WO2015098788A1 - Triazine-polymer-containing composition - Google Patents

Abstract

A triazine-polymer-containing composition that can be used to form, by low-temperature firing, a thin film that has a high refractive index and excellent transparency, and can also be used to form a fine pattern that has a high refractive index. The triazine-polymer-containing composition includes: a polymer that includes a repeating structural unit such as is represented, for example, by formula (23), the repeating structural unit having a triazine ring and a phenolic hydroxyl group; and at least two types of photocrosslinking agents.

Description

Triazine polymer-containing composition

The present invention relates to a triazine polymer-containing composition.

In recent years, electronic devices such as liquid crystal displays, organic electroluminescence (EL) displays, touch panels, optical semiconductor (LED) elements, solid-state imaging elements, organic thin film solar cells, dye-sensitized solar cells, and organic thin film transistors (TFTs) have been developed. At the same time, high-performance polymer materials have been required.
Specific characteristics required include 1) heat resistance, 2) transparency, 3) high refractive index, 4) high solubility, 5) low volume shrinkage, 6) high temperature and high humidity resistance, and 7) high film hardness. Etc.
In view of this point, the present inventors have found that a polymer containing a repeating unit having a triazine ring and an aromatic ring has a high refractive index, and the polymer alone has high heat resistance, high transparency, high refractive index, and high solubility. It has already been found that a low volume shrinkage can be achieved and it is suitable as a film-forming composition for producing an electronic device (Patent Document 1).

By the way, pattern formation using a transparent material is performed on a spacer, an insulating film, a protective film, etc. in a liquid crystal display element, and many negative photosensitive compositions have been proposed for this purpose so far.
In particular, in recent years, due to the increasing demand for high-definition liquid crystal displays and mobile phone displays, small patterns with a diameter of 10 μm or less have been demanded.
In touch panels, the need for a high refractive index layer is increasing in order to improve the visibility of transparent electrodes. However, the presence of an insulating film in the electrode wiring part affects the responsiveness. Therefore, it is necessary to remove the insulating layer with a width of 100 to 1000 μm.
Existing materials used for this purpose are insufficient in terms of refractive index, and it is difficult to improve the refractive index to over 1.7 while maintaining transparency.
In this regard, the polymer of Patent Document 1 can meet the demand in terms of refractive index, but there is room for improvement in terms of fine pattern formability.

Although Patent Document 2 discloses a pattern-forming composition containing a triazine ring-containing polymer, the polymer has a refractive index of less than 1.7, and a higher refractive index is required. Not suitable for use.

In addition, due to the trend toward thinner and lighter devices in recent years, the use of materials with low heat resistance such as plastic film substrates is increasing, and there is a need for design of materials and compositions that can be fired at low temperatures during thin film production. Is growing.

International Publication No. 2010/128661 JP 2004-156001 A

The present invention has been made in view of the above circumstances, and can form a thin film having a high refractive index and excellent transparency by low-temperature firing, and can also form a fine pattern having a high refractive index. An object is to provide a coalescence-containing composition.

As a result of intensive studies in order to achieve the above object, the present inventors have obtained a composition comprising a triazine ring-containing polymer substituted with an arylamino group having a predetermined functional group, and two kinds of crosslinking agents. As a result, it was found that a thin film having a high refractive index and excellent transparency can be formed by low-temperature firing, and a fine pattern having a high refractive index can be formed, thereby completing the present invention.

That is, the present invention
1. A triazine-based polymer-containing composition comprising a polymer containing a repeating unit structure represented by the following formula (1) and at least two kinds of crosslinking agents:

{In the formula, R and R 'each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group, and Ar ¹ represents an aryl group having a hydroxyl group, a carboxyl group, and / or a maleimide group. Ar ² represents at least one selected from the group represented by formulas (2) to (13).

[Wherein R ¹ to R ⁹² are independently of each other a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group which may have a branched structure having 1 to 10 carbon atoms, or a carbon number of 1 Represents an alkoxy group which may have a branched structure of ˜10, R ⁹³ and R ⁹⁴ represent a hydrogen atom or an alkyl group which may have a branched structure of 1 to 10 carbon atoms, W ¹ and W ² is independently a single bond, CR ⁹⁵ R ⁹⁶ (R ⁹⁵ and R ⁹⁶ are each independently a hydrogen atom or an alkyl group optionally having a branched structure of 1 to 10 carbon atoms ( However, these may be combined to form a ring.))), C═O, O, S, SO, SO ₂ , or NR ⁹⁷ (R ⁹⁷ is a hydrogen atom or a carbon number of 1). have a branched structure to 10 represent also alkyl groups.) represents, X ¹ Contact Fine X ² are independently of each other a single bond, an alkylene group which may have a branched structure having 1 to 10 carbon atoms, or the formula, (14)

(Wherein R ⁹⁸ to R ¹⁰¹ are each independently a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group which may have a branched structure having 1 to 10 carbon atoms, or 1 carbon atom) Represents an alkoxy group which may have a branched structure of ˜10, and Y ¹ and Y ² each independently represent an alkylene group which may have a single bond or a branched structure of 1 to 10 carbon atoms. Represents a group represented by: ]}
2. 1 triazine polymer-containing composition, wherein the crosslinking agent is a combination of a polyfunctional (meth) acrylic compound and a polyfunctional epoxy compound;
3. 2. A triazine polymer-containing composition of 2, wherein the content of the polyfunctional (meth) acrylic compound and the polyfunctional epoxy compound is 1: 1 to 3: 1 by mass ratio;
4). The triazine polymer-containing composition according to any one of 1 to 3, wherein the polymer includes a repeating unit structure represented by the following formula (18):

(Wherein R, R ′ and Ar ² represent the same meaning as described above.)
5. 4 triazine-based polymer-containing composition containing a repeating unit structure represented by the following formula (19):

(Wherein R, R ′ and Ar ² represent the same meaning as described above.)
6). 5 a triazine polymer-containing composition containing a repeating unit structure represented by the following formula (23):

7). And a triazine polymer-containing composition according to any one of 1 to 6, further comprising an oxirane ring-containing compound and a photocurable catalyst.
8). And a triazine polymer-containing composition according to any one of 1 to 6, further comprising an azide compound,
9. Any one of triazine-based polymer-containing compositions for forming a pattern;
10. A cured film obtained by curing the triazine-based polymer-containing composition of any one of 1 to 8,
11. A pattern prepared from the triazine-based polymer-containing composition of 9;
12 An electronic device comprising a substrate and ten cured films formed on the substrate;
13. An optical member comprising a substrate and ten cured films formed on the substrate;
14 An electronic device comprising a substrate and eleven patterns formed on the substrate is provided.

According to the present invention, it is possible to form a thin film having a high refractive index and excellent transparency, and it is possible to form a fine pattern by masking, exposing and curing, and then performing alkali development or the like.
In particular, since two kinds of crosslinking agents are used in combination, there is an advantage that a thin film can be formed by low-temperature firing.
The cured film and fine pattern produced from the composition of the present invention can exhibit characteristics such as high heat resistance, high refractive index, and low volume shrinkage due to the crosslinked triazine ring-containing polymer. Luminescence (EL) display, touch panel, optical semiconductor (LED) element, solid-state imaging device, organic thin film solar cell, dye-sensitized solar cell, organic thin film transistor (TFT), lens, prism, camera, binoculars, microscope, semiconductor exposure device, etc. It can be suitably used in the field of electronic devices and optical materials, such as one member for manufacturing the device.
In addition, the high refractive index pattern produced from the composition of the present invention requires a high refractive index pattern including the above-mentioned prevention of transparent electrode bone appearance such as touch panel, light extraction use of organic EL display and black matrix use. It can be suitably used for the intended use.

