JP7205466B2 - Triazine ring-containing polymer, resin composition, cured film and solid-state imaging device - Google Patents

Description

TECHNICAL FIELD The present invention relates to a resin composition containing a triazine ring-containing polymer, a cured film thereof, a method for producing the same, a substrate and a solid-state imaging device comprising the same.

2. Description of the Related Art In recent years, with the rapid development of digital cameras, camera-equipped mobile phones, etc., there is a demand for smaller solid-state imaging devices and higher pixel counts. Since the miniaturization of the solid-state imaging device leads to a decrease in sensitivity, efforts have been made to prevent the decrease in sensitivity by improving the light collection efficiency. Specifically, a method of arranging a condensing microlens above the color filter is adopted.

As a general method of manufacturing a microlens, a method of processing a resin film by dry etching is common. Organic materials such as polystyrene and acrylic are often used as materials for the resin film, and their refractive index is 1.5 to 1.6. is required.

In order to increase the refractive index of lens materials, various attempts have been made to increase the refractive index of polymer compounds, and the introduction of metal oxide particles, aromatics, halogen atoms, and heteroatoms has been investigated. . For example, a method of mixing a siloxane polymer with particles of a metal oxide such as titanium oxide or zirconia is known as the most powerful method for increasing the refractive index (Patent Document 1).

On the other hand, the introduction of metal oxides may impair the flexibility and crack resistance of the cured film, and triazine cyclic polymers that can achieve a high refractive index without the introduction of metal oxides are also known ( Patent document 2). Such a polymer does not contain a metal oxide and can exhibit a high refractive index by itself. Therefore, even when a dry process such as etching or ashing is performed, the etching rate becomes constant, a film having a uniform film thickness can be obtained, and the process margin is expanded when manufacturing devices.

Despite these advantages, the triazine ring polymer has poor heat resistance, and a decrease in transmittance due to coloration is observed in the microlens formation process and subsequent processes. It was difficult to use. The triazine ring polymer described in Patent Document 3 improves the heat resistance of the polymer by introducing a highly heat-resistant aromatic ring.

However, the triazine ring polymer as disclosed in Patent Document 3 has a problem that the transmittance decreases in a high-temperature and high-humidity durability test required for electronic devices such as solid-state imaging devices and organic electroluminescence (EL) displays. there were.

JP 2007-246877 A Japanese Unexamined Patent Application Publication No. 2009-1658 JP 2012-92261 A

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

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

In the formula, X or Y is -S- or -NR ¹ -, and R ¹ is a hydrogen atom or an organic group. n is an integer of 1 or more. Z ¹ is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, an acetyl group, a group formed by combining one or more of these groups, or these groups and a single bond, a group consisting of a combination of one or more groups selected from -S-, -O-, -NR ² -, -(CO)-NH-, -(CO)-O- and -(CO)- show. Z ¹ may further have a substituent, and R ² is a hydrogen atom or an organic group. Z ² is an aliphatic hydrocarbon group, an aryl group, a heterocyclic group, or a group consisting of a plurality of combinations of one or more of these groups, or these groups together with —S—, —SO ₂ —, —O—, -NR ³ -, -(CO)-NH-, -(CO)-O-, -(CO)-, and -NH-(CO)-NH- in combination with one or more groups show. ^Z2 may further have a substituent ^, and R3 is a hydrogen atom or an organic group.

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

Since the triazine polymer of the present invention has a large number of branched structures, the number of crosslinked structures is increased and the denseness of the film is improved. As a result, entry of water, oxygen, etc. can be prevented, and degradation reactions such as radical oxidative degradation can be prevented.

Films produced using the triazine ring-containing polymer of the present invention having the properties described above include liquid crystal displays, organic electroluminescence (EL) displays, optical semiconductor (LED) devices, solid-state imaging devices, organic thin-film solar cells, It can be suitably used as a member when producing electronic devices such as dye-sensitized solar cells and organic thin film transistors (TFTs). Buried films and planarization films on photodiodes, planarization films before and after color filters, microlenses, planarization films and conformal films on microlenses, which are components of solid-state imaging devices that are particularly required to have a high refractive index. can be suitably used as

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

In the formula, X or Y is -S- or -NR ¹ -, and R ¹ is a hydrogen atom or an organic group. n is an integer of 1 or more. Z ¹ is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, an acetyl group, a group formed by combining one or more of these groups, or these groups and a single bond, a group consisting of a combination of one or more groups selected from -S-, -O-, -NR ² -, -(CO)-NH-, -(CO)-O- and -(CO)- show. Z ¹ may further have a substituent, and R ² is a hydrogen atom or an organic group. Z ² is an aliphatic hydrocarbon group, an aryl group, a heterocyclic group, or a group consisting of a plurality of combinations of one or more of these groups, or these groups together with —S—, —SO ₂ —, —O—, -NR ³ -, -(CO)-NH-, -(CO)-O-, -(CO)-, and -NH-(CO)-NH- in combination with one or more groups show. ^Z2 may further have a substituent ^, and R3 is a hydrogen atom or an organic group.

The unit structure represented by the general formula (1) means that adjacent structural units ^are branched through Y centering on Z2. By having such a branched structure, the density of the cured film is increased, and not only the refractive index of the cured film is improved, but also the durability is improved.

When X and Y are -NH-, the refractive index is high and the transparency tends to be high, which is preferable.

In order to improve the refractive index, Z ¹ is preferably an aryl group, a heterocyclic substituent, or a derivative thereof. Examples of aryl groups include phenyl, o-chlorophenyl, m-chlorophenyl, p-chlorophenyl, o-fluorophenyl, p-fluorophenyl, o-methoxyphenyl, p-methoxyphenyl group, o-biphenylyl group, m-biphenylyl group, p-biphenylyl group, α-naphthyl group, β-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group and the like. Heterocyclic substituents include furan, pyrrole, thiophene, pyridine, triazine, thiadiazole and derivatives thereof.

Z ² is an aliphatic hydrocarbon group, an aryl group, a heterocyclic substituent, or a group consisting of a combination of one or more of these, or these groups together with -S-, -SO ₂ -, -O -, -NR ³ -, -(CO)-NH-, -(CO)-O-, -(CO)-, and -NH-(CO)-NH- in combination with one or more selected from represents a group. R3 is a hydrogen atom or an organic group ^, and ^Z2 may further have a substituent.

