TWI568772B - A triazine-containing polymer and a film-forming composition containing the polymer - Google Patents

Description

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

The present invention relates to a triazine ring-containing polymer and a film-forming composition containing the polymer. More specifically, the present invention relates to a triazine ring-containing hyperbranched polymer and a film containing the polymer. Use the composition.

Various attempts have been made to form high-performance polymer compounds. For example, a method of forming a high refractive index of a polymer compound is to introduce an aromatic ring, a halogen atom, or a sulfur atom. Among them, an episulfide polymer compound and an ethyl thioglycol polymer compound into which a sulfur atom is introduced have been used as a high refractive index lens for glasses.

Further, a method of achieving a higher refractive index of a polymer compound as a method of using an inorganic metal oxide is known.

For example, a method of increasing the refractive index by using a mixed material of a mixed siloxane polymer and a fine particle dispersion material in which zirconia or titanium oxide is dispersed is used (Patent Document 1).

Further, there is a method of introducing a condensed cyclic skeleton having a high refractive index into one part of a siloxane polymer (Patent Document 2).

In addition, many attempts have been made to impart heat resistance to a polymer compound. Specifically, introduction of an aromatic ring improves the heat resistance of the polymer compound, and is known. For example, the main chain has a polyaromatic hydrocarbon copolymer substituted with an aromatic repeating unit (Patent Document 3), and this polymer compound is mainly used for a heat resistant plastic.

The melamine resin is a triazine-based resin which is well known, but its decomposition temperature is much lower than that of a heat-resistant material such as graphite.

Heretofore, a heat-resistant organic material composed of carbon and nitrogen mainly uses an aromatic polyimine or an aromatic polyamine, and since these materials have a linear structure, the heat-resistant temperature is not high.

Further, the nitrogen-containing polymer material having heat resistance is, for example, a triazine-based condensation material (Patent Document 4).

However, in recent years, electronic devices such as liquid crystal displays, organic electroluminescence device (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) have been developed. High-performance polymer materials are required.

Specific properties required are, for example, 1) heat resistance, 2) transparency, 3) high refractive index, 4) light resistance, 5) high solubility, and 6) low volume shrinkage. In particular, optical materials are a problem due to deterioration of light, and therefore it is required to improve light resistance. In order to improve the light resistance, it is considered that the addition of the ultraviolet absorber or the introduction of a functional group having a stable radical to prevent deterioration or the like, but the polymer compound itself has few examples of high light resistance.

[Advanced technical literature] [Patent Literature]

[Patent Document 1] JP-A-2007-246877

[Patent Document 2] JP-A-2008-24832

[Patent Document 3] US Patent No. 5886130

[Patent Document 4] JP-A-2000-53659

[Summary of the Invention]

The present inventors have found that a hyperbranched polymer containing a repeating unit having a triazine ring and an alicyclic structure can achieve not only high heat resistance, high transparency, high refractive index, and high solubility by the polymer alone. It has a low volume shrinkage ratio and is excellent in light resistance, and can be used as a film-forming composition for producing an electronic device or an optical member (PCT/JP2011/068937).

However, the film composed of the super-branched polymer has problems such as difficulty in thick film formation, and needs to be improved when it is used as an optical material requiring a thick film.

The present invention has been made in view of such circumstances, and an object of the present invention is to provide a triazine ring-containing polymer having a film having a thickness of 1000 nm or more and a film having a high transparency and high light resistance, and a film of the polymer. A composition for formation.

In order to achieve the above object, the inventors of the present invention have conducted intensive studies on the above-mentioned superbranched polymer having an alicyclic structure excellent in light resistance, and found that the halogenated cyanuric urethane and the diamine containing an alicyclic structure are in an excess of amine conditions. The super-branched polymer having a terminal amine obtained by the reaction is combined with various cross-linking agents to form a film, and a thick film having high transparency and high light resistance can be easily formed, and the present invention has been completed.

In other words, the invention is

A super-branched polymer containing a triazine ring, characterized in that a cyanuric halide and a diamine compound having an alicyclic structure are used as an excess molar ratio of an amine group of the aforementioned diamine compound. The reaction product obtained by the reaction has at least one terminal amine group derived from the above diamine compound and contains a repeating unit structure represented by the following formula (1). (wherein R and R ' each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or an aralkyl group, and A represents an alkylene group having an alicyclic structure of 3 to 20).

2. The triazine ring-containing hyperbranched polymer according to the above item 1, wherein the halogenated cyanuric hydrazine and the aforementioned diamine compound having an alicyclic structure are halogenated cyanuric urethane: diamine compound =1: 2~1:6 to obtain the reaction.

3. The super-branched polymer containing a triazine ring according to Item 1 or 2, wherein the A represents at least one selected from the group consisting of the formulas (2) to (14), (wherein R ¹ and R ² each independently represent an alkylene group having a branched structure of a carbon number of 1 to 5).

4. The triazine ring-containing hyperbranched polymer according to the above item 3, wherein the aforementioned A is represented by the formula (14).

5. The triazine ring-containing hyperbranched polymer according to item 4 above, wherein the above R ¹ and R ² are each a methylene group.

A film-forming composition comprising the triazine ring-containing hyperbranched polymer according to any one of items 1 to 5 above and a crosslinking agent.

7. The film-forming composition according to the above item 6, wherein the crosslinking agent is a compound containing two or more blocked isocyanate groups in one molecule.

A film comprising the triazine ring-containing hyperbranched polymer according to any one of items 1 to 5 above.

A film characterized by the composition for forming a film according to the above item 6 or 7. The income of the person.

An optical member comprising a substrate and a film of the above item 8 or 9 formed on the substrate.

According to the present invention, it is possible to provide a triazine ring-containing polymer having a film having a thickness of 1000 nm or more and a film forming composition containing the polymer, which has high transparency and high light resistance.

The film containing the triazine ring-containing hyperbranched polymer of the present invention can be suitably used as a liquid crystal display, an organic electroluminescence device (EL) display, an optical semiconductor (LED) device, a solid-state imaging device, an organic thin film solar cell, and a pigment. It is used as a part of materials for sensitizing electronic devices such as solar cells and organic thin film transistors (TFTs). It can also be suitably used as a member for lenses requiring a high refractive index.

In particular, a thick film having high light resistance can be formed, and therefore it is expected to be applied to the field of optical materials.

[Formation of the Invention]

The invention is described in detail below.

