difficult to use the polymer without mixing a stabilizer such as an antioxidant. The triazine ring polymer described in patent document 3 has improved heat resistance by introducing an aromatic ring having high heat resistance.

However, triazine ring polymers as disclosed in patent document 3 have a problem of a decrease in transmittance in a durability test at high temperature and high humidity required for electronic devices such as solid-state imaging devices and organic Electroluminescence (EL) displays.

Disclosure of Invention

Problems to be solved by the invention

The present invention has been made in view of such circumstances, and an object thereof is to provide a triazine ring-containing polymer that is less in decrease in transmittance in a durability test under high temperature and high humidity, and a resin composition containing the polymer.

Means for solving the problems

A triazine ring-containing polymer characterized by containing a repeating unit structure represented by the following formula (1), and a resin composition containing the polymer.

[ chemical formula 1]

In which X or Y is-S-or-NR¹-，R¹Is a hydrogen atom or an organic group. n is an integer of 1 or more. Z¹Represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, an acetyl group, a combination of 1 or more of these groups, or a single bond, -S-, -O-, -NR²A combination of 1 or more of- (CO) -NH-, - (CO) -O-and- (CO) -And a group formed thereby. Z¹May further have a substituent R²Is a hydrogen atom or an organic group. Z²Represents an aliphatic hydrocarbon group, an aryl group, a heterocyclic group, a combination of 1 or more of them, or a combination of these groups and a substituent selected from-S-, -SO₂-、-O-、-NR³A combination of 1 or more of-, - (CO) -NH-, - (CO) -O-, - (CO) -and-NH- (CO) -NH-. Z²May further have a substituent R³Is a hydrogen atom or an organic group.

Effects of the invention

According to the present invention, the decrease in transmittance in the high-temperature and high-humidity resistance test is small, and the performance is sufficiently exhibited in electronic devices such as solid-state imaging elements and organic EL displays.

The triazine polymer of the invention increases the number of branched structures, thereby increasing the number of crosslinked structures and improving the compactness of the membrane. This prevents the ingress of water, oxygen, etc., and prevents the deterioration reaction such as radical oxidation degradation.

The film produced using the triazine ring-containing polymer of the present invention having the above-described characteristics can be suitably used as one component in the production of electronic devices such as liquid crystal displays, organic Electroluminescence (EL) displays, optical semiconductor (LED) devices, solid-state imaging devices, organic thin-film solar cells, dye-sensitized solar cells, and organic thin-film transistors (TFTs). In particular, the present invention can be suitably used as an embedded film and a planarizing film on a photodiode, planarizing films before and after a color filter, a microlens, and a planarizing film and a conformal film on a microlens, which are components of a solid-state imaging device required to have a high refractive index.

Detailed Description

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

[ chemical formula 2]

In which X or Y is-S-or-NR¹-，R¹Is a hydrogen atom or an organic group. N is an integer of 1 or more. Z¹Represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, an acetyl group, a combination of 1 or more of these groups, or a single bond, -S-, -O-, -NR²-, - (CO) -NH-, - (CO) -O-and- (CO) -in combination. Z¹May further have a substituent R²Is a hydrogen atom or an organic group. Z²Represents an aliphatic hydrocarbon group, an aryl group, a heterocyclic group, a combination of 1 or more of them, or a combination of these groups and a substituent selected from-S-, -SO₂-、-O-、-NR³A combination of 1 or more of-, - (CO) -NH-, - (CO) -O-, - (CO) -and-NH- (CO) -NH-. Z²May further have a substituent R³Is a hydrogen atom or an organic group.

The unit structure represented by the general formula (1) is represented by Z²The structural units adjacent to each other via Y as the center are branched. By having such a branched structure, the density of the cured film becomes high, and not only the refractive index of the cured film is improved, but also the durability is improved.

When X and Y are-NH-, they are preferable because they have a high refractive index and are easily highly transparent.

To increase the refractive index, Z¹Aryl, heterocyclic substituents and their derivatives are preferred. Examples of the aryl group include a phenyl group, an o-chlorophenyl group, an m-chlorophenyl group, a p-chlorophenyl group, an o-fluorophenyl group, a p-fluorophenyl group, an o-methoxyphenyl group, a p-methoxyphenyl group, an o-biphenyl group, an m-biphenyl group, a p-biphenyl group, an α -naphthyl group, a β -naphthyl group, a 1-anthryl group, a 2-anthryl group, a 9-anthryl group, a 1-phenanthryl group, a 2-phenanthryl group, a 3-phenanthryl group, a 4-phenanthryl group, and a 9-phenanthryl group. Examples of the heterocyclic substituent include furan, pyrrole, thiophene, pyridine, triazine, thiadiazole, and derivatives thereof.

Z²A substituent of aliphatic hydrocarbon group, aryl group, heterocyclic ring or a combination of more than 1 of them, or a combination of these groups and a substituent selected from-S-, -SO₂-、-O-、-NR³-、A combination of 1 or more of- (CO) -NH-, - (CO) -O-, - (CO) -and-NH- (CO) -NH-. R³Is a hydrogen atom or an organic group, Z²May further have a substituent.