The aliphatic hydrocarbon group for Z ² includes methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, cyclobutyl group, 1-methyl-cyclopropyl group, 2-methyl-cyclopropyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1, 1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, cyclopentyl group, 1-methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group, 2-ethyl-cyclopropyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3- dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group , 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, cyclohexyl group, 1-methyl-cyclopentyl group, 2-methyl-cyclopentyl group, 3-methyl-cyclopentyl group , 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group, 3-ethyl-cyclobutyl group, 1,2-dimethyl-cyclobutyl group, 1,3-dimethyl-cyclobutyl group, 2,2-dimethyl-cyclobutyl group, 2 , 3-dimethyl-cyclobutyl group, 2,4-dimethyl-cyclobutyl group, 3,3-dimethyl-cyclobutyl group, 1-n-propyl-cyclopropyl group, 2-n-propyl-cyclopropyl group, 1-isopropyl- cyclopropyl group, 2-isopropyl-cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, 1,2,3-trimethyl-cyclopropyl group, 2,2,3-trimethyl-cyclopropyl group, 1- ethyl-2-methyl-cyclopropyl group, 2-ethyl-1-methyl-cyclopropyl group, 2-ethyl-2-methyl- A group obtained by removing two hydrogen atoms from a cyclopropyl group, a 2-ethyl-3-methyl-cyclopropyl group, and the like can be mentioned.

Aromatic rings and heterocyclic rings contained in ^Z2 include phenyl group, biphenyl group, naphthyl group, binaphthyl group, anthryl group, furan, pyrrole, thiophene, pyridine, triazine, and thiadiazole. Z ² is such that these groups are -S-, -SO ₂ -, -O-, -NR ³ -, -(CO)-NH-, -(CO)-O-, -(CO)-, and - It is preferably a substituent in which a plurality of NH--(CO)--NH-- are linked. Among them, structures represented by the following general formulas (2) to (10) are preferably used.

In the formula, * indicates a bond directly connected to Y. W ¹ to W ³ are a single bond, —CR ⁶⁸ R ⁶⁹ —, —O— or —S—, and R ⁶⁸ and R ⁶⁹ are a hydrogen atom, an aryl group, a heterocyclic group or a hydrocarbon having 1 to 10 carbon atoms is the base. R ⁴ to R ⁶⁷ each independently represent an organic group.
W ⁴ is a single bond, -S-, -SO ₂ -, -O-, -NR ³ -, -(CO)-NH-, -NH-(CO)-, -(CO)-O-, - represents (CO)—, —O—(CO)— and —NH—(CO)—NH—, W ⁵ and W ⁶ are independently of each other a single bond, —CR ⁷⁰ R ⁷¹ —(R ⁷⁰ and R ⁷¹ independently represents water or an organic group), -(CO)-, -O-, -S-, -(SO)-, -SO ₂ -. W ⁷ to ⁹ are a single bond, —O—, —S— or —NR ⁷² —, and R ⁷² is a hydrogen atom or an organic group. ^W10 is N or a group represented by the following general formula (11).

^R73 represents a hydrogen atom or an organic group.

Furthermore, Z ² more preferably has the following structures (12) to (14).

With the above structure, not only can the triazine ring-containing polymer be obtained in good yield, but also the solubility in solvents is improved, making it easier to adjust the resin composition at any concentration.

The triazine ring-containing polymer in the present invention preferably has partial structures represented by the following general formulas (15) to (17). These are part of the terminal or side chain structure of the polymer. and chemical resistance can be improved.

In the formula, R ⁷⁴ is a substituent having one or more of an alkoxyryl group, a hydroxysilyl group and a hydrosilyl group. * is a linking group directly connected to Y in the formula (1).

The weight average molecular weight (Mw) of the triazine ring-containing polymer in the invention is not particularly limited, but is preferably 500 to 100,000. From the viewpoint of improving heat resistance and lowering the shrinkage rate, the weight average molecular weight of the triazine ring-containing polymer is preferably 2,000 or more, which further increases the solubility and reduces the viscosity of the resulting solution. From the point of view, 10,000 or less is preferable. A preferred degree of polymerization n is 2-20. The weight average molecular weight in the present invention is the average molecular weight obtained by standard polystyrene conversion by gel permeation chromatography (hereinafter referred to as GPC) analysis.

An example of the method for producing the triazine ring-containing polymer of the present invention will be described. The triazine ring-containing polymer of the present invention can be obtained by reacting a halogenated triazine compound, a monovalent reactive compound and a trivalent reactive compound in an organic solvent. Halogenated triazine compounds include cyanuric chloride. Here, the monovalent reactive compound is a compound having one amino group or one thiol group.

Examples of monovalent reactive compounds 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, 2,6-diiodoaniline, 3,5-diiodoaniline, p-toluidine, m-toluidine, o-toluidine, 2,6-dimethyl Aniline, 3,5-dimethylaniline, 2,4,6-trimethylaniline, 1-aminopyrene, 4-aminotriphenylamine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminobenzonitrile, 3-aminobenzonitrile, 4-aminobenzonitrile, p-anisidine, m-anisidine, o-anisidine, 1-amino-2-methylnaphthalene, 4-t-butylaniline, 2,3-dimethylaniline, 2,5 -dimethylaniline, 2-ethylaniline, 3-ethylaniline, 4-ethylaniline, 2-ethynylaniline, 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-aminobenzotrifluoride, 3-aminobenzotrifluoride, 4-aminobenzotrifluoride, 2-aminostyrene, 3-aminostyrene, 4-aminostyrene, benzenethiol, 2- fluorobenzenethiol, 3-fluorobenzenethiol, 4-fluorobenzenethiol, 2-naphthalenethiol, 4-(methylthio)benzenethiol, 2-bromobenzenethiol, 3-bromobenzenethiol ol, 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-hydroxybenzenethiol, 3-hydroxybenzenethiol, 4-hydroxybenzenethiol, 2-t-butylbenzenethiol, 3- t-butylbenzenethiol, 4-t-butylbenzenethiol, 2,5-dimethylbenzenethiol, 3,5-dimethylbenzenethiol, 2-ethylbenzenethiol, 3-ethylbenzenethiol, 4-ethylbenzenethiol, 2-isopropylbenzenethiol , 3-isopropylbenzenethiol, 4-isopropylbenzenethiol, 2-methoxybenzenethiol, 3-methoxybenzenethiol, 4-methoxybenzenethiol, 2-(trifluoromethyl)benzenethiol, 3-(trifluoromethyl)benzenethiol , 4-(trifluoromethyl)benzenethiol, 3,4-dimethoxybenzenethiol, aminopropyltrimethoxysilane, aminopropyltriethoxysilane, aminopropyltripropoxysilane, aminopropyltributoxysilane, aminoethyltrimethoxysilane, amino ethyltriethoxysilane, aminoethyltripropoxysilane, aminoethyltributoxysilane, p-aminophenyltrimethoxysilane, m-aminophenyltrimethoxysilane, o-aminophenyltrimethoxysilane, p-aminophenyltriethoxysilane, m -aminophenyltriethoxysilane, o-aminophenyltriethoxysilane, p-aminophenyltripropoxysilane, m-aminophenyltripropoxysilane, o-aminophenyltripropoxysilane, p-aminophenyltributoxysilane, m-amino Phenyltributoxysilane, o-aminophenyltributoxysilane and the like can be mentioned. Among them, for the purpose of obtaining a partial structure represented by general formula (14) or (15), 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- It is preferable to use at least amine compounds having silyl such as aminophenyltributoxysilane and o-aminophenyltributoxysilane.