The triazine ring-containing hyperbranched polymer of the present invention is obtained by reacting a cyanuric halide with a diamine compound having an alicyclic structure and reacting an amine group of the diamine compound into an excess molar ratio. It has at least one terminal amine group derived from the above-described diamine compound and contains a repeating unit structure represented by the following formula (1).

In the above formula, R and R ' each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or an aralkyl group.

In the present invention, the number of carbon atoms of the alkyl group is not particularly limited, but is preferably from 1 to 20, and more preferably from 1 to 10, more preferably from 1 to 3, in view of further improving the heat resistance of the polymer. The structure may be any of a chain shape, a branch shape, and a ring shape.

Specific examples of the alkyl group are methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, s-butyl, t-butyl, cyclobutyl, 1- Methyl-cyclopropyl, 2-methyl-cyclopropyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, Cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclobutyl, 1,2-dimethyl-cyclopropyl, 2,3-dimethyl -cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl Base-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl -n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl- N-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl- 1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl - Cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3-dimethyl -cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl-cyclobutyl, 2,4-dimethyl-cyclobutyl, 3,3-dimethyl-ring Butyl, 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, 2-ethyl-3-methyl-cyclopropyl, and the like.

The number of carbon atoms of the alkoxy group is not particularly limited, and is preferably from 1 to 20, and more preferably from 1 to 10, more preferably from 1 to 3, in view of further improving the heat resistance of the polymer. The structure of the alkyl moiety may be any of a chain, a branch, and a ring.

Specific examples of the alkoxy group are a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, an s-butoxy group, and a t-butoxy group. , n-pentyloxy, 1-methyl-n-butoxy, 2-methyl-n-butoxy, 3-methyl-n-butoxy, 1,1-dimethyl-n- Propyloxy, 1,2-dimethyl-n-propoxy, 2,2-dimethyl-n-propoxy, 1-ethyl-n-propoxy, n-hexyloxy, 1 -methyl-n-pentyloxy, 2-methyl-n-pentyloxy, 3-methyl-n-pentyloxy, 4-methyl-n-pentyloxy, 1,1-dimethyl -n-butoxy, 1,2-dimethyl-n-butoxy, 1,3-dimethyl-n-butoxy, 2,2-dimethyl-n-butoxy, 2 ,3-dimethyl-n-butoxy, 3,3-dimethyl-n-butoxy, 1-ethyl-n-butoxy, 2-ethyl-n-butoxy, 1 1,2-trimethyl-n-propoxy, 1,2,2,-trimethyl-n-propoxy, 1-ethyl-1-methyl-n-propoxy, 1- Ethyl-2-methyl-n-propoxy group and the like.

The carbon number of the aryl group is not particularly limited, but is preferably 6 to 40, and is considered to be improved. When the heat resistance of the polymer is more preferred, the carbon number is 6 to 16, more preferably 6 to 13.

Specific examples of the aryl group are phenyl, o-chlorophenyl, m-chlorophenyl, p-chlorophenyl, o-fluorophenyl, p-fluorophenyl, o-methoxyphenyl, p-methyl. Oxyphenyl, p-nitrophenyl, p-cyanophenyl, α-naphthyl, β-naphthyl, o-biphenyl, m-biphenyl, p-biphenyl, 1-oxime Base, 2-indenyl, 9-fluorenyl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9-phenanthryl.

The number of carbon atoms of the aralkyl group is not particularly limited, and is preferably from 7 to 20 carbon atoms, and the alkyl moiety may be any of a straight chain, a branch, and a ring.

Specific examples thereof are benzyl, p-methylphenylmethyl, m-methylphenylmethyl, o-ethylphenylmethyl, m-ethylphenylmethyl, p-ethylphenyl Base, 2-propylphenylmethyl, 4-isopropylphenylmethyl, 4-isobutylphenylmethyl, α-naphthylmethyl and the like.

The above-mentioned A is not particularly limited as long as it is an alkylene group having an alicyclic structure of 3 to 20, and the present invention is preferably a group represented by the formulae (2) to (14), and it is considered to further increase the obtained polymer. When it is light resistance, it is particularly preferably an alkylene group having a deducted alkane skeleton represented by the formula (14).

R ¹ and R ² described above independently of each other represent an alkylene group having a branched structure in a carbon number of 1 to 5.

The alkylene group has, for example, a methylene group, an ethyl group, a propyl group, a trimethylene group, a butyl group, a pentyl group, etc., and in consideration of further increasing the refractive index of the obtained polymer, it is preferably a carbon number. The alkyl group having 1 to 3 alkyl groups and the alkyl group having 1 to 2 carbon atoms are more preferably a methylene group or an ethyl group, and most preferably a methylene group.

Particularly, in the alkylene group of the above formula (14), it is preferred that both of R ¹ and R ² are a methylene group.

The weight average molecular weight of the super-branched polymer of the present invention is not particularly limited, but is preferably 400 to 500,000, more preferably 400 to 100,000, and is preferably 600 or more from the viewpoint of further improving heat resistance and reducing shrinkage. The viewpoint of improving the solubility and lowering the viscosity of the resulting solution is preferably 50,000. More preferably, it is 30,000 or less, more preferably 10,000 or less.

The weight average molecular weight of the present invention is an average molecular weight in terms of standard polystyrene by gel permeation chromatography (hereinafter referred to as GPC) analysis.

A method for producing a triazine ring-containing hyperbranched polymer used in the present invention will be described by way of example.

For example, as shown in the following Scheme (Scheme) 1, the superbranched polymer (17) is a halogenated cyanide urethane (15) and a norbornane diamine (16) as a norbornanediamine (16). The amine group is obtained by reacting a halogen atom of the halogenated cyanuric hydrazine (15) with an excess molar ratio in a suitable organic solvent.

Thus, a super-branched polymer (17) having an amine group derived from a raw material diamine group at at least one (triazine ring) terminal can be obtained by a reaction under an excess of an amine.

(wherein X is a halogen atom independently of each other.)

The amount of the raw material to be added may be any ratio of the amount of the amine-based super-branched polymer to the excess of the amine group, and may be any (15) 1 equivalent (mol), preferably diamine (16) 2 to 6 equivalents (mol), more preferably 2.5 to 6 equivalents (mol), still more preferably 3 to 5 equivalents (mol).

As the above organic solvent, various solvents which are usually used in such a reaction can be used, for example, tetrahydrofuran (THF), 1,4-dioxane, dimethyl hydrazine, N,N-dimethylformamide, N-methyl group. -2-pyrrolidone, tetramethylurea, hexamethylphosphoramine, N,N-dimethylacetamide, N-methyl-2-piperidone, N,N-dimethylacetamide, N ,N,N',N'-tetramethylmalonate, N-methylcaprolactam, N-ethinylpyrrolidine, N,N-diethylacetamide, N-ethyl -2-pyrrolidone, N,N-dimethylpropionate decylamine, N,N-dimethylisobutylguanamine, N-methylformamide, N,N'-dimethylpropanuril, etc. The amide solvent and a mixed solvent thereof.