As Z²Examples of the aliphatic hydrocarbon group(s) include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1-dimethyl-n-propyl, 1, 2-dimethyl-n-propyl, 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-butyl, tert-butyl, cyclobutyl, 1-methyl-cyclopropyl, 2-ethyl-cyclopropyl, N-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 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-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 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, 1-methyl-cyclopentyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1, 2-dimethyl-cyclobutyl, 1, 3-dimethyl-cyclobutyl, 2, 2-dimethyl-cyclobutyl, 2, 3-dimethyl-cyclobutyl, 2, 4-dimethyl-cyclobutyl, 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 group, 2-ethyl-3-methyl-cyclopropyl group, and the like, from which 2 hydrogen atoms have been removed.

As Z²Examples of the aromatic ring and the heterocyclic ring in (1) include phenyl, biphenyl, naphthyl, binaphthyl, anthracenyl, furan, pyrrole, thiophene, pyridine, triazine, and thiadiazole. Z²These groups are preferably substituted with-S-, -SO₂-、-O-、-NR³A substituent comprising a plurality of- (CO) -NH-, - (CO) -O-, - (CO) -and-NH- (CO) -NH-linked together. Among them, structures represented by the following general formulae (2) to (10) are suitably used.

[ chemical formula 3]

Wherein x represents a bond directly bonded to Y. W¹～W³Is a single bond, -CR⁶⁸R⁶⁹-, -O-or-S-, R⁶⁸And R⁶⁹Is a hydrogen atom, an aryl group, a heterocyclic group or a hydrocarbon group having 1 to 10 carbon atoms. R⁴～R⁶⁷Independently of one another, represent an organic group.

W⁴Represents a single bond, -S-, -SO₂-、-O-、-NR³-, - (CO) -NH-, -NH- (CO) -, - (CO) -O-, - (CO) -, -O- (CO) -and-NH- (CO) -NH-, W⁵And W⁶Independently of one another, represents a single bond, -CR⁷⁰R⁷¹-(R⁷⁰And R⁷¹Independently of one another, represents a hydrogen atom or an organic group. ) - (CO) -, -O-, -S-, - (SO) -, -SO₂-。W⁷～W⁹Is a single bond, -O-, -S-or-NR⁷²-，R⁷²Is a hydrogen atom or an organic group. W¹⁰Is N or a group represented by the following general formula (11).

[ chemical formula 4]

R⁷³Represents a hydrogen atom or an organic group.

Further, Z²More preferably, the following structures (12) to (14) are used.

[ chemical formula 5]

By adopting the above-mentioned structure, not only the triazine ring-containing polymer can be efficiently obtained, but also the solubility in a solvent is improved, and the resin composition can be easily adjusted to an arbitrary concentration.

The triazine ring-containing polymer of the present invention preferably has a partial structure represented by the following general formulae (15) to (17). These are a part of the structure of the terminal or side chain of the polymer, and by having these structures, not only the solubility of the polymer in an organic solvent is improved and the resin composition is easily produced, but also the substrate adhesion and chemical resistance of the cured film can be improved.

[ chemical formula 6]

In the formula, R⁷⁴The substituent is a substituent having 1 or more of alkoxysilyl group, hydroxysilyl group and hydrosilyl group. Is a linking group directly linked to Y in the aforementioned formula (1).

The weight average molecular weight (Mw) of the triazine ring-containing polymer in the present invention is not particularly limited, but is preferably 500 to 100,000. The weight average molecular weight of the triazine ring-containing polymer is preferably 2,000 or more from the viewpoint of further improving heat resistance and reducing shrinkage, and is preferably 10,000 or less from the viewpoint of further improving solubility and reducing viscosity of the resulting solution. The polymerization degree n is preferably 2 to 20. The weight average molecular weight in the present invention is an average molecular weight in terms of standard polystyrene based on gel permeation chromatography (hereinafter referred to as GPC) analysis.

The method for producing the triazine ring-containing polymer of the present invention will be described by way of example. The triazine ring-containing polymer of the present invention can be obtained by reacting a halogenotriazine compound with a 1-valent reactive compound and a 3-valent reactive compound in an organic solvent. Examples of the halogenotriazine compound include cyanuric chloride. Here, the 1-valent reactive compound refers to a compound having 1 amino group or thiol group.