A trivalent reactive compound is a compound having three amino groups or three thiol groups. Examples of trivalent reactive compounds 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 , 4,4′,4″-[1,3,5-triazine-2,4,6-triyltris(oxy)]trianiline, 1,3,5-triaminonaphthalene, 1,3,6-triaminonaphthalene , 1,3,7-triaminonaphthalene, 2,5,7-triaminonaphthalene, 1,3,6-thianthrene, 2,4,6-thianthrene, 2,4,5-thianthrene, 1,3,5 -tris(4-aminophenoxy)benzene, 5-(4-aminophenoxy)benzene-1,3-diamine, 4,4′,4″-triaminotriphenylamine, 3,5-diamino-N-(4 -aminophenyl)benzamide, 3,5-diamino-N-(4-aminophenyl)-4-methoxybenzamide, 1,3,5-benzenetrithiol, 4,4′,4″-trimercaptotriphenylamine, 3,5-dimercapto-N-(4-mercaptophenyl)benzamide, 1,3,5-tris(4-mercaptophenoxy)benzene, 5-(4-mercaptophenoxy)benzene-1,3-dimercaptan, etc. be done.

As the organic solvent, various solvents commonly used in this type of reaction can be used. Urea, N,N-dimethylacetamide, N-methyl-2-piperidone, N,N (dimethylethylene urea, N,N,N',N'-tetramethylmalonic acid amide, N-methylcaprolactam, N-acetylpyrrolidine , N,N-diethylacetamide, N-ethyl-2-pyrrolidone, N,N-dimethylpropionic acid amide, N,N-dimethylisobutyramide, N-methylformamide, N,N'-dimethylpropyleneurea, gamma-butyrolactone, etc. and mixed solvents thereof, of which N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylisobutyramide, gamma-butyrolactone and mixed solvents thereof are preferred.

Moreover, a catalyst may be contained for the purpose of shortening the reaction time. Preferred catalysts are inorganic bases and secondary or tertiary amine compounds.

Inorganic bases 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.

Secondary amines include dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diisobutylamine, di-sec-butylamine, di-tert-butylamine, dipentylamine, diisopentylamine, dihexylamine, dicyclohexylamine, dioctyl Amine, dibenzylamine, diphenylamine, piperidine, 3,5-dimethylpiperidine, 2-ethylpiperidine, 4-isopropylpiperidine, 2-methylpiperidine, 3-methylpiperidine, 4-methylpiperidine, 2,5-diphenylpyrrolidine, 2 ,6-dimethylpiperidine, 2,2,6,6-tetramethylpiperidine, N-isopropylaniline, N-ethylaniline and the like.

Tertiary amines 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 procedure for producing the triazine polymer, a monovalent reactive compound, a trivalent 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 completion of dropping, the solution is heated and reacted at a temperature of 100 to 130° C. for about 1 to 5 hours to obtain a solution of the triazine polymer. Thereafter, the mixture is cooled to room temperature, the precipitate is filtered, and the filtrate is reprecipitated and purified in an alkaline aqueous solution to isolate the triazine polymer. Finally, it is thoroughly rinsed with water and vacuum-dried in an oven at 60° C. to obtain polymer powder.

The triazine ring-containing polymer of the present invention described above can be used as a resin composition mixed with other compounds.

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

The solvent used for dissolving the polymer may be the same as or different from the solvent used during polymerization. This solvent is not particularly limited as long as it does not impair the compatibility with the polymer, and one kind or a plurality of kinds can be arbitrarily selected and used.

Specific examples of such solvents include toluene, p-xylene, o-xylene, m-xylene, ethylbenzene, styrene, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol, propylene glycol monoethyl ether. , ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol methyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, diethylene glycol diethyl ether, di Propylene 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, cyclohexanone, ethyl acetate, isopropyl acetate, normal propyl acetate, isobutyl acetate, normal butyl acetate, ethyl lactate, methanol, ethanol, Isopropanol, tert-butanol, allyl alcohol, normal propanol, 2-methyl-2-butanol, isobutanol, normal butanol, 2-methyl-1-butanol, 1-pentanol, 2-methyl-1-pentanol, 2- ethylhexanol, 1-methoxy-2-propanol, tetrahydrofuran, 1,4-dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, Dimethylsulfo oxide, N-cyclohexyl-2-pyrrolidinone and the like, and these may be used alone or in combination of two or more.

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

The film-forming composition of the present invention may contain components other than the triazine ring-containing polymer and the solvent, such as leveling agents, surfactants, cross-linking agents, etc., as long as they do not impair the effects of the present invention. good too.

Examples of surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol; Polyoxyethylene alkylallyl ethers such as ethers; polyoxyethylene/polyoxypropylene block copolymers; sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate sorbitan fatty acid esters such as; Nonionic surfactants such as sorbitan fatty acid esters, trade names "Ftop" EF301, EF303, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd. (formerly Jemco Co., Ltd.), trade names "Megafac" F171, F173 , R-08, R-30, F-553, F-554 (manufactured by DIC Corporation), “Florado” FC430, FC431 (manufactured by Sumitomo 3M), trade name “Asahi Guard” AG710, Surflon S- Fluorinated surfactants such as 382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.), 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, BYK-378 (manufactured by BYK-Chemie Japan Co., Ltd.) and the like.

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

The cross-linking 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.

Such compounds include melamine-based compounds having cross-linking substituents such as methylol groups and methoxymethyl groups, substituted urea-based compounds, compounds containing cross-linking substituents such as epoxy groups or oxetane groups, and blocked isocyanates. A compound containing, a compound having an acid anhydride group, a compound having a (meth)acryl group, a phenoplast compound, and the like. Among them, a compound containing a methylol group, an epoxy group, a blocked isocyanate group, or a (meth)acryl group is preferable from the viewpoint of heat resistance and storage stability.

In addition, the blocked isocyanate group is crosslinked by urea bonds and has a carbonyl group, so that the refractive index is not lowered, which is also preferable.
These compounds need only have at least one cross-linking substituent when used for polymer terminal treatment, and have at least two cross-linking substituents when used for cross-linking between polymers. There is a need.

The compound having a methylol group has two or more methylol groups in the molecule, and the methylol group undergoes an addition reaction with the triazine ring-containing polymer to proceed with cross-linking.

The epoxy compound has two or more epoxy groups in one molecule, and when exposed to a high temperature during thermosetting, the epoxy ring opens and crosslinks with the triazine ring-containing polymer of the present invention through an addition reaction. The reaction proceeds.