Among them, preferred are THF, 1,4-dioxane, N,N-dimethylformamide, N-methyl-2-pyrrolidone, dimethyl hydrazine, and a mixed solvent thereof.

The reaction temperature can be appropriately set within the range from the melting point of the solvent to be used to the boiling point of the solvent, preferably 0 to 150 ° C, more preferably 60 to 100 ° C.

Particularly, from the viewpoints of suppressing linearity and increasing branching degree, the reaction temperature is preferably from 60 to 150 ° C, more preferably from 80 to 150 ° C, still more preferably from 80 to 120 ° C.

The order of mixing the components may be any, and the solution containing the cyanuric halide cyanide (15) or the diamine (16) and the organic solvent is heated to 60 to 150 ° C, preferably 80 to 150 ° C, at this temperature, The method of adding a diamine (16) or a cyanogen halide cyanide (15) to the solution is preferred.

In this case, the component previously dissolved in the solvent and the component to be added later may be added, but the method of adding the cyanide urethane (15) to the heated solution of the diamine (16) Preferably.

The component to be added later may be added linearly or as a solution dissolved in an organic solvent as described above, and the latter method is preferable in consideration of easiness of handling or ease of control of the reaction.

Further, it may be added slowly by dropping or the like, or may be added in one portion.

In Fig. 1, after mixing the two compounds in a heated state, even if the reaction is carried out in one step (without stepwise increase in temperature), gelation does not occur, and the desired triazine ring-containing hyperbranched can be obtained. polymer.

In the above reaction, various bases which are usually used may be added during or after the polymerization.

Specific examples of the base include potassium carbonate, potassium hydroxide, sodium carbonate, sodium hydroxide, sodium hydrogencarbonate, sodium ethoxide, sodium acetate, lithium carbonate, lithium hydroxide, lithium oxide, potassium acetate, magnesium oxide, calcium oxide, and hydrogen. Cerium oxide, trilithium phosphate, trisodium phosphate, tripotassium phosphate, cesium fluoride, aluminum oxide, ammonia, trimethylamine, triethylamine, diisopropylmethylamine, diisopropylethylamine, N-methyl Pyridine, 2,2,6,6-tetramethyl-N-methylpiperidine, pyridine, 4-dimethylaminopyridine, N-methylmorpholine and the like.

The amount of the base added is 1 equivalent to the halogenated cyanuric hydrazine (15), preferably 1 to 100 equivalents, more preferably 1 to 10 equivalents. These bases can be used after forming an aqueous solution.

In the obtained polymer, it is preferred that the raw material component is not left, but a part of the raw material may remain without impairing the effects of the present invention.

In any of the illustrated methods, after the reaction is completed, the product can be easily purified by a reprecipitation method or the like.

In the production of the triazine ring-containing hyperbranched polymer of the present invention, after reacting the halogenated cyanuric hydrazine with the above diamine compound, the alkanolamine is added and then heated and stirred, although the reason is not clear, but the yield can be reduced. The coloration of the super-branched polymer improves the transparency of the film obtained therefrom.

Specific examples of the alkanolamine are methanolamine, ethanolamine, propanolamine, 1-amino-2-propanol, 1-amino-2-butanol, 1-amino-3-butanol, 4-amino group 1-butanol and the like.

In this case, the amount of the alkanolamine used is not particularly limited, and is preferably 0.05 to 500 equivalents, more preferably 0.05 to 120 equivalents, still more preferably 0.05 to 50 equivalents per equivalent of the cyanuric halide.

The treatment temperature at this time is preferably from 60 to 150 ° C, more preferably from 80 to 150 ° C, still more preferably from 80 to 120 ° C.

The film-forming composition of the present invention contains the above-mentioned super-branched polymer, and can be used, for example, by dissolving the super-branched polymer in a composition of various solvents.

The solvent for dissolving the polymer may be the same as or different from the solvent used for the polymerization. The solvent is not particularly limited as long as it does not affect the compatibility with the polymer, and one type or a plurality of types can be used arbitrarily.

Specific examples of such a solvent are toluene, p-xylene, o-xylene, m-xylene, ethylbenzene, styrene, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, Propylene glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol methyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether , propylene glycol monobutyl ether, ethylene glycol monobutyl ether, diethylene glycol diethyl ether, dipropylene glycol monomethyl ether, diethylene glycol Monomethyl ether, dipropylene glycol monoethyl ether, diethylene glycol monoethyl ether, triethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, γ-butyrolactone, acetone, methyl ethyl ketone, methyl Isopropyl ketone, diethyl ketone, methyl isobutyl ketone, methyl n-butyl ketone, cyclohexanone, ethyl acetate, isopropyl ketone, n-propyl acetate, isobutyl acetate, acetic acid Butyl ester, ethyl lactate, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, 1-pentanol, 2-methyl-2-butanol, 2-methyl 1-butanol, 1-hexanol, cyclohexanol, 2-methyl-1-pentanol, 1-heptanol, 1-octanol, 2-ethylhexanol, 1-methoxy-2 -butanol, diacetone alcohol, allyl alcohol, ethylene glycol, propylene glycol, hexanediol, triethylene glycol, decyl alcohol, tetrahydrofurfuryl alcohol, benzyl alcohol, diethylene glycol, 1,3-butylene glycol, 1 , 4-butanediol, 2,3-butanediol, diisopropyl ether, tetrahydrofuran, 1,4-dioxane, N,N-dimethylformamide, N,N-dimethylacetamide , N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidone, dimethyl hydrazine, N-cyclohexyl-2-pyrrolidone, etc., solubility and preservation stability from polymers More preferably, it is propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monobutyl ether, cyclohexanone or the like.

In this case, the solid content concentration in the film-forming composition is not particularly limited as long as it does not affect the storage stability, and the film thickness for the purpose of the blending may be appropriately set. Specifically, from the viewpoint of solubility and storage stability, the solid content concentration is preferably from 0.1 to 50% by mass, and when it is considered to form a thicker film, it is preferably from 1 to 30% by mass.

The film-forming composition of the present invention may contain other components such as a flat agent, a surfactant, a crosslinking agent, etc., within a range not affecting the effects of the present invention. Especially in order to improve the light fastness of the film obtained from the composition. For the purpose of strength or the like, it is preferred to contain a crosslinking agent.