Examples of the 1-valent reactive compound include aniline, 1-naphthylamine, 2-naphthylamine, 1-aminoanthracene, 2-aminoanthracene, 9-aminoanthracene, 2-chloroaniline, 3-chloroaniline, 4-chloroaniline, 2, 4-dichloroaniline, 2, 6-dichloroaniline, 3, 5-dichloroaniline, 2-bromoaniline, 3-bromoaniline, 4-bromoaniline, 2, 4-dibromoaniline, 2, 6-dibromoaniline, 3, 5-dibromoaniline, 2-fluoroaniline, 3-fluoroaniline, 4-fluoroaniline, 2, 4-difluoroaniline, 2, 6-fluoroaniline, 3, 5-fluoroaniline, 2-iodoaniline, 3-iodoaniline, 4-iodoaniline, 2, 4-diiodoaniline, 2, 4-iodoaniline, 1-aminoanthracene, 2-aminoanthracene, 9-aminoanthracene, 2-chloroaniline, 3-bromoaniline, 4-dichloroaniline, 2, 6-diiodoaniline, 3, 5-diiodoaniline, p-toluidine, m-toluidine, o-toluidine, 2, 6-dimethylaniline, 3, 5-dimethylaniline, 2,4, 6-trimethylaniline, 1-aminopyrene, 4-aminotriphenylamine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminobenzonitrile, 3-aminobenzonitrile, 4-aminobenzonitrile, p-methoxyaniline, m-methoxyaniline, o-methoxyaniline, 1-amino-2-methylnaphthalene, 4-tert-butylaniline, 2, 3-dimethylaniline, 2, 5-dimethylaniline, 2-ethylaniline, 3-ethylaniline, 4-ethylaniline, 2-ethynylaniline, 2-ethylaniline, 3-ethynylaniline, 4-ethynylaniline, 2-isopropylaniline, 3-isopropylaniline, 4-isopropylaniline, 2- (methylthio) aniline, 3- (methylthio) aniline, 4- (methylthio) aniline, 6-amino-1-naphthol, 5-amino-1-naphthol, 8-amino-2-naphthol, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2-aminotrifluorotoluene, 3-aminotrifluorotoluene, 4-aminotrifluorotoluene, 2-aminostyrene, 3-aminostyrene, 4-aminostyrene, benzenethiol, 2-fluorobenzenethiol, 3-fluorobenzenethiol, 4-fluorobenzenethiol, 2-naphthalenedithiol, 3-fluorobenzenethiol, 4-fluorobenzenethiol, 3-aminobutanethiol, 2-pyridinethiol, 4-pyridinethiol, 3-nitrobenzoic acid, 2,4- (methylthio) benzenethiol, 2-bromobenzenethiol, 3-bromobenzenethiol, 4-bromobenzenethiol, 2-chlorobenzenethiol, 3-chlorobenzenethiol, 4-chlorobenzenethiol, 2-iodobenzenethiol, 3-iodobenzenethiol, 4-iodobenzenethiol, p-toluenethiol, m-toluenethiol, o-toluenethiol, 2, 4-dimethylbenzenethiol, 3, 4-dimethylbenzenethiol, 2-hydroxyphenylthiol, 3-hydroxyphenylthiol, 4-hydroxyphenylthiol, 2-tert-butylbenzenethiol, 3-tert-butylbenzenethiol, 4-tert-butylbenzenethiol, 2, 5-dimethylbenzenethiol, 2-ethylbenzenethiol, 3-ethylbenzenethiol, 4-ethylbenzenethiol, 3-ethylbenzenethiol, 2-isopropylbenzenethiol, 3-isopropylbenzenethiol, 4-isopropylbenzenethiol, 2-methoxyphenylthiol, 3-methoxyphenylthiol, 4-methoxyphenylthiol, 2- (trifluoromethyl) benzenethiol, 3- (trifluoromethyl) benzenethiol, 4- (trifluoromethyl) benzenethiol, 3, 4-dimethoxybenzenethiol, aminopropyltrimethoxysilane, aminopropyltriethoxysilane, aminopropyltripropoxysilane, aminopropyltributoxysilane, aminoethyltrimethoxysilane, aminoethyltriethoxysilane, aminoethyltripropoxysilane, aminoethyltributoxysilane, p-aminophenyltrimethoxysilane, m-aminophenyltrimethoxysilane, o-aminophenyltrimethoxysilane, p-aminophenyltriethoxysilane, p-aminophenyltrimethoxysilane, n-methoxyphenylmercaptan, 3-methoxyphenylthiol, 3-methoxyphenyl, M-aminophenyl triethoxy silane, o-aminophenyl triethoxy silane, p-aminophenyl tripropoxy silane, m-aminophenyl tripropoxy silane, o-aminophenyl tripropoxy silane, p-aminophenyl tributoxy silane, m-aminophenyl tributoxy silane, o-aminophenyl tributoxy silane, etc. Wherein, for the purpose of obtaining a partial structure represented by the general formula (14) or (15), it is preferable to use at least an amine compound having a silyl group such as aminopropyltrimethoxysilane, aminopropyltriethoxysilane, aminopropyltripropoxysilane, aminopropyltributoxysilane, aminoethyltrimethoxysilane, aminoethyltriethoxysilane, aminoethyltripropoxysilane, aminoethyltributoxysilane, p-aminophenyltrimethoxysilane, m-aminophenyltrimethoxysilane, o-aminophenyltrimethoxysilane, p-aminophenyltriethoxysilane, m-aminophenyltriethoxysilane, o-aminophenyltriethoxysilane, p-aminophenyltripropoxysilane, m-aminophenyltripropoxysilane, o-aminophenyltripropoxysilane, p-aminophenyltributoxysilane, m-aminophenyltributoxysilane, o-aminophenyltributoxysilane and the like.