Specific examples of cross-linking agents include tris(2,3-epoxypropyl) isocyanurate, 1,4-butanediol diglycidyl ether, 1,2-epoxy-4-(epoxyethyl) cyclohexane, glycerol triglycidyl ether, and diethylene glycol. diglycidyl ether, 2,6-diglycidylphenyl glycidyl ether, 1,1,3-tris[p-(2,3-epoxypropoxy)phenyl]propane, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, 4,4 '-methylenebis(N,N-diglycidylaniline), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, trimethylolethane triglycidyl ether, bisphenol-A-diglycidyl ether, pentaerythritol polyglycidyl ether etc.

In addition, as commercial products, compounds having a methylol group, ML-26X, ML-24X, ML-236TMP, 4-methylol 3M6C, 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-34XL, 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 (the above, product names, manufactured by Honshu Chemical Industry Co., Ltd.), DM-BI25X-F, 46DMOC, 46DMOIPP, 46DMOEP, TM-BIP-A (the above, product names, Asahi Yu Kizai Kogyo Co., Ltd.), Nicalac MX-290, Nicalac MX-280, Nicalac MX-270, MW-100LM (all trade names, manufactured by Sanwa Chemical Co., Ltd.).

In addition, epoxy resins having at least two epoxy groups, PG-100 (manufactured by Osaka Gas Chemicals Co., Ltd.), YH-434, YH434L (manufactured by Tohto Kasei Co., Ltd.), epoxy resins having a cyclohexene oxide structure "Epolead" GT-401, GT-403, GT-301, GT-302, "Celoxide" 2021, 3000 (manufactured by Daicel Chemical Industries, Ltd.), a bisphenol type epoxy resin, " Epicoat" (currently jER) 807, 828, 1001, 1002, 1003, 1004, 1007, 1009, 1010, 828 (manufactured by Japan Epoxy Resin Co., Ltd.), "Epikote" (currently jER), VG-3101L (manufactured by Printec Co., Ltd.), phenolic novolac type epoxy resin, "Epikote" (currently jER) 152, 154 (manufactured by Japan Epoxy Resin Co., Ltd.), EPPN201, 202 (manufactured by Nippon Kayaku Co., Ltd.), EOCN-102, 103S, 104S, 1020, 1025, and 1027 (manufactured by Nippon Kayaku Co., Ltd.), which are cresol novolak epoxy resins ), “Epikote” (currently jER) 180S75 (manufactured by Japan Epoxy Resin Co., Ltd.), “Denacol” EX-252 (manufactured by Nagase ChemteX Co., Ltd.), which is an alicyclic epoxy resin, CY175, CY177 , CY179 (manufactured by CIBA-GEIGY AG), "Araldite" CY-182, CY-192, CY-184 (manufactured by CIBA-GEIGY AG), "Epicron" 200, 400 ( Above, manufactured by DIC Corporation), "Epikote" (currently jER) 871, 872 (manufactured by Japan Epoxy Resin Co., Ltd.), ED-5661, ED-5662 (manufactured by Celanese Coating Co., Ltd.) ), which are aliphatic polyglycidyl ethers, “Denacol” EX-611, EX-612, EX-614, EX-622, EX-411, EX-512, EX-522, EX- 421, EX-313, EX-314, EX-321 (manufactured by Nagase ChemteX Corporation) and the like can also be used.

The compound having an acid anhydride group is a carboxylic acid anhydride obtained by dehydrating and condensing two molecules of carboxylic acid, and when exposed to a high temperature during thermosetting, the anhydride ring is opened and the compound of the present invention is used. A cross-linking reaction proceeds through an addition reaction with the triazine ring-containing polymer.

Further, specific examples of acid anhydride compounds include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, and maleic anhydride. Acids, succinic anhydride, octyl succinic anhydride, those having one acid anhydride group in the molecule such as dodecenyl succinic anhydride; 1,2,3,4-cyclobutanetetracarboxylic dianhydride, pyromellitic acid anhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic dianhydride, bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic acid dianhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 1,2,3,4-butanetetracarboxylic acid di anhydride, 3,3′,4,4′-benzophenonetetracarboxylic dianhydride, 3,3′,4,4′-biphenyltetracarboxylic dianhydride, 2,2-bis(3,4-di Carboxyphenyl)hexafluoropropane dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride and the like having two acid anhydride groups in the molecule. .

The compound having a (meth)acrylic group has two or more (meth)acrylic groups in one molecule, and when exposed to a high temperature during thermosetting, the triazine ring-containing polymer of the present invention A cross-linking reaction proceeds through an addition reaction.

Examples of compounds having a (meth)acrylic group include ethylene glycol diacrylate, ethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, ethoxylated bisphenol A diacrylate, ethoxylated bisphenol A dimethacrylate, ethoxylated tri Methylolpropane triacrylate, ethoxylated trimethylolpropane trimethacrylate, ethoxylated glycerin triacrylate, ethoxylated glycerin trimethacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetramethacrylate, ethoxylated dipentaerythritol hexaacrylate, polyglycerin mono Ethylene oxide polyacrylate, polyglycerin polyethylene glycol polyacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, trimethylolpropane triacrylate acrylates, trimethylolpropane trimethacrylate, tricyclodecanedimethanol diacrylate, tricyclodecanedimethanol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate and the like.

The compound having the (meth) acrylic group is available as a commercial product, and specific examples thereof include NK Ester A-200, A-400, A-600, A-1000, A- TMPT, UA-53H, 1G, 2G, 3G, 4G, 9G, 14G, 23G, ABE-300, A-BPE-4, A-BPE-6, A- BPE-10, A-BPE-20, A-BPE-30, BPE-80N, BPE-100N, BPE-200, BPE-500, BPE-900, BPE-1300N, A - GLY-3E, A-GLY-9E, A-GLY-20E, A-TMPT-3EO, A-TMPT-9EO, ATM-4E, ATM-35E (Shin Nakamura Chemical Industry ( Co., Ltd.), KAYARAD (registered trademark) DPEA-12, PEG400DA, THE-330, RP-1040 (manufactured by Nippon Kayaku Co., Ltd.), M-210, M-350 (manufactured by Toagosei Co., Ltd.) Co., Ltd.), KAYARAD (registered trademark) DPHA, NPGDA, PET30 (manufactured by Nippon Kayaku Co., Ltd.), NK ester A-DPH, A-TMPT, A-DCP, A-HD -N, TMPT, DCP, NPG, and HD-N (all manufactured by Shin-Nakamura Chemical Co., Ltd.).