The surfactants are, for example, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl phenol ether, polyoxygen Polyoxyethylene alkyl allyl ethers such as vinyl nonylphenol ether; polyoxyethylene. Polyoxypropylene block copolymers; sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitol A sorbitan fatty acid ester such as an anhydride trioleate or sorbitan tristearate; polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, poly Polyoxyethylene sorbitan fatty acid esters such as oxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, etc. Nonionic surfactants, trade names EFtop EF301, EF303, EF352 (Mitsubishi Materia Electronic Chemical Co., Ltd. (product), Jegco), trade name Megafac F171, F173, F554, R-08, R-30 ( DIC (share) system, Fluorad FC430, FC431 (Sumitomo 3M (share) system), trade name Asahiguad AG710, Suflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd.) Fluorine-based surfactant, organic siloxane 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 (BYK.Japan (shares), Ltd.) and the like.

These surfactants may be used singly 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, more preferably 0.001 to 1 part by mass, more preferably 100 parts by mass of the super-branched polymer. 0.01 to 0.5 parts by mass.

The crosslinking agent is not particularly limited as long as it is a compound having a substituent reactive with the hyperbranched polymer of the present invention.

Such a compound is, for example, a melamine-based compound having a cross-linking to form a substituent such as a methylol group or a methoxymethyl group, a substituted urea-based compound, or a compound containing a crosslinking group such as an epoxy group or a glycidyl group to form a substituent. a compound having an isocyanate group, a compound having a blocked isocyanate group, a compound having an acid anhydride, a compound having a (meth)acrylinyl group, a phenoplast compound, or the like, but from the viewpoint of heat resistance or preservation stability It is preferably a compound containing an epoxy group, a blocked isocyanate group or a (meth)acryl fluorenyl group.

Further, since the blocked isocyanate group is crosslinked by a urea bond and has a carbonyl group, it is preferable from the viewpoint of not lowering the refractive index, low-temperature curability, and thick film formation.

When such a compound is used for terminal treatment of a polymer, it is only required to have at least one crosslink to form a substituent, and it is necessary to have at least two crosslinks to form a substituent when the polymers are crosslinked.

The epoxy compound has two or more epoxy groups in one molecule, and when it is at a high temperature at the time of thermosetting, the epoxy is ring-opened, and is subjected to an addition reaction with the super-branched polymer of the present invention. Responders.

Specific examples of the crosslinking agent are tris(2,3-epoxypropyl)trimeric isocyanate, 1,4-butanediol diglycidyl ether, 1,2-epoxy-4-(epoxy B) Base) cyclohexane, glycerol triglycidyl ether, diethylene glycol diglycidyl ether, 2,6-diglycidylphenyl glycidyl ether, 1,1,3-tri [p-(2,3- Epoxy Propyloxy)phenyl]propane, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, 4,4'-methylene bis(N,N-diglycidylaniline), 3,4-ring Oxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, trimethylolethane triglycidyl ether, bisphenol A-diglycidyl ether, pentaerythritol polyglycidyl ether, and the like.

Commercially available epoxy resin YH-434, YH434L (manufactured by Tohto Kasei Co., Ltd.), epoxy resin EPOLEAD GT-401 having a cyclohexene oxide structure, and GT-403 can be used. , with GT-301, with GT-302, CELLOXID2021, CELLOXID3000 (Daicel Chemical Industry Co., Ltd.), bisphenol A epoxy resin epitote (now jER) 1001, same 1002, same 1003, same 1004, same 1007, Same as 1009, 1010, 828 (above is Japan Epoxy Resin), bisphenol F epoxy resin Epikote (present-day jER) 807 (made by Japan Epoxy Resin), novolac epoxy resin Epikote (now jER) 152, the same 154 (above is Japan Epoxy Resin (share) system), EPPN 201, the same 202 (above is the Japanese chemical (stock) system), cresol novolac type epoxy resin EOCN-102, EOCN- 103S, EOCN-104S, EOCN-1020, EOCN-1025, EOCN-1027 (above is Nippon Chemical Co., Ltd.), Epikote (present-day jER) 180S75 (made by Japan Epoxy Resin Co., Ltd.), alicyclic epoxy Resin DENACOL EX-252 (manufactured by Nagasechemtex Co., Ltd.), CY175, CY177, CY179 (above, CIBA-GEIGY AG), araldite CY-182, CY-192, and CY-184 (above, CIBA-GEIGY AG) , EPICLON 2 00, the same 400 (above DIC (share) system), Epikote (now jER) 871, the same 872 (above is Japan Epoxy Resin (share) system), FD-5661, ED-5662 (above is Celanese Coating (share) system, aliphatic polyglycidyl ether DENACOL EX-611, with EX-612, with EX-614, with EX-622, with EX-411, with EX-512, with EX-522, with EX -421, the same EX-313, the same EX-314, the same EX-321 (nagasechemtex (share) system).

The acid anhydride compound is, for example, a carboxylic acid anhydride which dehydrates and condenses two molecules of a carboxylic acid, and when it is at a high temperature at the time of thermosetting, the acid anhydride ring is opened, and is subjected to an addition reaction with the super-branched polymer of the present invention. Cross-linking reaction.

Further, specific examples of the acid anhydride compound include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, maleic anhydride, and amber. An acid anhydride, octyl succinic anhydride, dodecene succinic anhydride or the like having one acid anhydride group in the molecule; 1,2,3,4-cyclobutane tetracarboxylic dianhydride, pyromellitic anhydride, 3,4 -Dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic dianhydride, 5-(2 , 5-dioxaxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 1,2,3,4-butanetetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2-bis(3,4-di Carboxyphenyl) hexafluoropropane dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride or the like having two acid anhydride groups in the molecule.

The (meth) acrylonitrile compound has two or more (meth) acrylonitrile groups in one molecule, and is subjected to an addition reaction with the hyperbranched polymer of the present invention at a high temperature at the time of thermosetting. Conduct cross-linking reaction.

A compound having a (meth) acrylonitrile group, for example, ethylene glycol diacrylate, ethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, ethoxy group 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 monooxirane polyacrylic acid Ester, polyglycerol polyethylene glycol polyacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, pentaerythritol triacrylate, pentaerythritol Trimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tricyclodecane dimethanol diacrylate, tricyclodecane dimethanol dimethacrylate, 1, 6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, and the like.