1 is a ¹ H-NMR spectrum diagram of a polymer compound [4] obtained in Example 1. FIG. FIG. 3 is a graph showing a TG-DTA measurement result of the polymer compound [4] obtained in Example 1.

Hereinafter, the present invention will be described in more detail.
The triazine polymer-containing composition according to the present invention includes a polymer containing a repeating unit structure represented by the following formula (1) and at least two kinds of crosslinking agents.

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. However, from the viewpoint of further increasing the refractive index, both of them may be hydrogen atoms. preferable.
In the present invention, the number of carbon atoms of the alkyl group is not particularly limited, but is preferably 1 to 20, and more preferably 1 to 10 carbon atoms in view of further improving the heat resistance of the polymer. Is even more preferable. Further, the structure may be any of a chain, a branch, and a ring.

Specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, s-butyl, t-butyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl. N-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2 , 2-dimethyl-n-propyl, 1-ethyl-n-propyl, cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclobutyl, 1,2-dimethyl-cyclopropyl, 2,3- Dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, n-hexyl, 1-methyl-n-pe Til, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3- Dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n- Butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, Cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclyl Butyl, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl-cyclobutyl, 2,4-dimethyl-cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl 2-n-propyl-cyclopropyl, 1-isopropyl-cyclopropyl, 2-isopropyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2, 3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl, 2-ethyl-3-methyl-cyclopropyl Groups and the like.

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

Specific examples of the alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, s-butoxy, t-butoxy, n-pentoxy, 1-methyl-n-butoxy, 2-methyl-n -Butoxy, 3-methyl-n-butoxy, 1,1-dimethyl-n-propoxy, 1,2-dimethyl-n-propoxy, 2,2-dimethyl-n-propoxy, 1-ethyl-n-propoxy, n -Hexyloxy, 1-methyl-n-pentyloxy, 2-methyl-n-pentyloxy, 3-methyl-n-pentyloxy, 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- Examples include propoxy, 1-ethyl-1-methyl-n-propoxy, 1-ethyl-2-methyl-n-propoxy group.

The number of carbon atoms of the aryl group is not particularly limited, but is preferably 6 to 40. In view of further improving the heat resistance of the polymer, 6 to 16 carbon atoms are more preferable, and 6 to 13 are even more preferable. preferable.
Specific examples of the aryl group include phenyl, o-chlorophenyl, m-chlorophenyl, p-chlorophenyl, o-fluorophenyl, p-fluorophenyl, o-methoxyphenyl, p-methoxyphenyl, p-nitrophenyl, p-cyanophenyl, α-naphthyl, β-naphthyl, o-biphenylyl, m-biphenylyl, p-biphenylyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4 -Phenanthryl, 9-phenanthryl group and the like.

The number of carbon atoms of the aralkyl group is not particularly limited, but preferably 7 to 20 carbon atoms, and the alkyl portion may be linear, branched or cyclic.
Specific examples thereof include benzyl, p-methylphenylmethyl, m-methylphenylmethyl, o-ethylphenylmethyl, m-ethylphenylmethyl, p-ethylphenylmethyl, 2-propylphenylmethyl, 4-isopropylphenylmethyl, Examples include 4-isobutylphenylmethyl, α-naphthylmethyl group and the like.

Ar ¹ is not particularly limited as long as it is an aryl group having a hydroxyl group, a carboxyl group and / or a maleimide group, but those represented by the following formulas (15) to (17) are preferred.

(In the formula, R ¹⁰² to R ¹¹⁰ each independently represent the same meaning as R ¹ above.)

Among these, those represented by the following formulas in which the substituents R ¹⁰² to R ¹¹⁰ are hydrogen atoms are preferable.

In particular, those represented by the following formula are preferable from the viewpoint of improving the solubility of the obtained cured product in an alkaline developer.

Among the aryl groups described above, those having a phenolic hydroxyl group are preferred in view of the high refractive index and transparency of the resulting cured film and the resolution of the fine pattern.
Therefore, the triazine ring-containing polymer of the present invention preferably includes a repeating unit structure represented by the following formula (18), and more preferably includes a repeating unit structure represented by the following formula (19).

(In the formula, R, R ′ and Ar ² represent the same meaning as described above.)

(In the formula, R, R ′ and Ar ² represent the same meaning as described above.)

Ar ² represents at least one selected from the group represented by formulas (2) to (13).

R ¹ to R ⁹² are independently of each other a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group that may have a branched structure having 1 to 10 carbon atoms, or a group having 1 to 10 carbon atoms. Represents an alkoxy group which may have a branched structure, W ¹ and W ² are each independently a single bond, CR ⁹⁵ R ⁹⁶ (R ⁹⁵ and R ⁹⁶ are each independently a hydrogen atom or carbon; An alkyl group which may have a branched structure of 1 to 10 (note that these may be combined to form a ring), C═O, O, S, SO, SO ₂ , or NR ⁹⁷ (R ⁹⁷ represents a hydrogen atom or an alkyl group which may have a branched structure having 1 to 10 carbon atoms), and R ⁹³ and R ⁹⁴ represent a hydrogen atom or a carbon number Represents an alkyl group which may have 1 to 10 branched structures;
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the alkyl group and alkoxy group are the same as those described above.
X ¹ and X ² each independently represent a single bond, an alkylene group which may have a branched structure having 1 to 10 carbon atoms, or a group represented by the formula (14).

R ⁹⁸ to R ¹⁰¹ are each independently a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group which may have a branched structure having 1 to 10 carbon atoms, or a carbon atom having 1 to 10 carbon atoms. An alkoxy group which may have a branched structure is represented, and Y ¹ and Y ² each independently represent an alkylene group which may have a single bond or a branched structure having 1 to 10 carbon atoms. Examples of the halogen atom, alkyl group and alkoxy group are the same as those described above.
Examples of the alkylene group that may have a branched structure having 1 to 10 carbon atoms include methylene, ethylene, propylene, trimethylene, tetramethylene, and pentamethylene groups.

In particular, Ar is preferably at least one of the formulas (2), (5) to (13), and the formulas (2), (5), (7), (8), (11) to (13) More preferably, at least one selected from Specific examples of the aryl group represented by the above formulas (2) to (13) include, but are not limited to, those represented by the following formulae.

Among these, an aryl group represented by the following formula is more preferable because a polymer having a higher refractive index can be obtained.

In particular, it is preferable to include a repeating unit structure represented by the following formula (20) in view of further improving the solubility in a highly safe solvent such as a resist solvent, and a repeating unit structure represented by the following formula (21). It is more preferable that it contains.

(In the formula, R, R 'and R ¹ to R ⁴ have the same meaning as described above.)

(In the formula, R, R 'and R ¹ to R ⁴ have the same meaning as described above.)

From such a viewpoint, as a particularly preferable repeating unit structure, one represented by the following formula (22) can be mentioned, and one represented by the following formula (23) is more preferable.

(In the formula, R and R ′ have the same meaning as described above.)