These cross-linking agents may be used alone or in combination of two or more. The amount of the cross-linking agent used is preferably 1 to 100 parts by mass with respect to 100 parts by mass of the triazine ring-containing polymer. Considering solvent resistance, the lower limit of the amount of the cross-linking agent used is preferably 10 parts by mass, more preferably 20 parts by mass, and considering controlling the refractive index, the upper limit is preferably 50 parts by mass. parts, more preferably 30 parts by mass.

By using a cross-linking agent, the cross-linking agent reacts with the reactive terminal substituents of the triazine ring-containing polymer, and effects such as improvement of film density, improvement of heat resistance, and improvement of thermal relaxation ability can be exhibited. There is
The above other components can be added in any step during preparation of the composition of the present invention.

A desired film can be formed by applying the film-forming composition of the present invention to a substrate and then heating it as necessary.

The composition may be applied by any method, such as spin coating, dipping, flow coating, inkjet, spraying, bar coating, gravure coating, slit coating, roll coating, transfer printing, and brushing. Methods such as coating, blade coating, and air knife coating can be used.

In addition, as the base material, silicon, glass coated with indium tin oxide (ITO), glass coated with indium zinc oxide (IZO), polyethylene terephthalate (PET), plastic, glass, quartz, and ceramics. etc., and a flexible base material having flexibility can also be used.

The calcination temperature is not particularly limited for the purpose of evaporating the solvent, and the calcination can be performed at, for example, 40 to 400°C. In these cases, the temperature may be changed in two or more steps for the purpose of developing a more uniform film-forming property or advancing the reaction on the substrate.

The baking method is not particularly limited. For example, a hot plate or an oven may be used to evaporate under an appropriate atmosphere such as air, an inert gas such as nitrogen, or vacuum. The sintering temperature and sintering time may be selected in accordance with the process steps of the target electronic device, and the sintering conditions may be selected such that the physical properties of the obtained film are suitable for the required characteristics of the electronic device.

The film composed of the composition of the present invention thus obtained can achieve high heat resistance, high transparency, high refractive index, high solubility, and low volume shrinkage, so it can be used for liquid crystal displays, organic electroluminescence (EL), and ) display, optical semiconductor (LED) device, solid-state imaging device, organic thin-film solar cell, dye-sensitized solar cell, organic thin-film transistor (TFT), and other electronic devices.

The composition of the present invention may optionally contain other resins (thermoplastic resins or thermosetting resins).

A specific example of the resin is not particularly limited. Examples of thermoplastic resins include polyolefin resins such as PE (polyethylene), PP (polypropylene), EVA (ethylene-vinyl acetate copolymer), EEA (ethylene-ethyl acrylate copolymer); PS (polystyrene). , HIPS (high impact polystyrene), AS (acrylonitrile-styrene copolymer), ABS (acrylonitrile-butadiene-styrene copolymer), MS (methyl methacrylate-styrene copolymer) polystyrene resins; polycarbonate resins; Vinyl chloride resin; Polyamide resin; Polyimide resin; (Meth) acrylic resin such as PMMA (polymethyl methacrylate); -Polyester resins such as 3-hydroxybutyric acid, polycaprolactone, polybutylene succinate, polyethylene succinate/adipate; polyphenylene ether resins; modified polyphenylene ether resins; polyacetal resins; polysulfone resins; polyphenylene sulfide resins; modified starch; cellulose acetate, cellulose triacetate; chitin, chitosan; lignin; is mentioned. These resins may be used alone or in combination of two or more. The amount used is preferably 1 to 10,000 parts by mass with respect to 100 parts by mass of the triazine ring-containing polymer. It is preferably 1 to 1,000 parts by mass.

For example, a composition with a (meth)acrylic resin can be obtained by blending a (meth)acrylate compound into the composition and polymerizing the (meth)acrylate compound.
Examples of (meth)acrylate compounds include methyl (meth)acrylate, ethyl (meth)acrylate, ethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, (Meth)acrylate, polypropylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, trimethylolpropane tri Oxyethyl (meth) acrylate, tricyclodecanedimethanol di (meth) acrylate, tricyclodecanyl di (meth) acrylate, trimethylolpropane trioxypropyl (meth) acrylate, tris-2-hydroxyethyl isocyanurate tri (meth) ) acrylate, tris-2-hydroxyethyl isocyanurate di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, pentaerythritol di(meth)acrylate, glycerin methacrylate acrylate, pentaerythritol tri(meth)acrylate, tri Methylolpropane 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 carried out by light irradiation or heating in the presence of a photoradical initiator or thermal radical initiator.
Examples of photoradical polymerization initiators include acetophenones, benzophenones, Michler's benzoyl benzoate, amyloxime ester, tetramethylthiuram monosulfide and thioxanthones.

In particular, a photocleavable photoradical polymerization initiator is preferred. The photo-cleavable photoradical polymerization initiator is described in Latest UV Curing Techniques (page 159, published by: Kazuhiro Takasusu, published by: Technical Information Institute, 1991).

Commercially available radical photopolymerization initiators include, for example, Ciba Japan Co., Ltd. product name: "Irgacure" 184, 369, 651, 500, 819, 907, 784, 2959, CGI1700, CGI1750, CGI1850, CG24-61 , “Darocure” 1116, 1173, manufactured by BASF, trade name: “Lucirin” TPO, manufactured by UCB, trade name: “Uvecryl” P36, manufactured by Fratelli Lamberti, trade name: “Ezacure” KIP150, KIP65LT, KIP100F, KT37, KT55, KTO46, KIP75/B and the like.

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

<Method for Forming Microlens Array>
An example of a process for forming a microlens array will be described as one form of a method for forming microlenses. If necessary, the irregularities on the surface of the element are filled by spin-coating with a transparent resin to make it flat. A uniform coating of lens material is applied to the flattened surface. A resist is uniformly applied on the lens material. A stepper device is used to irradiate the resist with ultraviolet rays using the reticle as a mask to expose the space between the lenses. The exposed portion is decomposed and removed with a developer to form a pattern. Obtained by heating a hemispherical pattern. At this time, the resist melts into a liquid phase, becomes hemispherical, and then changes into a solid phase. The layer of lens material is then etched by dry etching. In this way, a lens array in which hemispherical lenses are arranged can be formed.

Another embodiment of the lens array omits the use of the resist described above and includes a method of patterning the lens material by exposure. In this embodiment, the patterned lens material is directly melted to obtain hemispherical lenses.