The 3-valent reactive compound is a compound having 3 amino groups or thiol groups. Examples of the 3-valent reactive compound include 1,3, 5-triaminobenzene, 4,5, 6-triaminopyridine, 3,4, 5-triaminopyridine, 2,4, 5-triaminoquinoline, 2,4, 6-triaminoquinoline, 2,4, 7-triaminoquinoline, 2,4, 8-triaminoquinoline, 3,5, 7-triaminoquinoline, 3,6, 8-triaminoquinoline, 4' - [1,3, 5-triazine-2, 4, 6-triyltris (oxy) ] triphenylamine, 1,3, 5-triaminonaphthalene, 1,3, 6-triaminonaphthalene, 1,3, 7-triaminonaphthalene, 2,5, 7-triaminonaphthalene, 1,3, 6-thianthrene, 2,4, 6-thianthrene, 1,3, 6-thianthrene, 2,4, 5-thianthrene, 1,3, 5-tris (4-aminophenoxy) benzene, 5- (4-aminophenoxy) benzene-1, 3-diamine, 4 '-triaminotriphenylamine, 3, 5-diamino-N- (4-aminophenyl) benzamide, 3, 5-diamino-N- (4-aminophenyl) -4-methoxybenzamide, 1,3, 5-benzenetrithiol, 4', 4' -trithiotriphenylamine, 3, 5-dimercapto-N- (4-mercaptophenyl) benzamide, 1,3, 5-tris (4-mercaptophenoxy) benzene, 5- (4-mercaptophenoxy) benzene-1, 3-dithiol, and the like.

As the organic solvent, various solvents generally used in such a reaction can be used, and examples thereof include N, N-dimethylformamide, N, N-dimethylisobutylamide, N-methyl-2-pyrrolidone, tetramethylurea, 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-dimethylisobutylamide, N-methylformamide, N, N ' -dimethylpropyleneurea, N, N ' -dimethylisobutylamide, N-methylisobutylamide, N, N ' -dimethylisobutylamide, N-methylisobutylenecarboxamide, N, N-dimethylisobutylamide, N-methylisobutylenecar, Solvents such as γ -butyrolactone, and mixed solvents thereof. Among them, N-methyl-2-pyrrolidone, N-dimethylacetamide, N-dimethylisobutylamide, γ -butyrolactone, and a mixture thereof are preferable.

In addition, a catalyst may be contained for the purpose of shortening the reaction time. As the catalyst, an inorganic base, a secondary amine compound or a tertiary amine compound is preferable.

Examples of the inorganic base include potassium carbonate, potassium hydroxide, sodium carbonate, sodium hydroxide, sodium hydrogen carbonate, sodium ethoxide, sodium acetate, triethylamine, lithium carbonate, lithium hydroxide, lithium oxide, potassium acetate, magnesium oxide, calcium oxide, barium hydroxide, trilithium phosphate, trisodium phosphate, tripotassium phosphate, cesium fluoride, and aluminum oxide.

Examples of the secondary amine include dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diisobutylamine, di-sec-butylamine, di-tert-butylamine, dipentylamine, diisopentylamine, dihexylamine, dicyclohexylamine, dioctylamine, dibenzylamine, diphenylamine, piperidine, 3, 5-dimethylpiperidine, 2-ethylpiperidine, 4-isopropylpiperidine, 2-methylpiperidine, 3-methylpiperidine, 4-methylpiperidine, 2, 5-diphenylpyrrolidine, 2, 6-dimethylpiperidine, 2,6, 6-tetramethylpiperidine, N-isopropylaniline, and N-ethylaniline.

Examples of the tertiary amine include trimethylamine, triethylamine, tripropylamine, triisopropylamine, tributylamine, triisobutylamine, tri-sec-butylamine, tripentylamine, triisopentylamine, trihexylamine, tricyclohexylamine, trioctylamine, tribenzylamine, triphenylamine, diisopropylethylamine, 1-methylpiperidine, 1-methyl-2, 2,6, 6-tetramethylpiperidine, and the like.

As a process for producing a triazine polymer, a 1-valent reactive compound, a 3-valent reactive compound and a catalyst are dissolved in a solvent, and a solution of a halogenated triazine compound dissolved in the solvent is added dropwise. After the completion of the dropwise addition, the reaction is carried out for about 1 to 5 hours at a temperature of 100 to 130 ℃ to obtain a triazine polymer solution. After that, the triazine polymer can be isolated by cooling to room temperature, filtering the precipitate, and reprecipitating and purifying the filtrate in an aqueous alkali solution. Finally, the polymer powder can be obtained by fully washing with water and vacuum-drying in an oven at 60 ℃.

The triazine ring-containing polymer of the present invention can be used as a resin composition mixed with other compounds, and examples thereof include compositions with a leveling agent, a surfactant, a crosslinking agent, a resin, and the like.