The weight average molecular weight of the polymer in the present invention is not particularly limited, but is preferably 500 to 500,000, more preferably 500 to 100,000. From the viewpoint of further improving the heat resistance and reducing the shrinkage rate. It is preferably 2000 or more, preferably 50000 or less, more preferably 30000 or less, and even more preferably 10,000 or less from the viewpoint of further increasing the solubility and decreasing the viscosity of the obtained solution.
In addition, the weight average molecular weight in this invention is an average molecular weight obtained by standard polystyrene conversion by gel permeation chromatography (henceforth GPC) analysis.

The triazine ring-containing polymer used in the present invention can be produced by the technique disclosed in Patent Document 1 described above.
For example, as shown in Scheme 1 below, a triazine ring-containing polymer having a repeating structure (26) is obtained by reacting a triazine compound (24) having a phenylamino group and a diamino compound (25) in a suitable organic solvent. Can be obtained.
The compound represented by the above formula (24) can be produced from a cyanuric halide and 3-aminophenol by a known method. Further, the reaction may be carried out by adding a diamino compound into the reaction system of cyanuric halide and 3-aminophenol.

(Wherein X represents a halogen atom independently of each other. R and R ′ represent the same meaning as described above.)

In the above reaction, the amount of each raw material charged is arbitrary as long as the target polymer is obtained, but is preferably 0.01 to 10 equivalents of diamino compound (25) to 1 equivalent of triazine compound (24). 0.1 to 0.8 equivalent or 1 to 5 equivalent is more preferable.
The reaction temperature may be appropriately set in the range from the melting point of the solvent to be used to the boiling point of the solvent, but is preferably about −30 to 150 ° C., more preferably −10 to 100 ° C.

As the organic solvent, various solvents usually used in this kind of reaction can be used, for example, tetrahydrofuran, dioxane, dimethyl sulfoxide; N, N-dimethylformamide, N-methyl-2-pyrrolidone, tetramethylurea, Hexamethylphosphoramide, N, N-dimethylacetamide, N-methyl-2-piperidone, N, N-dimethylethyleneurea, 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'-dimethylpropylene urea Amide solvents such as, and mixed solvents thereof
Among these, N, N-dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, and a mixed system thereof are preferable, and N, N-dimethylacetamide, N-methyl-2-pyrrolidone are particularly preferable. Is preferred.

The order of blending the components is arbitrary, but a method of adding the diamino compound (25) to a solution containing the triazine compound (24) and the organic solvent is preferable.
Components added later may be added neat or in a solution dissolved in an organic solvent as described above, but the latter method is preferred in view of ease of operation and ease of reaction control. It is.
The addition may be gradually added by dropping or the like, or may be added all at once.

In the above reaction, various bases usually used during polymerization or after polymerization may be added.
Specific examples of this base include potassium carbonate, potassium hydroxide, sodium carbonate, sodium hydroxide, sodium hydrogen carbonate, sodium ethoxide, sodium acetate, lithium carbonate, lithium hydroxide, lithium oxide, potassium acetate, magnesium oxide, oxidized Calcium, barium hydroxide, trilithium phosphate, trisodium phosphate, tripotassium phosphate, cesium fluoride, aluminum oxide, ammonia, trimethylamine, triethylamine, diisopropylamine, diisopropylethylamine, N-methylpiperidine, 2,2,6 , 6-tetramethyl-N-methylpiperidine, pyridine, 4-dimethylaminopyridine, N-methylmorpholine and the like.
The amount of the base added is preferably 1 to 100 equivalents and more preferably 1 to 10 equivalents with respect to 1 equivalent of the triazine compound (24). These bases may be used as an aqueous solution.
Although it is preferable that the raw material component does not remain in the obtained polymer, a part of the raw material may remain as long as the effect of the present invention is not impaired.
In any of the scheme methods, after completion of the reaction, the product can be easily purified by a reprecipitation method or the like.

In the present invention, a part of halogen atoms of at least one terminal triazine ring is substituted with alkyl, aralkyl, aryl, alkylamino, alkoxysilyl group-containing alkylamino, aralkylamino, arylamino, alkoxy, aralkyloxy, aryloxy. , And may be capped with an ester group or the like.
Among these, alkylamino, alkoxysilyl group-containing alkylamino, aralkylamino, and arylamino groups are preferable, alkylamino and arylamino groups are more preferable, and arylamino groups are more preferable.
Examples of the alkyl group and alkoxy group are the same as those described above.

Specific examples of the ester group include methoxycarbonyl and ethoxycarbonyl groups.
Specific examples of the aryl group include phenyl, o-chlorophenyl, m-chlorophenyl, p-chlorophenyl, o-fluorophenyl, p-fluorophenyl, o-methoxyphenyl, p-methoxyphenyl, p-nitrophenyl, p-cyanophenyl, α-naphthyl, β-naphthyl, o-biphenylyl, m-biphenylyl, p-biphenylyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4 -Phenanthryl, 9-phenanthryl group and the like.
Specific examples of the aralkyl group include benzyl, p-methylphenylmethyl, m-methylphenylmethyl, o-ethylphenylmethyl, m-ethylphenylmethyl, p-ethylphenylmethyl, 2-propylphenylmethyl, 4-isopropylphenyl. Examples include methyl, 4-isobutylphenylmethyl, α-naphthylmethyl group and the like.

Specific examples of the alkylamino group include methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino, isobutylamino, s-butylamino, t-butylamino, n-pentylamino, 1-methyl- n-butylamino, 2-methyl-n-butylamino, 3-methyl-n-butylamino, 1,1-dimethyl-n-propylamino, 1,2-dimethyl-n-propylamino, 2,2-dimethyl -N-propylamino, 1-ethyl-n-propylamino, n-hexylamino, 1-methyl-n-pentylamino, 2-methyl-n-pentylamino, 3-methyl-n-pentylamino, 4-methyl -N-pentylamino, 1,1-dimethyl-n-butylamino, 1,2-dimethyl-n-butylamino, 1,3-dimethyl -N-butylamino, 2,2-dimethyl-n-butylamino, 2,3-dimethyl-n-butylamino, 3,3-dimethyl-n-butylamino, 1-ethyl-n-butylamino, 2- Ethyl-n-butylamino, 1,1,2-trimethyl-n-propylamino, 1,2,2-trimethyl-n-propylamino, 1-ethyl-1-methyl-n-propylamino, 1-ethyl- And 2-methyl-n-propylamino group.

Specific examples of the aralkylamino group include benzylamino, methoxycarbonylphenylmethylamino, ethoxycarbonylphenylmethylamino, p-methylphenylmethylamino, m-methylphenylmethylamino, o-ethylphenylmethylamino, m-ethylphenylmethyl. Amino, p-ethylphenylmethylamino, 2-propylphenylmethylamino, 4-isopropylphenylmethylamino, 4-isobutylphenylmethylamino, naphthylmethylamino, methoxycarbonylnaphthylmethylamino, ethoxycarbonylnaphthylmethylamino group, etc. .
Specific examples of the arylamino group include phenylamino, methoxycarbonylphenylamino, ethoxycarbonylphenylamino, naphthylamino, methoxycarbonylnaphthylamino, ethoxycarbonylnaphthylamino, anthranylamino, pyrenylamino, biphenylamino, terphenylamino, fluorenyl An amino group etc. are mentioned.