<Solid-state image sensor>
A solid-state imaging device according to a preferred embodiment of the present invention has microlenses made of a cured product of the triazine resin composition of the present invention. A solid-state imaging device has a microlens array on a semiconductor light receiving device, and is incorporated so that the microlens array and the color filter are adjacent to each other. A solid-state imaging device is manufactured by sequentially forming a color filter and a microlens from the substrate side on a substrate having a light receiving device. The light-receiving element functions as an image sensor by receiving light that passes through the transparent resin film, the lens, and the color filter in this order. Specifically, the transparent resin film functions as an antireflection film to improve the light collecting efficiency of the microlens, and the light efficiently collected by the microlens is detected by the light receiving element through the color filter. These function over the pixels of the light receiving elements that detect the light corresponding to each of RGB. Therefore, even when the pixels of the light-receiving element and the individual lenses of the microlens are arranged at high density, a very clear image can be obtained. The cured product of the triazine resin composition of the present invention can be suitably used as transparent pixels to be interposed in the lens or RGB pixel array.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to the following Examples.
Abbreviations are shown below.
NMP: N-methylpyrrolidone TAPOB: 1,3,5-tris(4-aminophenoxy)benzene TADE: 5-(4-aminophenoxy)benzene-1,3-diamine 3,3'-DDS: 3,3' -diaminodiphenylsulfone TABA: 3,5-diamino-N-(4-aminophenyl)benzamide)
TCT: cyanuric chloride DMSO: dimethylsulfoxide MDM: diethylene glycol dimethyl ether.

<Measurement of molecular weight>
Using a GPC apparatus HLC-8220GPC (manufactured by Tosoh Corporation), the molecular weight in terms of polystyrene was measured with a tetrahydrofuran solution.

<Synthesis Example 1> Synthesis of Triazine Polymer 1 In a 500 mL four-necked flask, m-anisidine (12.24 g, 99.41 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.) as ^a component of Z1, ^TAPOB ( 13.24 g, 33 mmol, manufactured by Seika Co., Ltd.) and triethylamine (22.01 g, 205.45 mmol) were added, dissolved in NMP (90 g), and heated to 40° C. in an oil bath. After that, as a triazine component, a solution of TCT (12.22 g, 66.28 mmol, manufactured by Tokyo Kasei Kogyo Co., Ltd.) dissolved in 49 g of NMP was added dropwise over 30 minutes. After stirring for 1 hour after the completion of dropping, the mixture was further heated at 130° C. for 1 hour and cooled to room temperature. The resulting reaction solution was filtered to remove the precipitate and the filtrate was recovered. The filtrate was added dropwise to a 5% sodium carbonate aqueous solution to purify the product by reprecipitation. The resulting precipitate was filtered and dried in a vacuum dryer at 120° C. for 6 hours to obtain 25.5 g of the intended triazine polymer P-1. The polystyrene-equivalent molecular weight measured by GPC was Mw=6800.

<Synthesis Example 2>
In a 500 mL four-necked flask, m-anisidine (14.69 g, 119.3 mmol, manufactured by Tokyo Kasei Kogyo Co., Ltd.) as ^a component of Z1, ^TAPOB (10.59 g, 26.51 mmol, Seika Co., Ltd.) as a component of Z2. ), triethylamine (20.78 g, 205.45 mmol) was added, dissolved in NMP (90 g), and heated to 40° C. in an oil bath. After that, as a triazine component, a solution of TCT (12.22 g, 66.28 mmol, manufactured by Tokyo Kasei Kogyo Co., Ltd.) dissolved in 49 g of NMP was added dropwise over 30 minutes. After stirring for 1 hour after the completion of dropping, the mixture was further heated at 130° C. for 1 hour and cooled to room temperature. The resulting reaction solution was filtered to remove the precipitate and the filtrate was recovered. The filtrate was added dropwise to a 5% sodium carbonate aqueous solution to purify the product by reprecipitation. The resulting precipitate was filtered and dried in a vacuum dryer at 120° C. for 6 hours to obtain 23.2 g of the intended triazine polymer P-2. The polystyrene-equivalent molecular weight measured by GPC was Mw=1800.

<Synthesis Example 3>
In a 500 mL four-necked flask, m-anisidine (9.8 g, 79.53 mmol, manufactured by Tokyo Kasei Kogyo Co., Ltd.) as ^a component of Z1, ^TAPOB (15.89 g, 39.77 mmol, Seika Co., Ltd.) as a component of Z2. ), triethylamine (20.78 g, 205.45 mmol) was added, dissolved in NMP (90 g), and heated to 40° C. in an oil bath. After that, as a triazine component, a solution of TCT (12.22 g, 66.28 mmol, manufactured by Tokyo Kasei Kogyo Co., Ltd.) dissolved in 49 g of NMP was added dropwise over 30 minutes. After stirring for 1 hour after the completion of dropping, the mixture was further heated at 130° C. for 1 hour and cooled to room temperature. The resulting reaction solution was filtered to remove the precipitate and the filtrate was recovered. The filtrate was added dropwise to a 5% sodium carbonate aqueous solution to purify the product by reprecipitation. The resulting precipitate was filtered and dried in a vacuum dryer at 120° C. for 6 hours to obtain 25.7 g of the desired triazine polymer P-3. The polystyrene-equivalent molecular weight measured by GPC was Mw=28,200.

<Synthesis Example 4>
Triazine polymer P-4 ( 25.4 g) were synthesized. The polystyrene equivalent molecular weight measured by GPC was Mw=4400.

<Synthesis Example 5>
Triazine polymer P- 5 (25.5 g) was synthesized. The polystyrene-equivalent molecular weight measured by GPC was Mw=5,300.

<Synthesis Example 6>
In a 500 mL four-necked flask, m-anisidine (11.43 g, 92.79 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.) and 3,3′ ^- DDS (13.17 g, 53.02 mmol, Seika Co., Ltd.) were added as components of Z1. ), triethylamine (20.78 g, 205.45 mmol) was added, dissolved in NMP (90 g), and heated to 40° C. in an oil bath. After that, a solution of TCT (12.22 g, 66.28 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 49 g of NMP was added dropwise over 30 minutes. After stirring for 1 hour after the completion of dropping, the mixture was further heated at 130° C. for 1 hour and cooled to room temperature. The resulting reaction solution was filtered to remove the precipitate and the filtrate was recovered. The filtrate was added dropwise to a 5% sodium carbonate aqueous solution to purify the product by reprecipitation. The resulting precipitate was filtered and dried in a vacuum dryer at 120° C. for 6 hours to obtain 26.5 g of the desired triazine polymer P-6. The polystyrene-equivalent molecular weight measured by GPC was Mw=7,100.