These compositions can be used as a film-forming composition, and can be suitably used as a film-forming composition dissolved in various solvents.

The solvent used for dissolving the polymer may be the same solvent as that used in the polymerization or may be a different solvent. The solvent is not particularly limited as long as compatibility with the polymer is not impaired, and 1 or more kinds can be arbitrarily selected and used.

Specific examples of such solvents include toluene, p-xylene, o-xylene, m-xylene, ethylbenzene, styrene, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol 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, and the like, 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 n-butyl ketone, cyclohexanone, ethyl acetate, isopropyl acetate, n-propyl acetate, isobutyl acetate, n-butyl acetate, ethyl lactate, methanol, ethanol, isopropanol, t-butanol, allyl alcohol, n-propanol, 2-methyl-2-butanol, isobutanol, n-butanol, 2-methyl-1-butanol, 1-pentanol, 2-methyl-1-pentanol, 2-ethylhexanol, 1-methoxy-2-propanol, tetrahydrofuran, 1, 4-dioxane, and the like, N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, 1, 3-dimethyl-2-imidazolidinone, dimethylsulfoxide, N-cyclohexyl-2-pyrrolidone, and the like, and these may be used alone or in combination of 2 or more.

In this case, the concentration of the solid component in the film-forming composition is not particularly limited as long as it is within a range that does not affect the storage stability, and may be appropriately set according to the target film thickness. Specifically, the solid content concentration is preferably 0.1 to 50% by mass, more preferably 0.1 to 20% by mass, from the viewpoint of solubility and storage stability.

The film-forming composition of the present invention may contain other components, for example, a leveling agent, a surfactant, a crosslinking agent, and the like, in addition to the triazine ring-containing polymer and the solvent, 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 alkylallyl 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; nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; trade names of "FTOP" EF301, EF303, EF352 (available from Mitsubishi Material electronics Co., Ltd.) (available from old GeMCO), "Megafac" F171, F173, R-08, R-30, F-553, F-554 (available from DIC (Co., Ltd.), "Fluorad" FC430, FC431 (available from Sumitomo 3M), "ASAHIGATE" AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (available from Asahi Nitro Co., Ltd.), and fluorine-based surfactants such as organosiloxane polymers KP341 (available from shin-Etsu chemical Co., Ltd.), BYK-302, BYK-307, BYK-322, BYK-323, BYK-330, BYK-333, BYK-370, BYK-375, BYK-378 (available from PAN-CHEMYO).

These surfactants may be used alone, or 2 or more of them may be used in combination. The amount of the surfactant to be used is preferably 0.0001 to 5 parts by mass, more preferably 0.001 to 1 part by mass, and still more preferably 0.01 to 0.5 part by mass, per 100 parts by mass of the triazine ring-containing polymer.

The crosslinking agent is not particularly limited as long as it is a compound having a substituent capable of reacting with the triazine ring-containing polymer of the present invention.

Examples of such compounds include melamine compounds having a substituent formed by crosslinking such as a methylol group or a methoxymethyl group, substituted urea compounds, compounds having a substituent formed by crosslinking such as an epoxy group or an oxetane group, compounds containing a blocked isocyanate, compounds having an acid anhydride group, compounds having a (meth) acryloyl group, and phenolic plastic compounds. Among them, compounds containing a methylol group, an epoxy group, a blocked isocyanate group, and a (meth) acryloyl group are preferable from the viewpoint of heat resistance and storage stability.

Further, the blocked isocyanate group is preferable in that it is crosslinked by a urea bond and does not decrease the refractive index due to the carbonyl group.

These compounds need to have at least 1 crosslinking-forming substituent in the case of being used for the terminal treatment of the polymer, and at least 2 crosslinking-forming substituents in the case of being used for the crosslinking treatment of the polymers with each other.

As the compound having a hydroxymethyl group, the following compounds are mentioned: the polymer has 2 or more methylol groups in a molecule, and the methylol groups undergo an addition reaction with the triazine ring-containing polymer to undergo crosslinking.

As the epoxy compound, the following epoxy compounds were used: the triazine ring-containing polymer of the present invention has 2 epoxy groups in one molecule, and when exposed to high temperature during thermal curing, the epoxy groups open a ring, and a crosslinking reaction proceeds by an addition reaction with the triazine ring-containing polymer of the present invention.

Specific examples of the crosslinking agent include tris (2, 3-epoxypropyl) isocyanurate, 1, 4-butanediol diglycidyl ether, 1, 2-epoxy-4- (epoxyethyl) cyclohexane, glycerol triglycidyl ether, diethylene glycol diglycidyl ether, 2, 6-diglycidyl phenyl glycidyl ether, 1, 3-tris [ p- (2, 3-epoxypropoxy) phenyl ] propane, 1, 2-cyclohexanedicarboxylic acid diglycidyl ester, 4' -methylenebis (N, N-diglycidylaniline), 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexanecarboxylate, trimethylolethane triglycidyl ether, bisphenol-A-diglycidyl ether, and mixtures thereof, Pentaerythritol polyglycidyl ether, and the like.