The alkoxysilyl group-containing alkylamino group may be any of monoalkoxysilyl group-containing alkylamino, dialkoxysilyl group-containing alkylamino, trialkoxysilyl group-containing alkylamino group, and specific examples thereof include 3-trimethoxysilyl. Propylamino, 3-triethoxysilylpropylamino, 3-dimethylethoxysilylpropylamino, 3-methyldiethoxysilylpropylamino, N- (2-aminoethyl) -3-dimethylmethoxysilylpropylamino, N- (2- Aminoethyl) -3-methyldimethoxysilylpropylamino, N- (2-aminoethyl) -3-trimethoxysilylpropylamino group and the like.

Specific examples of the aryloxy group include phenoxy, naphthoxy, anthranyloxy, pyrenyloxy, biphenyloxy, terphenyloxy, and fluorenyloxy groups.
Specific examples of the aralkyloxy group include benzyloxy, p-methylphenylmethyloxy, m-methylphenylmethyloxy, o-ethylphenylmethyloxy, m-ethylphenylmethyloxy, p-ethylphenylmethyloxy, 2-propyl Examples include phenylmethyloxy, 4-isopropylphenylmethyloxy, 4-isobutylphenylmethyloxy, α-naphthylmethyloxy groups and the like.

These groups can be easily introduced by substituting a halogen atom on the triazine ring with a compound that gives a corresponding substituent. For example, as shown in the following formula scheme 2, an aniline (derivative) or the like can be introduced. By adding and reacting an organic monoamine, a triazine ring-containing polymer (27) having a phenylamino group at at least one terminal is obtained.

(In the formula, X, R and R ′ have the same meaning as described above.)

As the organic monoamine, any of alkyl monoamine, aralkyl monoamine, and aryl monoamine can be used.
Alkyl monoamines include methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, s-butylamine, t-butylamine, n-pentylamine, 1-methyl-n-butylamine, 2-methyl- n-butylamine, 3-methyl-n-butylamine, 1,1-dimethyl-n-propylamine, 1,2-dimethyl-n-propylamine, 2,2-dimethyl-n-propylamine, 1-ethyl-n -Propylamine, n-hexylamine, 1-methyl-n-pentylamine, 2-methyl-n-pentylamine, 3-methyl-n-pentylamine, 4-methyl-n-pentylamine, 1,1-dimethyl -N-butylamine, 1,2-dimethyl-n-butylamine, 1,3-dimethyl-n- Tylamine, 2,2-dimethyl-n-butylamine, 2,3-dimethyl-n-butylamine, 3,3-dimethyl-n-butylamine, 1-ethyl-n-butylamine, 2-ethyl-n-butylamine, 1, 1,2-trimethyl-n-propylamine, 1,2,2-trimethyl-n-propylamine, 1-ethyl-1-methyl-n-propylamine, 1-ethyl-2-methyl-n-propylamine, Examples include 2-ethylhexylamine.

Specific examples of aralkyl monoamines include benzylamine, p-methoxycarbonylbenzylamine, p-ethoxycarbonylbenzylamine, p-methylbenzylamine, m-methylbenzylamine, o-methoxybenzylamine and the like.
Specific examples of the aryl monoamine include aniline, p-methoxycarbonylaniline, p-ethoxycarbonylaniline, p-methoxyaniline, 1-naphthylamine, 2-naphthylamine, anthranylamine, 1-aminopyrene, 4-biphenylylamine, o- And phenylaniline, 4-amino-p-terphenyl, 2-aminofluorene, and the like.

In this case, the amount of the organic monoamine used is preferably 0.05 to 500 equivalents, more preferably 0.05 to 120 equivalents, and even more preferably 0.05 to 50 equivalents based on the halogenated cyanuric compound. .
The reaction temperature is preferably 60 to 150 ° C, more preferably 80 to 150 ° C, and still more preferably 80 to 120 ° C.
However, the mixing of the three components of the organic monoamine, the halogenated cyanuric compound and the diaminoaryl compound may be carried out at a low temperature. In this case, the temperature is preferably about −50 to 50 ° C., and about −20 to 50 ° C. Is more preferable, and −20 to 10 ° C. is more preferable. After the low temperature charging, it is preferable to carry out the reaction by raising the temperature to the polymerization temperature at once (in one step).
In addition, the two components of the cyanuric halide compound and the diaminoaryl compound may be mixed at a low temperature. In this case, the temperature is preferably about −50 to 50 ° C., more preferably about −20 to 50 ° C., More preferably, it is −20 to 10 ° C. It is preferable to carry out the reaction by adding an organic monoamine after the low-temperature charging and raising the temperature to a temperature for polymerization (in one step).
Moreover, you may perform reaction which makes a halogenated cyanuric compound and a diaminoaryl compound react with presence of such an organic monoamine using the organic solvent similar to the above-mentioned.

In the composition of the present invention, at least two kinds of crosslinking agents are used together with the triazine ring-containing polymer. The crosslinking agent is not particularly limited as long as it is a compound having a substituent capable of reacting with the above-described triazine ring-containing polymer.
Examples of such compounds include melamine compounds having a crosslinkable substituent such as a methylol group and methoxymethyl group, substituted urea compounds, compounds containing a crosslinkable substituent such as an epoxy group or an oxetane group, and blocked isocyanates. A compound containing acid, a compound having an acid anhydride, a compound having a (meth) acryl group, a phenoplast compound, and the like, but from the viewpoint of heat resistance and storage stability, an epoxy group, a blocked isocyanate group, (meth) acrylic A compound containing a group is preferable, and in particular, two types selected from a compound having a blocked isocyanate group and a polyfunctional epoxy compound and a polyfunctional (meth) acryl compound that give a photocurable composition without using an initiator. Preferably, a polyfunctional epoxy compound and a polyfunctional (meth) acrylic compound Seen together is more preferable.
These compounds may have at least one crosslink forming substituent when used for polymer terminal treatment, and at least two crosslink forming substituents when used for cross-linking treatment between polymers. It is necessary to have.

The polyfunctional epoxy compound is not particularly limited as long as it has two or more epoxy groups in one molecule.
Specific examples include tris (2,3-epoxypropyl) isocyanurate, 1,4-butanediol diglycidyl ether, 1,2-epoxy-4- (epoxyethyl) cyclohexane, glycerol triglycidyl ether, diethylene glycol diglycidyl. Ether, 2,6-diglycidylphenyl glycidyl ether, 1,1,3-tris [p- (2,3-epoxypropoxy) phenyl] propane, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, 4,4'- Methylenebis (N, N-diglycidylaniline), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, trimethylolethane triglycidyl ether, bisphenol-A-diglycidyl ether, pentaerythris Ritol polyglycidyl ether and the like can be mentioned.