<Synthesis Example 7>
In a 500 mL four-necked flask, 3-methylthioaniline (16.61 g, 119.3 mmol, manufactured by Tokyo Kasei Kogyo Co., Ltd.) as ^a component of Z1, ^TAPOB (10.59 g, 26.5 mmol, Seika (10.59 g, 26.5 mmol) as a component of Z2 Co., Ltd.) was added, dissolved in NMP (90 g), and heated to 40° C. in an oil bath. After that, as a triazine component, a solution of TCT (12.22 g, 66.28 mmol, manufactured by Tokyo Kasei Kogyo Co., Ltd.) dissolved in 49 g of NMP was added dropwise over 30 minutes. After stirring for 1 hour after the completion of dropping, the mixture was further heated at 130° C. for 1 hour and cooled to room temperature. The resulting reaction solution was filtered to remove the precipitate and the filtrate was recovered. The filtrate was added dropwise to a 5% sodium carbonate aqueous solution to purify the product by reprecipitation. The resulting precipitate was filtered and dried in a vacuum dryer at 120° C. for 6 hours to obtain 28 g of the desired triazine polymer P-1. The polystyrene-equivalent molecular weight measured by GPC was Mw=2,100.

<Synthesis Example 8>
In a 500 mL four-neck flask, 3-methylthioaniline (15.69 g, 112.68 mmol, manufactured by Tokyo Kasei Kogyo Co., Ltd.) as a component of Z ¹ , aminopropyltriethoxysilane ( 1.47 g, 6.6 mmol, Shin-Etsu Chemical Co., Ltd.) TAPOB (10.59 g, 26.5 mmol, Seika Co., Ltd.) was added as a component of Z ² , dissolved in NMP (90 g), and heated to 40 ° C. in an oil bath. heated to After that, as a triazine component, a solution of TCT (12.22 g, 66.28 mmol, manufactured by Tokyo Kasei Kogyo Co., Ltd.) dissolved in 49 g of NMP was added dropwise over 30 minutes. After stirring for 1 hour after the completion of dropping, the mixture was further heated at 130° C. for 1 hour and cooled to room temperature. The resulting reaction solution was filtered to remove the precipitate and the filtrate was recovered. The filtrate was added dropwise to a 5% sodium carbonate aqueous solution to purify the product by reprecipitation. The resulting precipitate was filtered and dried in a vacuum dryer at 120° C. for 6 hours to obtain 28 g of the desired triazine polymer P-1. The polystyrene-equivalent molecular weight measured by GPC was Mw=2,300.

<Synthesis Example 9>
In a 500 mL four-neck flask, 3-methylthioaniline (15.69 g, 112.68 mmol, manufactured by Tokyo Kasei Kogyo Co., Ltd.) as a component of Z ¹ , m-aminophenyltrimethoxy as a component having a terminal or side chain silyl group Silane (1.41 g, 6.6 mmol, manufactured by Gelest) ^TAPOB (10.59 g, 26.5 mmol, manufactured by Seika Co., Ltd.) was added as a component of Z2, dissolved in NMP (90 g), and dried in an oil bath. Heated to 40°C. After that, as a triazine component, a solution of TCT (12.22 g, 66.28 mmol, manufactured by Tokyo Kasei Kogyo Co., Ltd.) dissolved in 49 g of NMP was added dropwise over 30 minutes. After stirring for 1 hour after the completion of dropping, the mixture was further heated at 130° C. for 1 hour and cooled to room temperature. The resulting reaction solution was filtered to remove the precipitate and the filtrate was recovered. The filtrate was added dropwise to a 5% sodium carbonate aqueous solution to purify the product by reprecipitation. The resulting precipitate was filtered and dried in a vacuum dryer at 120° C. for 6 hours to obtain 28 g of the desired triazine polymer P-1. The polystyrene-equivalent molecular weight measured by GPC was Mw=2,200.

Table 1 shows the composition of the polymer synthesized in each synthesis example.

Example 1
5 g of the triazine polymer P-1 obtained in Synthesis Example 1, 4 g of DMSO, and 16 g of MDM were mixed, shaken and stirred, and then filtered through a 0.45 μm diameter filter to obtain Composition 1. For the resulting composition, production of a cured film, refractive index measurement, transmittance measurement, high temperature and high humidity test, and adhesion test were carried out by the following methods. Table 2 shows the composition, and Table 3 shows the evaluation results.

<Production of test substrate>
A silicon wafer and a 5 cm square glass substrate (manufactured by AGC Techno Glass Co., Ltd., thickness 0.5 mm) were each coated with the composition of the example with a spinner so that the film thickness after curing was 0.5 μm. After that, it was pre-baked on a hot plate at 100° C. for 5 minutes and further baked in a hot air oven at 230° C. for 60 minutes to obtain a test substrate. The film thickness was measured using Lambda Ace STM-602 (trade name, manufactured by Dainippon Screen Co., Ltd.) at a refractive index of 1.70.

<Film thickness measurement>
With respect to the silicon wafer test substrate, the thickness of the pre-baked film and the cured film was measured at a refractive index of 1.70 using Lambda Ace STM-602 (trade name, manufactured by Dainippon Screen Co., Ltd.).

<Refractive index measurement>
For the silicon wafer test substrate, the refractive index at a wavelength of 633 nm was measured at 23° C. using a Refractometer Prism Coupler PC-2000 manufactured by Metricon.

<Transmittance measurement>
A 5 cm square glass test substrate was measured at a wavelength of 400 to 800 nm using an ultraviolet-visible spectrophotometer "UV-260" (manufactured by Shimadzu Corporation). As a background measurement, the transmittance of the glass substrate alone was measured, and the transmittance of the composition was calculated by subtracting the transmittance of the glass substrate from the transmittance of the test substrate. For the measured values, the value at 400 nm and the average value from 450-800 nm were compared.

<High temperature and high humidity test>
After holding the test substrate at 85° C. and 85% for 200 hours using a compact acceleration tester SH-222 (manufactured by Espec Co., Ltd.), the refractive index and transmittance were measured.

<Adhesion test>
A 5 cm square glass test substrate was evaluated for adhesion according to IJIS "K5600-5-6 (established April 20, 1999)". Specifically, on the surface of the cured film, parallel straight lines of 11 orthogonal vertical and horizontal lines were drawn at intervals of 1 mm so as to reach the substrate of the glass plate with a cutter knife, and 100 squares of 1 mm × 1 mm were drawn. made. A cellophane adhesive tape (width = 18 mm, adhesive strength = 3.7 N / 10 mm) is attached to the surface of the cut cured film, rubbed with an eraser (JIS S6050 acceptable product) to adhere, hold one end of the tape, and hold it at a right angle to the plate. The number of squares remaining when the film was held and instantaneously peeled off was visually evaluated. The peeling area of the squares was evaluated as follows, and 3 or more was regarded as acceptable.
5: Peeling area = 0%
4: Peeling area = <5%
3: Peeling area = 5 to 14%
2: Peeling area = 15 to 34%
1: Peeling area = 35% to 64%
0: Peeling area = 65% to 100%.

Example 2
A composition 2 was obtained in the same manner except that the triazine polymer P-1 used in Example 1 was changed to P-2. The obtained composition was subjected to test substrate preparation, film thickness measurement, refractive index measurement, transmittance measurement, high temperature and high humidity test, and adhesion test. Table 2 shows the composition, and Table 3 shows the evaluation results.