Further, commercially available products include ML-26X, ML-24X, ML-236TMP, 4-hydroxymethyl-3M 6C, ML-MC, ML-TBC, DML-MBPC, DML-MBOC, DML-OCHP, DML-PC, DML-PCHP, DML-PTBP, DML-34X, DML-EP, DML-POP, DML-OC, dimethylol-Bis-C, dimethylol-BisOC-P, DML-BisOC-Z, DML-BisOCHP-Z, DML-PFP, DML-PSBP, DML-MB25, DML-MTrisPC, DML-Bis25X-34, DML-Bis25X-PCHP, 2, 6-dimethoxymethyl-4-t-butylphenol, 2, 6-dimethoxymethyl-p-cresol, 2, 6-diacetoxymethyl-p-cresol, TriML-P, TriML-35XL, TriML-TrisCR-HAP, TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (trade name, manufactured by Nippon chemical industries, Ltd.), DM-BI25X-F, 46DMOC, 46 OIDMPP, 46DMOEP, TM-BIP-A (trade name, manufactured by Asahi organic materials industries, Ltd.), Nikalac MX-290, Nikalac MX-280, Nikalac MX-270, MW-100LM (trade name, manufactured by Nikalac Co., Ltd.), and so forth.

In addition, "Epolead" GT-401, "Epolead" GT-403, "Epolead" GT-301, "Epolead" GT-302, "Celloxide" 2021, "Celloxide" 3000 (Daxika chemical industry Co., Ltd.), "Epikote" (now jER)807, "Epikote" 828, "Epote" 1001, "Epike" 1002, "Epotike" 1003, "Epote" 1004, "Epike" 3000, "Epikote" 1009, "Epike" 1007, "Epike" 828 "(above Japanese epoxy resin strain) (now called" PRITE "), and" Epike "76" (now JER) novolac "(now called" VG-152) as epoxy resins having at least 2 epoxy groups can be used, Epikote 154 (manufactured by Nippon epoxy resin Co., Ltd.), EPPN201, EPPN202 (manufactured by Nippon chemical Co., Ltd.), EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, EOCN-1027 (manufactured by Nippon chemical Co., Ltd.), Epikote (manufactured by jER Co., Ltd.), 180S75 (manufactured by Nippon epoxy resin Co., Ltd.), Denacol EX-252 (manufactured by Nagase ChemteX Co., Ltd.), CY175, CY177, CY179 (manufactured by CIBA-GEIGY A.G), "ARDIALTE" CY-182, "ARALDITE" CY-192, "ARDIALTE" CY-IGY "(manufactured by CIBA-IGY A.G), and" Epiclon "200 (manufactured by Epikote" 400) are manufactured by Epik K "(manufactured by Epik epoxy resin Co., Ltd.," Epik-184 (manufactured by Nippon chemical Co., Ltd.), "Epik-E" (manufactured by Nippon chemical Co., Ltd.), "Epik-E) (manufactured by Nippon chemical Co., Ltd.)," Epik-Q., "As manufactured by Nippon epoxy resin Co., manufactured by Nippon chemical Co., Ltd.", "Ex-, ED-5661, ED-5662 (manufactured by Celanese Coating Co., Ltd.), aliphatic polyglycidyl ether such as "Denacol" EX-611, "Denacol" EX-612, "Denacol" EX-614, "Denacol" EX-622, "Denacol" EX-411, "Denacol" EX-512, "Denacol" EX-522, "Denacol" EX-421, "Denacol" EX-313, "Denacol" EX-314, "Denacol" EX-321 (manufactured by Nagase ChemteX Co., Ltd.), and the like.

As the compound having an acid anhydride group, the following compounds are mentioned: when the carboxylic anhydride obtained by dehydrating condensation of 2 molecules of carboxylic acid is exposed to high temperature during thermal curing, the anhydride ring is opened, and the crosslinking reaction proceeds by an addition reaction with the triazine ring-containing polymer of the present invention.

Specific examples of the acid anhydride compound include: compounds having 1 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, octylsuccinic anhydride, and dodecenylsuccinic anhydride; 1,2,3, 4-cyclobutanetetracarboxylic dianhydride, pyromellitic anhydride, 3, 4-dicarboxy-1, 2,3, 4-tetrahydro-1-naphthalenesuccinic 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', 4,4 '-benzophenone tetracarboxylic dianhydride, 3', and compounds having 2 acid anhydride groups in the molecule, such as 4, 4' -biphenyltetracarboxylic dianhydride, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride, and 1, 3-dimethyl-1, 2,3, 4-cyclobutanetetracarboxylic dianhydride.

As the compound having a (meth) acryloyl group, the following compounds are mentioned: has 2 or more (meth) acryloyl groups in one molecule, and when exposed to high temperature at the time of thermal curing, undergoes a crosslinking reaction with the triazine ring-containing polymer of the present invention through an addition reaction.