In addition, as commercially available products, epoxy resins having at least two epoxy groups, YH-434, YH434L (manufactured by Tohto Kasei Co., Ltd.), epoxy resins having a cyclohexene oxide structure, Epolide GT-401 and GT -403, GT-301, GT-302, Celoxide 2021, 3000 (manufactured by Daicel Chemical Industries, Ltd.), bisphenol A type epoxy resin, Epicoat (currently jER) 1001, 1002, 1003, 1004, 1007, 1009, 1010, 828 (Japan Epoxy Resin Co., Ltd.), Bisphenol F type epoxy resin, Epicoat (currently jER) 807 (Japan Epoxy Resin Co., Ltd.) , Epicoat (a phenol novolac type epoxy resin) , JER) 152, 154 (above, manufactured by Japan Epoxy Resins Co., Ltd.), EPPN 201, 202 (above, manufactured by Nippon Kayaku Co., Ltd.), cresol novolac type epoxy resin, EOCN-102, 103S, 104S, 1020, 1025, 1027 (Nippon Kayaku Co., Ltd.), Epicort (currently jER) 180S75 (Japan Epoxy Resin Co., Ltd.), Denacol EX, which is an alicyclic epoxy resin -252 (manufactured by Nagase ChemteX Corporation), CY175, CY177, CY179 (above, manufactured by CIBA-GEIGY A.G), Araldite CY-182, CY-192, CY-184 (above, CIBA-GEIGY A) G), Epicron 200, 400 (above DIC Corporation), Epicort (currently jER) 71, 872 (Japan Epoxy Resin Co., Ltd.), ED-5661, ED-5661 (Celanese Coating Co., Ltd.), aliphatic polyglycidyl ether, Denacol EX-611, EX -612, EX-614, EX-622, EX-411, EX-512, EX-522, EX-522, EX-421, EX-313, EX-314, EX-321 (Nagase Chem) Tex Co., Ltd.) can also be used.

The polyfunctional (meth) acrylic compound is not particularly limited as long as it has two or more (meth) acrylic groups in one molecule.
Specific examples include ethylene glycol diacrylate, ethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, ethoxylated bisphenol A diacrylate, ethoxylated bisphenol A dimethacrylate, ethoxylated trimethylolpropane triacrylate, and ethoxylated. Trimethylolpropane trimethacrylate, ethoxylated glycerol triacrylate, ethoxylated glycerol trimethacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetramethacrylate, ethoxylated dipentaerythritol hexaacrylate, polyglycerol monoethylene oxide polyacrylate, polyglycerol Polyethylene Glycol polyacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, Examples include tricyclodecane dimethanol diacrylate, tricyclodecane dimethanol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, and the like.

Polyfunctional (meth) acrylic compounds can be obtained as commercial products. Specific examples thereof include NK ester A-200, same A-400, same A-600, same A-1000, same A- 9300 (Tris (2-acryloyloxyethyl) isocyanurate), A-9300-1CL, A-TMPT, UA-53H, 1G, 2G, 3G, 4G, 9G, 14G, 23G, ABE-300, A-BPE-4, A-BPE-6, A-BPE-10, A-BPE-20, A-BPE-30, BPE-80N, BPE- 100N, BPE-200, BPE-500, BPE-900, BPE-1300N, A-GLY-3E, A-GLY-9E, A-GLY-20E, A-TMPT-3EO, Same A- MPT-9EO, AT-20E, ATM-4E, ATM-35E (Shin Nakamura Chemical Co., Ltd.), KAYARAD (registered trademark) DPEA-12, PEG400DA, THE-330, RP -1040 (above, Nippon Kayaku Co., Ltd.), M-210, M-350 (above, Toagosei Co., Ltd.), KAYARAD (registered trademark) DPHA, NPGDA, PET30 (above, Nippon Kayaku) NK Ester A-DPH, A-TMPT, A-DCP, A-HD-N, TMPT, DCP, NPG, HD-N (above, Shin-Nakamura Chemical Co., Ltd.) NK Oligo U-15HA (manufactured by Shin-Nakamura Chemical Co., Ltd.), NK polymer Vanare Resin GH-1203 (manufactured by Shin-Nakamura Chemical Co., Ltd.), and the like.

The acid anhydride compound is not particularly limited as long as it is a carboxylic acid anhydride obtained by dehydration condensation of two molecules of carboxylic acid. Specific examples thereof include phthalic anhydride, tetrahydrophthalic anhydride, hexahydroanhydride. One in the molecule such as phthalic acid, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, maleic anhydride, succinic anhydride, octyl succinic anhydride, dodecenyl succinic anhydride Having an acid anhydride group; 1,2,3,4-cyclobutanetetracarboxylic 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- Oxotetrahydro-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-dicarboxyphenyl) hexafluoropropane dianhydride, 1, Examples thereof include those having two acid anhydride groups in the molecule such as 3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride.

As a compound containing a blocked isocyanate, when the isocyanate group (—NCO) has two or more blocked isocyanate groups blocked by an appropriate protective group in one molecule, it is exposed to a high temperature during thermosetting. The protective group (block part) is not particularly limited as long as it is dissociated by thermal dissociation and the resulting isocyanate group causes a crosslinking reaction with the resin. For example, a group represented by the following formula Examples thereof include compounds having two or more in the molecule (note that these groups may be the same or different from each other).

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

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

A compound containing a blocked isocyanate is also available as a commercial product. Specific examples thereof include B-830, B-815N, B-842N, B-870N, B-874N, B-882N, B -7005, B-7030, B-7075, B-5010 (Mitsui Chemicals Polyurethane Co., Ltd.), Duranate (registered trademark) 17B-60PX, TPA-B80E, MF-B60X, MF-K60X, E402-B80T (above, manufactured by Asahi Kasei Chemicals Corporation), Karenz MOI-BM (registered trademark) (above, manufactured by Showa Denko Co., Ltd.), and the like.

The aminoplast compound is not particularly limited as long as it has two or more methoxymethylene groups in one molecule. For example, hexamethoxymethylmelamine CYMEL (registered trademark) 303, tetrabutoxymethylglycoluril 1170 Cymel series such as Tetramethoxymethylbenzoguanamine 1123 (Nippon Cytec Industries, Ltd.), Nicalac (registered trademark) MW-30HM, MW-390, MW-100LM, which are methylated melamine resins Examples thereof include melamine compounds such as MX-750LM, Nicarac series such as MX-270 and MX-280, which are methylated urea resins, and MX-280 and MX-290 (manufactured by Sanwa Chemical Co., Ltd.).
The oxetane compound is not particularly limited as long as it has two or more oxetanyl groups in one molecule. For example, OXT-221, OX-SQ-H, OX-SC containing oxetanyl group (above And Toagosei Co., Ltd.).

The phenoplast compound has two or more hydroxymethylene groups in one molecule, and when exposed to a high temperature during thermosetting, a crosslinking reaction proceeds with the polymer of the present invention by a dehydration condensation reaction. Is.
Examples of the phenoplast compound include 2,6-dihydroxymethyl-4-methylphenol, 2,4-dihydroxymethyl-6-methylphenol, bis (2-hydroxy-3-hydroxymethyl-5-methylphenyl) methane, Bis (4-hydroxy-3-hydroxymethyl-5-methylphenyl) methane, 2,2-bis (4-hydroxy-3,5-dihydroxymethylphenyl) propane, bis (3-formyl-4-hydroxyphenyl) methane Bis (4-hydroxy-2,5-dimethylphenyl) formylmethane, α, α-bis (4-hydroxy-2,5-dimethylphenyl) -4-formyltoluene and the like.
The phenoplast compound is also available as a commercial product, and specific examples thereof include 26DMPC, 46DMOC, DM-BIPC-F, DM-BIOC-F, TM-BIP-A, BISA-F, BI25X-DF. BI25X-TPA (above, manufactured by Asahi Organic Materials Co., Ltd.).