Example 3
Composition 3 was obtained in the same manner except that the triazine polymer P-1 used in Example 1 was changed to P-3. The obtained composition was subjected to test substrate preparation, film thickness measurement, refractive index measurement, transmittance measurement, high temperature and high humidity test, and adhesion test. Table 2 shows the composition, and Table 3 shows the evaluation results.

Example 4
A composition 4 was obtained in the same manner except that the triazine polymer P-1 used in Example 1 was changed to P-4. The obtained composition was subjected to test substrate preparation, film thickness measurement, refractive index measurement, transmittance measurement, high temperature and high humidity test, and adhesion test. Table 2 shows the composition, and Table 3 shows the evaluation results.

Example 5
Composition 5 was obtained in the same manner except that the triazine polymer P-1 used in Example 1 was changed to P-5. The obtained composition was subjected to test substrate preparation, film thickness measurement, refractive index measurement, transmittance measurement, high temperature and high humidity test, and adhesion test. Table 2 shows the composition, and Table 3 shows the evaluation results.

Example 6
4.75 g of the triazine polymer P-3 obtained in Synthesis Example 3, 0.25 g of MW-100LM (manufactured by Sanwa Chemical), 4 g of DMSO, and 16 g of MDM were mixed, and after shaking and stirring, the particle diameter was 0.45 μm. Composition 1 was obtained by filtration through a filter with a diameter of 100 mm. Test substrate preparation, refractive index measurement, transmittance measurement, high-temperature and high-humidity test, and adhesion test were carried out on the resulting composition by the following methods. Table 2 shows the composition, and Table 3 shows the evaluation results.

Example 7
4.75 g of the triazine polymer P-3 obtained in Synthesis Example 3, 0.25 g of VG-3101L (manufactured by Printec), 4 g of DMSO, and 16 g of MDM were mixed, and after shaking and stirring, a particle diameter of 0.45 μm was obtained. to obtain composition 1. Test substrate preparation, refractive index measurement, transmittance measurement, high-temperature and high-humidity test, and adhesion test were carried out on the resulting composition by the following methods. Table 2 shows the composition, and Table 3 shows the evaluation results.

Example 8
4.5 g of triazine polymer P-3 obtained in Synthesis Example 3, 0.25 g of MW-100LM (manufactured by Sanwa Chemical), 0.25 g of VG-3101L (manufactured by Printec), 4 g of DMSO, MDM was mixed, shaken and stirred, and then filtered through a 0.45 μm diameter filter to obtain composition 1. Test substrate preparation, refractive index measurement, transmittance measurement, high-temperature and high-humidity test, and adhesion test were carried out on the resulting composition by the following methods. Table 2 shows the composition, and Table 3 shows the evaluation results.

Example 9
A composition 2 was obtained in the same manner except that the triazine polymer P-1 used in Example 1 was changed to P-7. The obtained composition was subjected to test substrate preparation, film thickness measurement, refractive index measurement, transmittance measurement, high temperature and high humidity test, and adhesion test. Table 2 shows the composition, and Table 3 shows the evaluation results.

Example 10
A composition 2 was obtained in the same manner except that the triazine polymer P-1 used in Example 1 was changed to P-8. The obtained composition was subjected to test substrate preparation, film thickness measurement, refractive index measurement, transmittance measurement, high temperature and high humidity test, and adhesion test. Table 2 shows the composition, and Table 3 shows the evaluation results.

Example 11
A composition 2 was obtained in the same manner except that the triazine polymer P-1 used in Example 1 was changed to P-9. The obtained composition was subjected to test substrate preparation, film thickness measurement, refractive index measurement, transmittance measurement, high temperature and high humidity test, and adhesion test. Table 2 shows the composition, and Table 3 shows the evaluation results.

Comparative example 1
A comparative composition 1 was obtained in the same manner except that the triazine polymer P-1 used in Example 1 was changed to P-6. The obtained composition was subjected to test substrate preparation, film thickness measurement, refractive index measurement, transmittance measurement, high temperature and high humidity test, and adhesion test. Table 2 shows the composition, and Table 3 shows the evaluation results.

Comparative example 2
A comparative composition 2 was obtained in the same manner except that the triazine polymer P-3 used in Example 6 was changed to P-6. The obtained composition was subjected to test substrate preparation, film thickness measurement, refractive index measurement, transmittance measurement, high temperature and high humidity test, and adhesion test. Table 2 shows the composition, and Table 3 shows the evaluation results.

Comparative example 3
A comparative composition 3 was obtained in the same manner except that the triazine polymer P-3 used in Example 7 was changed to P-6. The obtained composition was subjected to test substrate preparation, film thickness measurement, refractive index measurement, transmittance measurement, high temperature and high humidity test, and adhesion test. Table 2 shows the composition, and Table 3 shows the evaluation results.

Comparative example 4
A comparative composition 4 was obtained in the same manner except that the triazine polymer P-3 used in Example 8 was changed to P-6. The obtained composition was subjected to test substrate preparation, film thickness measurement, refractive index measurement, transmittance measurement, high temperature and high humidity test, and adhesion test. Table 2 shows the composition, and Table 3 shows the evaluation results.

The triazine polymer used in the examples maintained a high transmittance of 95% or more even after the high temperature and high humidity test.

The triazine ring polymer of the present invention and the resin composition containing the same can be used for liquid crystal displays, organic electroluminescence (EL) displays, quantum dot displays, optical semiconductor (LED) devices, solid-state imaging devices, organic thin-film solar cells, and dye sensitization. It can be suitably used as a member when producing electronic devices such as solar cells and organic thin film transistors (TFTs). In particular, it can be suitably used as a microlens, which is a member of a solid-state imaging device that requires a high refractive index.

Claims (5)

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

In the formula, X and Y are -S- or -NR ¹ -, and R ¹ is a hydrogen atom or an organic group. n is an integer of 1 or more. Z ¹ is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, an acetyl group, a group formed by combining one or more of these groups, or these groups and a single bond, a group consisting of a combination of one or more groups selected from -S-, -O-, -NR ² -, -(CO)-NH-, -(CO)-O- and -(CO)- show. Z ¹ may further have a substituent, and R ² is a hydrogen atom or an organic group. ^Z2 is represented by either (12), (13) or (14) below .

The triazine ring-containing polymer according to claim 1 , which has a partial structure represented by the following general formulas (15) to (17).

In the formula, R ⁷⁴ is a substituent having one or more of an alkoxyryl group, a hydroxysilyl group and a hydrosilyl group. * is a linking group directly connected to Y in the formula (1). A resin composition comprising the triazine ring-containing polymer according to claim 1 or 2 . A cured film obtained from the resin composition according to claim 3 . A solid-state imaging device comprising the cured film according to claim 4 .