Examples of the compound having a (meth) acryloyl group 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 glycerol triacrylate, ethoxylated glycerol trimethacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetramethacrylate, ethoxylated dipentaerythritol hexaacrylate, polyglycerol monoepoxyethylene polyacrylate, polyglycerol polyethylene glycol polyacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, neopentyl glycol diacrylate, ethylene glycol diacrylate, propylene, 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 the like.

The compound having a (meth) acryloyl group can be obtained as a commercially available product, and specific examples thereof include: NK ESTER A-200, NK ESTER A-400, NK ESTER A-600, NK ESTER A-1000, NK ESTER A-TMPT, NK ESTER UA-53H, NK ESTER 1G, NK ESTER 2G, NK ESTER 3G, NK ESTER4G, NK ESTER9G, NK ESTER 14G, NK ESTER 23G, NK ESTER ABE-300, NK ESTER A-BPE-4, NK ESTER A-BPE-6, NK ESTER A-BPE-10, NK ESTER A-BPE-20, ESTER A-BPE-30, NK ESTER BPE-80N, NK ESTER BPE-100N, NK ESTER BPE-200, NK ESTER BPE-500, ESNK TER BPE-900, NK TERE-1300N, NK TERE-3Y-3, NK ESTER A-GLY-9E, NK ESTER A-GLY-20E, NK ESTER A-TMPT-3EO, NK ESTER A-TMPT-9EO, NK ESTER ATM-4E, NK ESTER ATM-35E (manufactured by Xinzhongcun chemical industry Co., Ltd.); KAYARAD (registered trademark) DPEA-12, KAYARAD PEG400DA, KAYARAD THE-330, KAYARAD RP-1040 (manufactured by KAYARAD, Inc.), M-210, M-350 (manufactured by TOYOBA SYNTHESIS, Inc.), KAYARAD (registered trademark) DPHA, KAYARAD NPGDA, KAYARAD PET30 (manufactured by KAYARAD, Inc.), NKESTER A-DPH, NK ESTER A-TMPT, NK ESTER A-DCP, NK ESTER A-HD-N, NK ESTER TMPT, NKESTER DCP, NK ESTER NPG, NK ESTER HD-N (manufactured by Newzhongcun chemical industry, Inc.), and the like.

These crosslinking agents may be used alone, or 2 or more kinds may be used in combination. The amount of the crosslinking agent used is preferably 1 to 100 parts by mass per 100 parts by mass of the triazine ring-containing polymer. The lower limit of the amount of the crosslinking agent is preferably 10 parts by mass, more preferably 20 parts by mass, in view of solvent resistance, and the upper limit is preferably 50 parts by mass, more preferably 30 parts by mass, in view of controlling the refractive index.

By using the crosslinking agent, the crosslinking agent reacts with the reactive terminal substituent group of the triazine ring-containing polymer, and effects such as improvement of film density, improvement of heat resistance, and improvement of heat relaxation ability may be exhibited.

The other components can be added in any step in the preparation of the composition of the present invention.

The composition for film formation of the present invention can be applied to a substrate and then heated as necessary to form a desired film.

The coating method of the composition is arbitrary, and for example, a spin coating method, a dipping method, a flow coating method, an ink jet method, a spray coating method, a bar coating method, a gravure coating method, a slit coating method, a roll coating method, a transfer printing method, a brush coating method, a blade coating method, an air knife coating method, or the like can be used.

Examples of the substrate include substrates made of silicon, glass on which an Indium Tin Oxide (ITO) film is formed, glass on which an Indium Zinc Oxide (IZO) film is formed, polyethylene terephthalate (PET), plastic, glass, quartz, ceramics, and the like, and flexible substrates having flexibility can also be used.

The firing temperature is not particularly limited for the purpose of evaporating the solvent, and may be, for example, 40 to 400 ℃. In these cases, a temperature change of 2 stages or more may be applied for the purpose of exhibiting higher uniform film formation properties and performing a reaction on the substrate.

The firing method is not particularly limited, and for example, it is sufficient to evaporate the material in an appropriate atmosphere such as the atmosphere, an inert gas such as nitrogen, or a vacuum using a hot plate or an oven. The firing temperature and the firing time may be selected as appropriate for the process step of the target electronic device, and may be selected as appropriate for the physical property value of the obtained film to be suitable for the required characteristics of the electronic device.

The film formed from the composition of the present invention thus obtained can achieve high heat resistance, high transparency, high refractive index, high solubility, and low volume shrinkage, and therefore can be suitably used as one component in the production of electronic devices such as liquid crystal displays, organic Electroluminescence (EL) displays, optical semiconductor (LED) elements, solid-state imaging elements, organic thin-film solar cells, dye-sensitized solar cells, and organic thin-film transistors (TFTs).

In the composition of the present invention, other resins (thermoplastic resins or thermosetting resins) may be blended as necessary.