Among these, a polyfunctional (meth) acrylic compound is suitable from the viewpoint that the refractive index lowering due to the crosslinking agent blending can be suppressed and the curing reaction proceeds rapidly, and among these, the triazine ring-containing polymer is preferred. Since it is excellent in compatibility, the polyfunctional (meth) acrylic compound having the following isocyanuric acid skeleton is more preferable.
Examples of the polyfunctional (meth) acrylic compound having such a skeleton include NK ester A-9300 and A-9300-1CL (both manufactured by Shin-Nakamura Chemical Co., Ltd.).

(Wherein R ¹¹¹ to R ¹¹³ are each independently a monovalent organic group having at least one (meth) acryl group at the end).

Further, from the viewpoint of further improving the curing rate and improving the solvent resistance, acid resistance, and alkali resistance of the resulting cured film, it is liquid at 25 ° C. and its viscosity is 5000 mPa · s or less, preferably 1 To 3000 mPa · s, more preferably 1 to 1000 mPa · s, and even more preferably 1 to 500 mPa · s, a polyfunctional (meth) acrylic compound (hereinafter referred to as a low-viscosity crosslinking agent) alone or in combination of two or more. Alternatively, it is preferable to use in combination with the polyfunctional (meth) acrylic compound having the isocyanuric acid skeleton.
Such low-viscosity cross-linking agents are also commercially available. For example, among the polyfunctional (meth) acrylic compounds described above, NK ester A-GLY-3E (85 mPa · s, 25 ° C.), A-GLY -9E (95 mPa · s, 25 ° C), A-GLY-20E (200 mPa · s, 25 ° C), A-TMPT-3EO (60 mPa · s, 25 ° C), A-TMPT-9EO, ATM The chain length between (meth) acrylic groups such as -4E (150 mPa · s, 25 ° C.), ATM-35E (350 mPa · s, 25 ° C.) (manufactured by Shin-Nakamura Chemical Co., Ltd.) is relatively Long crosslinking agents.

Furthermore, in consideration of improving the alkali resistance of the cured film obtained, NK ester A-GLY-20E (made by Shin-Nakamura Chemical Co., Ltd.) and ATM-35E (made by Shin-Nakamura Chemical Co., Ltd.) ) And a polyfunctional (meth) acrylic compound having the above isocyanuric acid skeleton.

The total amount of the crosslinking agent used is preferably 1 to 100 parts by mass with respect to 100 parts by mass of the triazine ring-containing polymer, but considering the solvent resistance, the lower limit is preferably 2 parts by mass, more preferably 5 parts by mass. In view of controlling the refractive index, the upper limit is preferably 20 parts by mass, more preferably 15 parts by mass.
The use ratio of two or more kinds of crosslinking agents is not particularly limited, but when a polyfunctional (meth) acrylic compound and a polyfunctional epoxy compound, which are the preferred combinations described above, are used in combination, the polyfunctional (meth) acrylic is used. The content of the compound and the polyfunctional epoxy compound can be about 1:10 to 10: 1 by mass ratio, preferably 1: 1 to 5: 1, more preferably 1: 1 to 3: 1.

In the composition of the present invention, an initiator corresponding to each crosslinking agent can be blended. As described above, when a polyfunctional epoxy compound and a polyfunctional (meth) acrylic compound are used as the crosslinking agent, photocuring proceeds without using an initiator to give a cured film. An initiator can be used.

When a polyfunctional epoxy compound is used as a crosslinking agent, a photoacid generator or a photobase generator can be used.
The photoacid generator may be appropriately selected from known ones. For example, onium salt derivatives such as diazonium salts, sulfonium salts, and iodonium salts can be used.
Specific examples thereof include aryldiazonium salts such as phenyldiazonium hexafluorophosphate, 4-methoxyphenyldiazonium hexafluoroantimonate, 4-methylphenyldiazonium hexafluorophosphate; diphenyliodonium hexafluoroantimonate, di (4-methylphenyl) Diaryliodonium salts such as iodonium hexafluorophosphate and di (4-tert-butylphenyl) iodonium hexafluorophosphate; triphenylsulfonium hexafluoroantimonate, tris (4-methoxyphenyl) sulfonium hexafluorophosphate, diphenyl-4-thiophenoxy Phenylsulfonium hexafluoroantimonate, diphenyl-4-thiophenoxy Enylsulfonium hexafluorophosphate, 4,4′-bis (diphenylsulfonio) phenyl sulfide-bishexafluoroantimonate, 4,4′-bis (diphenylsulfonio) phenyl sulfide-bishexafluorophosphate, 4,4 '-Bis [di (β-hydroxyethoxy) phenylsulfonio] phenylsulfide-bishexafluoroantimonate, 4,4'-bis [di (β-hydroxyethoxy) phenylsulfonio] phenylsulfide-bis-hexafluorophosphate 4- [4 '-(benzoyl) phenylthio] phenyl-di (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- [4'-(benzoyl) phenylthio] phenyl-di (4-fluorophenyl) sulfur Triarylsulfonium salts such as triphenylsulfonium hexafluorophosphate and the like.

As these onium salts, commercially available products may be used. Specific examples thereof include Sun-Aid SI-60, SI-80, SI-100, SI-60L, SI-80L, SI-100L, SI-L145, SI- L150, SI-L160, SI-L110, SI-L147 (Sanshin Chemical Industry Co., Ltd.), UVI-6950, UVI-6970, UVI-6974, UVI-6990, UVI-6990 (above, Union Carbide) Co., Ltd.), CPI-100P, CPI-100A, CPI-200K, CPI-200S (above, manufactured by San Apro Co., Ltd.), Adekaoptomer SP-150, SP-151, SP-170, SP-171 (above, Asahi Denka Kogyo Co., Ltd.), Irgacure 261 (BASF), CI-2481, CI-2624, CI-2 39, CI-2064 (above, manufactured by Nippon Soda Co., Ltd.), CD-1010, CD-1011, CD-1012 (above, made by Sartomer), DS-100, DS-101, DAM-101, DAM-102 , DAM-105, DAM-201, DSM-301, NAI-100, NAI-101, NAI-105, NAI-106, SI-100, SI-101, SI-105, SI-106, PI-105, NDI -105, BENZOIN TOSYLATE, MBZ-101, MBZ-301, PYR-100, PYR-200, DNB-101, NB-101, NB-201, BBI-101, BBI-102, BBI-103, BBI-109 ( (Midori Chemical Co., Ltd.), PCI-061T, PCI-062T, PCI-020T PCI-022T (manufactured by Nippon Kayaku Co., Ltd.), can be mentioned IBPF, IBCF (manufactured by Sanwa Chemical Co., Ltd.), and the like.

On the other hand, the photobase generator may be appropriately selected from known ones, such as Co-amine complex, oxime carboxylic acid ester, carbamic acid ester, quaternary ammonium salt photobase generator. Can be used.
Specific examples thereof include 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-carbamoylhydroxylamide, O-carbamoyloxime, [[(2,6-dinitrobenzyl) oxy] carbonyl] cyclohexylamine, bis [[(2 -Nitrobenzyl) oxy] carbonyl] hexane 1,6-diamine, 4- (methylthiobenzoyl) -1-methyl-1-morpholinoethane, (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane, N- (2-nitrobenzyloxycarbonyl) pyrrolidine, hexaamminecobalt (III) tris (triphenylmethylborate), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2,6-dimethyl- 3,5-di Cetyl-4- (2′-nitrophenyl) -1,4-dihydropyridine, 2,6-dimethyl-3,5-diacetyl-4- (2 ′, 4′-dinitrophenyl) -1,4-dihydropyridine and the like Can be mentioned.
Commercially available photobase generators may be used, and specific examples thereof include TPS-OH, NBC-101, ANC-101 (all of which are product names, manufactured by Midori Chemical Co., Ltd.).