The above compound having a (meth) acrylonitrile group can be obtained from a commercial product, and specific examples thereof include Nkester 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 (above is New Nakamura Chemical Industry Co., Ltd.), KAYARAD (registered trademark) DPEA-12, same as PEG400DA, same as THE-330, same as RP-1040 (above is Nippon Chemical Co., Ltd.) ), M-210, M-350 (above is East Asia Synthetic (Share)), KAYARAD (registered trademark) DPHA, with NPGDA, with PET30 (above is Nippon Chemical Co., Ltd.), NKester A-DPH, Same as A-TMPT, Same as A-DCP, the same A-HD-N, the same TMPT, the same DCP, the same NPG, the same HD-N (the above is the new Nakamura Chemical Industry Co., Ltd.).

The compound containing a blocked isocyanate group is a blocked isocyanate group having two or more isocyanate groups (-NCO) in one molecule and a suitable protecting group block, and is at a high temperature at the time of thermosetting, a protective group (block) Partly) generating thermal dissociation and detachment, and generating a cross-linking reaction between the produced isocyanate group and the super-branched polymer of the present invention, for example, having two or more molecules in one molecule (the groups may be the same or different from each other) A compound of the group represented by the following formula.

(wherein R _b represents an organic group of a block moiety.)

Such a compound is obtained, for example, by reacting a suitable block agent with respect to a compound having two or more isocyanate groups in one molecule.

a compound having two or more isocyanate groups in one molecule, for example, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, methylene bis(4-cyclohexyl isocyanate), trimethylhexamethylene Polyisocyanates of bis-isocyanates or such dimers, terpolymers and the like, and reactants with diols, triols, diamines, or triamines.

The block agent is, for example, methanol, ethanol, isopropanol, n-butanol, 2-ethoxyhexanol, 2-N,N-dimethylaminoethanol, 2-ethoxyethanol, cyclohexanol, etc. Alcohols; phenols such as phenol, o-nitrophenol, p-chlorophenol, o-, m- or p-cresol; indoleamines such as ε-caprolactam, acetone oxime, methyl Ethyl ketoxime , methyl isobutyl ketone oxime, cyclohexanone oxime, acetophenone oxime, benzophenone oxime and the like; pyrazole, 3,5-dimethylpyrazole, 3-methylpyrazole, etc. Pyrazoles; mercaptans such as dodecanethiol and benzenethiol.

The compound containing a blocked isocyanate group can be obtained from a commercial item, and specific examples thereof are B-830, B-815N, B-842N, B-870N, B-874N, B-882N, B-7005, B-7030, B-7075, B-5010 (above is Mitsui Chemicals Co., Ltd.), duranate (registered trademark) 17B-60PX, same TPA-B80E, same MF-B60X, same MF-K60X, same as E402-B80T (above is Asahi Kasei Chemicals (manufactured by the company), Karenz MOI-BM (registered trademark) (above is the Showa Denko (share) system).

The compound containing an isocyanate group, for example, a compound having two or more isocyanate groups in one molecule, particularly preferably a polyfunctional isocyanate compound of the type of isocyanurate, which is also commercially available, for example, duranate ( Registered trademark) 24A-100, 22A-75P, 21S-75E, TPA-100, TKA-100, MFA-75B, MHG-80B, TLA-100, TSE-100, TSA-100, TSS-100, TSE-100 , P301-75E, E402-80B, E405-70B, AE700-100, D101, D201, A201H, etc.

A phenoplast compound has two or more methoxymethylene groups in one molecule and is crosslinked by a de-methanol condensation reaction with the super-branched polymer of the present invention at a high temperature at the time of thermosetting. Responder.

The melamine-based compound is, for example, hexamethoxymethyl melamine CYMEL (registered trademark) 303, tetrabutoxymethyl glycoluril with 1170, tetramethoxymethylbenzoguanamine and 1123 (above is Japanese Cytec) Industries (shares), etc. Cymel series, methylated melamine resin NIKALAC (registered trademark) MW-30HM, same MW-390, same MW-100LM, same MX-750LM, methylated urea resin with MX-270 The NIKALAC series, such as MX-280 and MX-290 (the above are (Stock) III and Chemical).

The oxime oxide (OXETANE) compound has two or more epoxy propyl groups in one molecule, and at a high temperature at the time of thermosetting, cross-linking reaction with the super-branched polymer of the present invention by an addition reaction By.

Examples of the compound having an oxetanyl group include OXT-221, OX-SQ-H, and OX-SC (manufactured by Toagosei Co., Ltd.) containing a glycidyl group.

The phenolic plastic compound is one which has two or more hydroxymethylene groups in one molecule and which is subjected to an addition reaction with the super-branched polymer of the present invention at a high temperature at the time of thermosetting.

Phenolic plastic compounds such as 2,6-dihydroxymethyl-4-methylphenol, 2,4-dihydroxymethyl-6-methylphenol, bis(2-hydroxy-3-hydroxymethyl-5-methyl) Phenyl)methane, bis(4-hydroxy-3-hydroxymethyl-5-methylphenyl)methane, 2,2-bis(4-hydroxy-3,5-dihydroxymethylphenyl)propane, Bis(3-methylindol-4-hydroxyphenyl)methane, bis(4-hydroxy-2,5-dimethylphenyl)methanemethyl, α,α-bis(4-hydroxy-2,5 -Dimethylphenyl)-4-methylindenyltoluene or the like.

Phenolic plastic compounds are commercially available, and specific examples thereof are 26DMPC, 46DMOC, DM-BIPC-F, DM-BIOC-F, TM-BIP-A, BISA-F, BI25X-DF, BI25X-TPA (above Organic materials industry (shares) system, etc.

These crosslinking agents may be used singly or in combination of two or more. The amount of the crosslinking agent used is preferably from 1 to 100 parts by mass based on 100 parts by mass of the super-branched polymer. However, when solvent resistance is considered, the lower limit thereof is preferably 10 parts by mass, more preferably 20 parts by mass. When the refractive index is controlled, the upper limit thereof is preferably 50 parts by mass, more preferably 30 parts by mass.

By using a crosslinking agent, the crosslinking agent reacts with the terminal amine group which is reactive with the super-branched polymer, and the effect of improving film density, heat resistance, heat-reducing ability, and the like can be obtained.

The above other ingredients may be added at any step in the preparation of the composition of the present invention.

The film-forming composition of the present invention is applied to a substrate and then heated to form a desired film.

The coating method of the composition may be any method, and for example, a spin coating method, a dipping method, a flow coating method, an inkjet method, a spray method, a bar coating method, a gravure coating method, a slit coating method, and a roll may be employed. A method such as a coating method, a transfer printing method, a brush coating method, a blade coating method, or an air knife coating method.