Specific examples of the resin are not particularly limited. Examples of the thermoplastic resin include polyolefin resins such as PE (polyethylene), PP (polypropylene), EVA (ethylene-vinyl acetate copolymer), EEA (ethylene-ethyl acrylate copolymer), and the like; polystyrene resins such AS PS (polystyrene), HIPS (high impact polystyrene), AS (acrylonitrile-styrene copolymer), ABS (acrylonitrile-butadiene-styrene copolymer), MS (methyl methacrylate-styrene copolymer), and the like; a polycarbonate resin; vinyl chloride resin; a polyamide resin; a polyimide resin; (meth) acrylic resins such as PMMA (polymethyl methacrylate); polyester resins such as PET (polyethylene terephthalate), polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, PLA (polylactic acid), poly-3-hydroxybutyric acid, polycaprolactone, polybutylene succinate, and polyethylene succinate/adipate; a polyphenylene ether resin; a modified polyphenylene ether resin; a polyacetal resin; polysulfone resin; polyphenylene sulfide resin; a polyvinyl alcohol resin; polyglycolic acid; modified starch; cellulose acetate, cellulose triacetate; chitin, chitosan; examples of the thermosetting resin include a phenol resin, a urea resin, a melamine resin, an unsaturated polyester resin, a polyurethane resin, and an epoxy resin. These resins may be used alone or in combination of 2 or more, and the amount thereof is preferably 1 to 10,000 parts by mass, more preferably 1 to 1,000 parts by mass, per 100 parts by mass of the triazine ring-containing polymer.

For example, the composition with a (meth) acrylic resin can be obtained by blending a (meth) acrylate compound in the composition and polymerizing the (meth) acrylate compound.

Examples of the (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, tricyclodecanyl di (meth) acrylate, trimethylolpropane triethoxy propyl (meth) acrylate, tris-2-hydroxyethyl isocyanurate tri (meth) acrylate, tris-2-hydroxyethyl isocyanurate di (meth) acrylate, ethylene glycol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, pentaerythritol di (meth) acrylate, glycerol methacrylate acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane trimethacrylate, allyl (meth) acrylate, vinyl (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, urethane (meth) acrylate, and the like.

Polymerization of these (meth) acrylate compounds can be performed by irradiation with light or heating in the presence of a photo radical initiator or a thermal radical initiator.

Examples of the photo radical polymerization initiator include acetophenones, benzophenones, Michler's benzoyl benzoate (Michler's benzyl benzoate), pentoxime esters, tetramethylthiuram monosulfide, and thioxanthones.

The photocleavage type photo radical polymerization initiator is particularly preferred. The photocleavage type photo-radical polymerization initiator is described in the latest UV curing technology (159 page, publisher: Gao-Bo-Yi-hong, release institute (strain) technical information Association, 1991).

Examples of commercially available photo radical polymerization initiators include: trade name manufactured by CIBA JAPAN (Strain): "Irgacure" 184, 369, 651, 500, 819, 907, 784, 2959, CGI1700, CGI1750, CGI1850, CG24-61, "Darocur" 1116, 1173; trade name manufactured by BASF corporation: "Lucirin" TPO; trade name manufactured by UCB: "Ubecryl" P36; trade name manufactured by Fratelli-Lamberti Co: "Esacure" KIP150, KIP65LT, KIP100F, KT37, KT55, KTO46, KIP75/B, etc.

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

< method for Forming microlens array >

As one embodiment of the microlens forming method, an example of a process for forming a microlens array will be described. If necessary, the surface of the element is flattened by filling the irregularities by spin coating with a transparent resin. The lens material is uniformly coated on the planarized surface. The resist is uniformly coated on the lens material. The resist was irradiated with ultraviolet rays using a stepper (reticle) as a mask, and the space between lenses was exposed. The photosensitive portion is decomposed and removed with a developer to form a pattern. A hemispherical pattern is obtained by heating. At this time, the resist melts to become a liquid phase, becomes a hemisphere state, and then changes to a solid phase. The layer of lens material is then etched by dry etching. This enables formation of a lens array in which hemispherical lenses are arranged.

Another embodiment of the lens array is a method of patterning a lens material by exposure without using the above-described resist. In this embodiment, the patterned lens material is directly melted to obtain a hemispherical lens.

< solid-state imaging element >

The solid-state imaging element according to a preferred embodiment of the present invention has a microlens formed of a cured product of the triazine resin composition of the present invention. The solid-state imaging device has a microlens array on a semiconductor light receiving element, and is assembled so that the microlens array is adjacent to a color filter. The solid-state imaging device is manufactured by forming a color filter and a microlens in this order from the substrate side on a substrate having a light receiving element. The light receiving element receives light that has reached through the transparent resin film, the lens, and the color filter in this order, and functions as an image sensor. Specifically, the transparent resin film functions as an antireflection film, the light collection efficiency of the microlens is improved, and the light collected efficiently by the microlens is detected by the light receiving element via the color filter. These function as all pixels of a light receiving element that detects light corresponding to each of RGB. Therefore, even when the pixels of the light receiving element and the respective lenses of the microlenses are arranged at high density, an extremely clear image can be obtained. As the transparent pixel interposed between the lens and the RGB pixel arrangement, a cured product of the triazine resin composition of the present invention can be suitably used.