When a photoacid or base generator is used, it is preferably used in the range of 0.1 to 15 parts by mass, more preferably in the range of 1 to 10 parts by mass with respect to 100 parts by mass of the polyfunctional epoxy compound.
If necessary, an epoxy resin curing agent may be blended in an amount of 1 to 100 parts by mass with respect to 100 parts by mass of the polyfunctional epoxy compound.

On the other hand, when a polyfunctional (meth) acrylic compound is used, a radical photopolymerization initiator can be used.
The radical photopolymerization initiator may be appropriately selected from known ones, such as acetophenones, benzophenones, Michler's benzoylbenzoate, amyloxime esters, oxime esters, tetramethylthiuram monosulfide, and thioxanthones. Is mentioned.
In particular, photocleavable photoradical polymerization initiators are preferred. The photocleavable photoradical polymerization initiator is described in the latest UV curing technology (p. 159, publisher: Kazuhiro Takahisa, publisher: Technical Information Association, Inc., published in 1991).
Examples of commercially available radical photopolymerization initiators include BASF Corporation trade names: Irgacure 127, 184, 369, 379, 379EG, 651, 500, 754, 819, 903, 907, 784, 2959, CGI 1700, CGI 1750, CGI 1850. , CG24-61, OXE01, OXE02, Darocur 1116, 1173, MBF, manufactured by BASF, Inc. Product name: Lucirin TPO, manufactured by UCB, Inc. Product name: Uvekril P36, manufactured by Fratteri Lamberti, Inc. KT37, KT55, KTO46, KIP75 / B etc. are mentioned.
When using a radical photopolymerization initiator, it is preferably used in the range of 0.1 to 200 parts by weight, preferably in the range of 1 to 150 parts by weight, with respect to 100 parts by weight of the polyfunctional (meth) acrylate compound. Is more preferable.

It is preferable that various solvents are added to the composition of the present invention to dissolve the triazine ring-containing polymer.
Examples of the solvent include water, toluene, p-xylene, o-xylene, m-xylene, ethylbenzene, styrene, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol, propylene glycol monoethyl ether, ethylene Glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol methyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, diethylene glycol diethyl ether, dipropylene Recall 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, di Ethyl ketone, methyl isobutyl ketone, methyl normal butyl ketone, cyclopentanone, 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 (DMAc), N-methylpyrrolidone, 1,3-dimethyl-2-imidazo Jin Won, dimethyl sulfoxide, N- cyclohexyl-2-pyrrolidinone and the like. These may be used singly or may be used in combination of two or more.

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

As long as the effects of the present invention are not impaired, other components other than the triazine ring-containing polymer, the crosslinking agent and the solvent, for example, a leveling agent, a surfactant, a silane coupling agent and the like are added to the composition of the present invention. An agent may be included.
Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether; polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol Polyoxyethylene alkyl allyl 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 polyoxyethylene sorbitan monolaurate, polyoxyethyleneso Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as bitane monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, trade name EFTOP EF301, EF303, EF352 (Mitsubishi Materials Electronics Kasei Co., Ltd. (formerly Gemco Co., Ltd.)), trade names MegaFuck F171, F173, R-08, R-30, R-40, F-553, F-554, RS-75, RS-72-K (manufactured by DIC Corporation), Florard FC430, FC431 (manufactured by Sumitomo 3M Corporation), trade names Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105 , SC106 (Asahi (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 Big 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 preferred.
In addition, the said other component can be added at the arbitrary processes at the time of preparing the composition of this invention.

The composition of the present invention can be applied to a substrate, then heated as necessary to evaporate the solvent, and then heated or irradiated with light to form a desired cured film.
The coating method of the composition is arbitrary, for example, spin coating method, dip method, flow coating method, ink jet method, jet dispenser method, spray method, bar coating method, gravure coating method, slit coating method, roll coating method, transfer Methods such as printing, brush coating, blade coating, and air knife coating can be employed.

As the base material, silicon, glass with indium tin oxide (ITO) formed, glass with indium zinc oxide (IZO) formed, polyethylene terephthalate (PET), plastic, glass, quartz, ceramics A flexible substrate having flexibility can be used.
The firing temperature is not particularly limited for the purpose of evaporating the solvent. For example, it can be carried out at 40 to 400 ° C. However, the composition of the present invention forms a thin film by low-temperature firing at less than 150 ° C., particularly 60 to 130 ° C. can do.
The baking method is not particularly limited, and for example, it may be evaporated using a hot plate or an oven in an appropriate atmosphere such as air, an inert gas such as nitrogen, or in a vacuum.
The firing temperature and firing time may be selected in accordance with the process steps of the target electronic device, and the firing conditions may be selected so that the physical properties of the obtained film meet the required characteristics of the electronic device.
The conditions for the light irradiation are not particularly limited, and an appropriate irradiation energy and time may be adopted depending on the triazine ring-containing polymer and the crosslinking agent to be used.
Moreover, when producing the cured film by light irradiation of the composition, a fine pattern can be formed by light irradiation through a mask and development with a developer.
In this case, development after exposure can be performed by immersing the exposure resin in, for example, an organic solvent developer or an aqueous developer.
Specific examples of the organic solvent developer include NMP, γ-butyrolactone, DMSO and the like, while specific examples of the aqueous developer include sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium. An aqueous alkali solution such as hydroxide can be used.

When setting it as a negative pattern formation composition, you may mix | blend an oxirane ring containing compound and a photocurable catalyst with the said composition further.
Examples of the oxirane ring-containing compound include those having one or more, preferably two or more oxirane rings in the molecule. Specific examples thereof include glycidyl ether type epoxy resins, glycidyl ester type epoxy resins, and alicyclic epoxies. Resins, epoxy-modified polybutadiene resins, oxetane compounds and the like. These may be used alone or in combination of two or more.
The amount of the oxirane-containing compound is not particularly limited, but can be about 10 to 400 parts by mass with respect to 100 parts by mass of the triazine ring-containing polymer.

Examples of the photocurable catalyst include a photocation generator. Specific examples of the photocation generator include triarylsulfonium salts such as triphenylsulfonium hexafluorophosphate and triphenylsulfonium hexafluoroantimonate; triaryl selenium salts; diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate and the like. And diaryliodonium salts. These may be used alone or in combination of two or more.
The blending amount of the photocurable catalyst is not particularly limited, but can be about 0.1 to 100 parts by mass with respect to 100 parts by mass of the triazine ring-containing polymer.

The preparation method of the said negative pattern formation composition is not specifically limited, What is necessary is just to mix | blend and prepare each component in arbitrary orders. At that time, the above-described solvent may be used.
The composition can be cured by, for example, irradiating ultraviolet light or the like at 1 to 4000 mJ / cm ² after being applied by the method described above. Light irradiation may be performed using various known methods such as a high-pressure mercury lamp, a metal halide lamp, a xenon lamp, an LED, and laser light.
If necessary, when using a base material having a low heat resistance of about 80 to 180 ° C. before and after exposure, it may be heated preferably at 80 ° C. or more and less than 150 ° C., more preferably at 80 to 130 ° C.
Development after exposure can be performed by immersing the exposure resin in the organic solvent developer or aqueous developer described above.