The substrate is, for example, germanium, glass formed with an indium tin oxide (ITO) film, glass formed with an indium zinc oxide (IZO) film, polyethylene terephthalate (PET), plastic, glass, quartz, A flexible substrate having flexibility can also be used as a substrate made of ceramics or the like.

The firing temperature is not particularly limited as long as it evaporates the solvent, and can be carried out, for example, at 40 to 400 °C. When the crosslinking agent having the above-mentioned blocked isocyanate group is used, it may be heated at a low temperature of about 40 to 200 °C. In such cases, in order to have a higher uniform film forming property or to perform a reaction on a substrate In time, it is also possible to set a temperature change of two or more stages.

The baking method is not particularly limited, and for example, it can be evaporated in an appropriate atmosphere such as an 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 according to the conditions of the process steps of the electronic device suitable for the purpose, and the physical properties of the obtained film may be selected to suit the required characteristics of the electronic device.

The thickness of the film composed of the composition of the present invention thus obtained is not particularly limited, and the present invention can form a thick film as one of its characteristics, and therefore it may be 1000 nm or more or 1500 nm or more.

The film of the present invention can achieve high heat resistance, high transparency, high refractive index, high solubility, low volume shrinkage, and high light resistance, and thus can be suitably used as a liquid crystal display, an organic electroluminescence device (EL) display, and light. A member or an optical member is used for an electronic device such as a semiconductor (LED) element, a solid-state imaging device, an organic thin film solar cell, a dye-sensitized solar cell, or an organic thin film transistor (TFT).

The resin of the present invention may be added with other resins (thermoplastic resin or thermosetting resin) as necessary.

Specific examples of the resin are not particularly limited. The thermoplastic resin is, for example, a polyolefin resin such as PE (polyethylene), PP (polypropylene), EVA (ethylene-vinyl acetate copolymer), EEA (ethylene-ethyl acrylate copolymer); cyclic olefin Resin; PS (polystyrene), HIPS (high impact polystyrene), AS (acrylonitrile-styrene copolymer), ABS (acrylonitrile-butadiene-styrene copolymer), MS (methyl Methyl acrylate-styrene copolymer, etc. Polystyrene resin; polycarbonate resin; vinyl chloride resin; polyamide resin; polyimine resin; (meth)acrylic resin such as PMMA (polymethyl methacrylate); PET (polyphenylene terephthalate) Ethylene formate), polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, PLA (polylactic acid), poly-3-hydroxybutyric acid, polycaprolactone, polybutylene Polyester resin such as olefin succinate, polyethylene succinate/adipate; polyphenylene ether resin; modified polyphenylene ether resin; polyacetal resin; polyfluorene resin; polyphenylene sulfide resin; Alcohol resin; polyglutamic acid; modified starch; cellulose acetate, cellulose triacetate; chitin, chitosan; lignin, etc., thermosetting resin such as phenol resin, urea resin, melamine resin , unsaturated polyester resin, polyurethane resin, epoxy resin, and the like.

These resins may be used singly or in combination of two or more kinds, and the amount thereof is preferably from 1 to 10,000 parts by mass, more preferably from 1 to 1,000 parts by mass, per 100 parts by mass of the above-mentioned superbranched polymer.

For example, a composition of a (meth)acrylic resin is obtained by adding a (meth) acrylate compound to a composition and polymerizing a (meth) acrylate compound.

Examples of the (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, ethylene glycol di (meth) acrylate, and 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 trihydroxyethyl (meth)acrylate, tricyclodecane dimethanol di(methyl) Acrylate, three Cyclodecyl di(meth) acrylate, trimethylolpropane trihydroxypropyl (meth) acrylate, tris-2-hydroxyethyl trimeric isocyanate tri(meth) acrylate, tri-2-hydroxyl Ethyltrimeric isocyanate di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, pentaerythritol di(meth)acrylate, glycerol methacrylate acrylate, pentaerythritol tris(methyl) ) acrylate, trimethylolpropane trimethacrylate, allyl (meth) acrylate, vinyl (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, A urethane (meth) acrylate or the like.

The polymerization of these (meth) acrylate compounds can be carried out by light irradiation or heating in the presence of a photoradical initiator or a thermal radical initiator.

The photoradical initiators are, for example, acetophenones, benzophenones, benzamidine benzoate, amyloxim ester, tetramethylthiuram monosulfide and thiophene. Tons of ketones, etc.

Particularly preferred is a photocleaving type photoradical polymerization initiator. The light-cracking type photoradical polymerization initiator is described in the latest UV hardening technology (159 pages, issuer: Takahiro Ichihiro, issuer: (share) Technical Information Association, issued in 1991).

Commercially available photoradical polymerization initiators are, for example, manufactured by BASF Corporation: Irgacure 184, 369, 651, 500, 819, 907, 784, 2959, trade names: CGI1700, CGI1750, CGI1850, CG24-61, trade name :DAROCUR 1116,1173, trade name: Lucirin TPO, UCB company name: ubecryl P36, fratelli. Lamberti company name: Ezacure KIP150, KIP65LT, KIP100F, KT37, KT55, KTO46, KIP75/B, etc.

The photoradical polymerization 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.

The solvent for polymerization is, for example, the same as the solvent exemplified above for the film-forming composition.

[Examples]

The present invention will be more specifically illustrated by the following examples and comparative examples, but the present invention is not limited to the following examples. Each measuring device used in the examples is as follows.

[ ¹ H-NMR]

Device: JEOL-ECX300 (300MHz)

Determination of solvent: DMSO-d6

Reference material: tetramethyl decane (TMS) (δ0.0ppm)

[ ¹³ C-NMR]

Device: JEOL-ECA700 (700MHz)

Determination of solvent: DMSO-d6

Reference material: DMSO (δ39.5ppm)

Measuring temperature: room temperature

[GPC]

Device: HTC-8320 GPC made by Tosoh Corporation

Column: Shodex KF-802.5+KF-803L

Column temperature: 40 ° C

Solvent; 20 mM triethylamine added tetrahydrofuran

Detector: UV (254nm)

Checking line: standard polystyrene

[UV-visible spectrophotometer]

Device: (share) Shimadzu SU-3600 made by Shimadzu Corporation

[Ellipsometer (ellipsometer)]

Device: J.A.Woollam. Japan Multi-incidence Angle Spectroscopic Ellipsometer VASE

[Differential Thermal Scale (TG-DTA)]

Device: (stock) science system TG-8120

Heating rate: 15 ° C / min

Measuring temperature: 25~750°C

[Light resistance test]

Device: Q-Sun Xe-1 manufactured by Q-Lab Corporation

Illuminance: 0.55W/cm ² (@340nm)

Black panel temperature: 80 ° C

[Measurement of film thickness]

Ellipsometer

[1] Synthesis of super-branched polymers containing triazine rings [Example 1]

Under a nitrogen atmosphere, 189.6 g of N,N-dimethylacetamide was added to a 1000 mL four-necked flask, and then decanediamine [2] 138.81 g (0.9 mol, manufactured by Mitsui Chemicals Co., Ltd.) was added thereto. , heated to 85 ° C. Then, 2,4,6-trichloro-1,3,5-triazine [1] 55.18 g (0.3 mol, manufactured by EVONIK DEGUSSA) was dissolved in 352.1 g of dimethylacetamide, and it was kept at -10 °C. The solution was dropped and polymerization started. After 1 hour of the dropwise addition, 59.50 g of cyclohexylamine (0.6 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) and 90.13 g of DL-1-amino-2-propanol (1.2 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) were used. Under the mixed droplets, the mixture was stirred for 60 minutes. The reaction system was returned to room temperature, and the reaction liquid was added to 2500 g of ion-exchanged water for reprecipitation. The precipitate was filtered, and the filtrate was redissolved in THF 864 g. 28% ammonia solution 200 g. This solution was dropped into 4000 g of ion-exchanged water, reprecipitated, and the precipitate was filtered. The obtained solid matter was dried under reduced pressure at 150 ° C for 8 hours to obtain 56.6 g of the desired hyperbranched polymer [3] (hereinafter abbreviated as TNB-C).

The results of ¹ H-NMR spectrum measurement of TNB-C are shown in Fig. 1, and the results of ¹³ C-NMR spectrum measurement are shown in Fig. 18. The obtained TNB-C is a compound having a structural unit represented by the formula (1). Further, no signal of the characteristic aminopropanol was observed at 21 ppm, 48 ppm, and 65 ppm as measured by ¹³ C-NMR. Therefore, it was found that the obtained compound was not introduced with aminopropyl alcohol.

The weight average molecular weight Mw of the TNB-C measured by polystyrene conversion of GPC was 5,300, and the polydispersity Mw/Mn was 8.70.

<Measurement of refractive index and transmittance>

The TNB-C (0.1 g) obtained in Example 1 was dissolved in 0.9 g of propylene glycol monomethyl ether to obtain a colorless transparent solution. The obtained solution was spin-coated on a glass substrate at 100 rpm, 5 seconds, 800 rpm, and 30 seconds using a spin coater, and baked at 100 ° C for 1 minute, and baked at 250 ° C for 5 minutes to remove the solvent. A film (thickness 3517 nm) was obtained. The refractive index of the obtained film was measured, and the refractive index at 550 nm was measured to be 1.5997.

Further, the film obtained as described above was measured for a transmittance of 400 to 800 nm. The result is shown in Figure 2.

<heat resistance test>

The obtained TNB-C (4.970 mg) was placed in a platinum flat pan and measured by a TG-DTA at a heating rate of 15 ° C/min. As a result, the 5% weight loss was 433 ° C. The result is shown in Figure 3.

[2] Production of a film-forming composition (thermosetting composition) and a film [Embodiment 2]

0.25 g of TNB-C 1.0 g, Cymel 303 (manufactured by MT AQUAPOLYMER Co., Ltd.), and 0.0005 g of Megafac F-554 (manufactured by DIC Co., Ltd.) were dissolved in PGME 4.80 g and cyclohexanone 0.17 g to prepare a solid concentration of 20 Mass % solution (hereinafter referred to as TNB-CC2).

Using the obtained TNB-CC2, spin coating was performed for a film thickness of 2000 nm, and baking was performed at 100 ° C for 2 minutes, followed by baking at 150 ° C for 10 minutes to obtain a film (hereinafter abbreviated as TNB-CC2F).

[Example 3]

0.35 g of TNB-C 1.0 g, Cymel 303 (manufactured by MT AQUAPOLYMER Co., Ltd.), and 0.0005 g of Megafac F-554 (manufactured by DIC Co., Ltd.) were dissolved in PGME 5.20 g and cyclohexanone 0.19 g to prepare a solid concentration of 20 Mass % solution (hereinafter referred to as TNB-CC3).

Using the obtained TNB-CC3, spin coating was performed for a film thickness of 2000 nm, and baking was performed at 100 ° C for 2 minutes, followed by baking at 150 ° C for 10 minutes to obtain a film (hereinafter abbreviated as TNB-CC3F).

[Example 4]

0.45 g of TNB-C 1.0 g, Cymel 303 (manufactured by MT AQUAPOLYMER Co., Ltd.), and 0.0005 g of Megafac F-554 (manufactured by DIC Co., Ltd.) were dissolved in PGME 5.60 g and cyclohexanone 0.20 g to prepare a solid concentration of 20 Mass % solution (hereinafter referred to as TNB-CC4).

The obtained TNB-CC4 was spin-coated for the purpose of a film thickness of 2000 nm, baked at 100 ° C for 2 minutes, and then fired at 150 ° C for 10 minutes to obtain a film (hereinafter abbreviated as TNB-CC4F).

[Example 5]

0.055 g of TNB-C 1.0 g, B-882N (manufactured by Mitsui Chemicals Co., Ltd.), and 0.0005 g of Megafac F-554 (manufactured by DIC Co., Ltd.) were dissolved in PGME 4.40 g and cyclohexanone 0.10 g to prepare a solid fraction. A solution having a concentration of 20% by mass (hereinafter referred to as TNB-CB1).

The obtained TNB-CB1 was spin-coated for the purpose of a film thickness of 2000 nm, baked at 100 ° C for 2 minutes, and then fired at 150 ° C for 10 minutes to obtain a film (hereinafter abbreviated as TNB-CB1F).

[Embodiment 6]

0.15 g of TNB-C 1.0 g, B-882N (manufactured by Mitsui Chemicals Co., Ltd.), and 0.0005 g of Megafac F-554 (manufactured by DIC Co., Ltd.) were dissolved in PGME 4.80 g and cyclohexanone 0.17 g to prepare a solid component. A solution having a concentration of 20% by mass (hereinafter referred to as TNB-CB2).

Using the obtained TNB-CB2, spin coating was applied for a film thickness of 2000 nm, and baking was performed at 100 ° C for 2 minutes, followed by firing at 150 ° C. A film (hereinafter abbreviated as TNB-CB2F) was obtained in 10 minutes.

[Embodiment 7]

0.175 g of TNB-C 1.0 g, B-882N (manufactured by Mitsui Chemicals Co., Ltd.), and 0.0005 g of Megafac F-554 (manufactured by DIC Co., Ltd.) were dissolved in PGME 5.20 g and cyclohexanone 0.19 g to prepare a solid fraction. A solution having a concentration of 20% by mass (hereinafter referred to as TNB-CB3).

The obtained TNB-CB3 was spin-coated for the purpose of a film thickness of 2000 nm, baked at 100 ° C for 2 minutes, and then fired at 150 ° C for 10 minutes to obtain a film (hereinafter abbreviated as TNB-CB3F).

[Embodiment 8]

0.233 g of TNB-C 1.0 g, B-882N (manufactured by Mitsui Chemicals Co., Ltd.), and 0.0005 g of Megafac F-554 (manufactured by DIC Co., Ltd.) were dissolved in PGME 5.60 g and cyclohexanone 0.20 g to prepare a solid fraction. A solution having a concentration of 20% by mass (hereinafter referred to as TNB-CB4).

The obtained TNB-CB4 was spin-coated for a film thickness of 2000 nm, baked at 100 ° C for 2 minutes, and then fired at 150 ° C for 10 minutes to obtain a film (hereinafter abbreviated as TNB-CB4F).

<Measurement of refractive index, transmittance, and film thickness>

The film produced in the above Examples 2 to 8 was measured for transmittance, refractive index, and film thickness.

The transmittances of the films obtained in Examples 2 to 8 are as shown in Figs. 4 to 10, respectively. The refractive index and film thickness are shown in Table 1.

<Solvent tolerance test>

The film produced in each of Examples 2 to 8 was immersed in PGME for 5 minutes, and the film thickness after removal of PGME by spray drying was measured, and the solvent resistance was evaluated. The results of the residual film ratio are shown in Table 1.

As shown in Table 1, it was found that the terminal functional group of the super-branched polymer was combined with various crosslinking agents to obtain a curable coating film having a thickness of 1700 nm or more and excellent solvent resistance.

As shown in FIGS. 4 to 10, the obtained cured film has high transparency from the visible light region to the near-ultraviolet region.

Further, the polyolefin, PMMA, and cycloolefin polymer have a refractive index of about 1.49 to 1.55, but as shown in Table 1, the super-branched polymer composed of an alicyclic structure and a triazine ring is compared with the other. Etc., showing a higher refractive index.

<Light resistance test>

The film produced in the above Examples 2 to 8 was subjected to light resistance for 240 hours to carry out a light resistance test. Further, the refractive index after the light resistance test was measured.

The transmittances of the films obtained in Examples 2 to 8 after the light resistance test were as shown in Figs. 11 to 17, respectively, and the refractive indices are shown in Table 2.

As shown in FIGS. 11 to 17 and Table 2, it was found that the light resistance test of the xenon lamp did not change with the refractive index and the transmittance, and was a high light resistance material. Due to its high light resistance, it is expected to be used in the field of optical materials.

Fig. 1 is a ¹ H-NMR spectrum chart of the superbranched polymer [3] obtained in Example 1.

Fig. 2 is a view showing the transmittance of a film produced in Example 1.

Fig. 3 is a graph showing the results of TG-DTA measurement of the hyperbranched polymer [3] obtained in Example 1.

Fig. 4 is a view showing the transmittance of a film produced in Example 2.

Fig. 5 is a graph showing the transmittance of a film produced in Example 3.

Fig. 6 is a graph showing the transmittance of a film produced in Example 4.

Fig. 7 is a graph showing the transmittance of a film produced in Example 5.

Fig. 8 is a graph showing the transmittance of a film produced in Example 6.

Fig. 9 is a graph showing the transmittance of a film produced in Example 7.

Fig. 10 is a view showing the transmittance of a film produced in Example 8.

Fig. 11 is a graph showing the transmittance after 240 hours of light irradiation of the film produced in Example 2.

Fig. 12 is a graph showing the transmittance after 240 hours of light irradiation of the film produced in Example 3.

Fig. 13 is a graph showing the transmittance after 240 hours of light irradiation of the film produced in Example 4.

Fig. 14 is a graph showing the transmittance after 240 hours of light irradiation of the film produced in Example 5.

Fig. 15 is a graph showing the transmittance after 240 hours of light irradiation of the film produced in Example 6.

Fig. 16 is a graph showing the transmittance after 240 hours of light irradiation of the film produced in Example 7.

Fig. 17 is a graph showing the transmittance after 240 hours of light irradiation of the film produced in Example 8.

Fig. 18 is a chart showing the ¹³ C-NMR spectrum of the superbranched polymer [3] obtained in Example 1.

Claims (10)

A super-branched polymer containing a triazine ring, characterized in that a cyanuric halide and a diamine compound having an alicyclic structure are reacted with an excess of a molar ratio of an amine group of the aforementioned diamine compound. The obtained one has at least one terminal amine group derived from the aforementioned diamine compound, and contains a repeating unit structure represented by the following formula (1). (wherein R and R ' each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or an aralkyl group, and A represents an alkylene group having an alicyclic structure of 3 to 20 membered rings). The triazine ring-containing hyperbranched polymer according to claim 1, wherein the halogenated cyanuric urethane and the aforementioned diamine compound having an alicyclic structure are represented by a molar ratio of a cyanuric urethane: a diamine Compound = 1 : 2 ~ 1: 6 was obtained by reaction. The triazine ring-containing hyperbranched polymer according to claim 1 or 2, wherein the A represents at least one selected from the group consisting of the formulas (2) to (14). (wherein R ¹ and R ² each independently represent an alkylene group having a branched structure of a carbon number of 1 to 5). A triazine ring-containing hyperbranched polymer according to claim 3, wherein the aforementioned A is represented by the formula (14). The triazine ring-containing hyperbranched polymer of claim 4, wherein the foregoing R ¹ and R ² are methylene groups. A composition for forming a film, which comprises the triazine ring-containing hyperbranched polymer and a crosslinking agent according to any one of claims 1 to 5. The film-forming composition according to claim 6, wherein the crosslinking agent is a compound containing two or more blocked isocyanate groups in one molecule. A film characterized by containing a triazine ring-containing hyperbranched polymer according to any one of claims 1 to 5. A film obtained by the film-forming composition according to claim 6 or 7 of the patent application. An optical member characterized by comprising a substrate and a film of claim 8 or 9 formed on the substrate.