On the other hand, when a positive pattern forming composition is used, an azide compound may be further added to the above composition.
As the azide compound, a compound having one or more, preferably two or more 1,2-naphthoquinonediazide groups is preferable, and specific examples thereof include 2,3,4-trihydroxy-benzophenone and 1,2-naphthoquinone- (2) 1,2-naphthoquinone diazide sulfonic acid derivatives such as esters with -diazide-5-sulfonic acid.
The amount of the oxirane-containing compound is not particularly limited, but can be about 4 to 60 parts by mass with respect to 100 parts by mass of the triazine ring-containing polymer.

The method for preparing the positive pattern forming composition is not particularly limited, and may be prepared by blending the components in any order. At that time, the above-described solvent may be used.
After the composition is applied by the above-described method, it can be cured by, for example, irradiation with ultraviolet light at 1 to 2000 mJ / cm ² by the above-described light irradiation method. Also in this case, if necessary, the substrate may be heated at a temperature of about 80 to 180 ° C. before and after exposure and preferably at a temperature of 80 to 150 ° C., more preferably 80 to 130 ° C. .
Development after exposure can be performed by immersing the exposure resin in the organic solvent developer or aqueous developer described above.

Various additives may be added to the pattern forming compositions as necessary. Additives include thermal cation generators such as benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 1-naphthylmethyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 4-hydroxyphenyldimethylsulfonium methyl sulfate; 2 , 5-diethylthioxanthone, anthracene, 9,10-ethoxyanthracene and the like, and the additives exemplified in the film-forming composition.

Since the cured film and fine pattern of the present invention obtained as described above can achieve high heat resistance, high refractive index, and low volume shrinkage, liquid crystal display, organic electroluminescence (EL) display, touch panel, optical semiconductor Electronic devices such as (LED) elements, solid-state imaging devices, organic thin film solar cells, dye-sensitized solar cells, organic thin film transistors (TFTs), lenses, prism cameras, binoculars, microscopes, and parts for manufacturing semiconductor exposure devices And can be suitably used in the field of optical materials.

EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to the following Example. In addition, each measuring apparatus used in the Example is as follows.
[ ¹ H-NMR]
Apparatus: Varian NMR System 400NB (400 MHz
) JEOL-ECA700 (700MHz)
Measuring solvent: DMSO-d6
Reference substance: Tetramethylsilane (TMS) (δ0.0ppm)
[GPC]
Equipment: Modified to SHIMADZU SCL-10Avp GPC Column: Shodex KF-804L + KF-805L
Column temperature: 60 ° C
Solvent: NMP (1% LiCl added)
Detector: UV (254 nm)
Calibration curve: Standard polystyrene [UV-visible spectrophotometer]
Apparatus: SHIMADSU UV-3600 manufactured by Shimadzu Corporation
[Ellipsometer]
Equipment: Multi-angle-of-incidence spectroscopic ellipsometer VASE manufactured by JA Woollam Japan
[Differential thermal balance (TG-DTA)]
Equipment: TG-8120, manufactured by Rigaku Corporation
Temperature increase rate: 10 ° C / min Measurement temperature: 25 ° C-750 ° C
[electronic microscope]
Electron microscope S-4800 manufactured by JEOL Ltd.

[1] Synthesis of triazine ring-containing polymer [Example 1] Synthesis of polymer compound [4]

Under nitrogen, 3-aminophenol [2] (11.00 g, 0.1 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) was added to a 500 mL four-necked flask, and 104.14 g of N-methyl-2-pyrrolidone (NMP) was added. Dissolved and cooled to below 0 ° C. Thereafter, 2,4,6-trichloro-1,3,5-triazine [1] (18.34 g, 0.1 mol, manufactured by Evonik Degussa) was added and stirred for 1 hour, and then dissolved in 154.96 g of NMP. -Phenylenediamine [3] (16.14 g, 0.15 mol) was added dropwise so that the internal temperature was kept below 30 ° C. After dropping, the mixture was heated to 90 ° C. and reacted for 3 hours, and 50.34 g of triethylamine was added to terminate the polymerization.
The produced triethylamine hydrochloride was removed by filtration, and the filtrate was added dropwise to 1290 g of ion-exchanged water for reprecipitation. The obtained precipitate was filtered, the filtrate was redissolved in 200 g of acetone, and further reprecipitated in 1500 g of ion-exchanged water. The product obtained by filtering the precipitate was dried at 100 ° C. for 8 hours to obtain 26.6 g of the target polymer [4] (hereinafter referred to as L-TmDA-100).
The measurement result of ¹ H-NMR spectrum of L-TmDA-100 is shown in FIG. Moreover, the weight average molecular weight Mw measured by GPC of L-TmDA-100 in terms of polystyrene was 8,200, and the polydispersity Mw / Mn was 2.15.

When 5.200 mg of the polymer compound [4] obtained in Example 1 above was added to a platinum pan and measured with TG-DTA at a heating rate of 15 ° C./min, the 5% weight loss was 392 ° C. It was. The result is shown in FIG.

[2] Preparation of composition [Example 2]
Under nitrogen, 12.00 g of L-TmDA-100 obtained in Example 1 was added to a 200 mL eggplant flask, and 18.00 g of propylene glycol monomethyl ether (PGME) was added as a solvent. L-TmDA-100-M) was prepared.
The obtained L-TmDA-100-M was diluted to 10% by mass with PGME, and the refractive index was measured to be 1.7494 (@ 550 nm).

[3] Fabrication of fine pattern [Example 3]
L-TmDA-100-M 18.95 g prepared in Example 2, polyfunctional acrylate (AT-20E, manufactured by Shin-Nakamura Chemical Co., Ltd.) 0.74 g, polyfunctional epoxy (Epolide GT-401, Daicel Chemical Industries ( Co., Ltd.) 0.37 g, photo radical initiator (Irgacure OXE02, manufactured by BASF) 0.52 g, photoacid generator (CPI-210S, manufactured by San Apro Co., Ltd.) 0.45 g, and PGME 24.0 g were added to form a solid. 45 g of a composition (LP-W) having a content of 20% by mass was prepared.
The composition was filtered using a 0.45 μm filter and then applied onto a glass substrate using a spin coater. A coating film was formed by baking (soft baking) on a hot plate at 100 ° C. for 30 seconds. This coating film was irradiated with ultraviolet rays having an irradiation amount of 365 m at 200 mJ / cm ² by an ultraviolet irradiation device MA6 (manufactured by SUSS). Then, post-bake on a hot plate at 100 ° C. for 25 minutes, develop by immersing in a NMD-3 developer (manufactured by Tokyo Ohka Kogyo Co., Ltd.) at 23 ° C. for a certain period of time, and rinse with running pure water. went. After development, lines / spaces of 10/10 μm, 7/7 μm, and 5/5 μm were resolved without residue.
As a result of visual observation under a sodium lamp, no foreign matter was found on the cured film formed on the glass substrate. Furthermore, when observed with an electron microscope, no foreign matter was found on the cured film.

[4] Production of cured film [Example 4]
L-TmDA-100-M 18.95 g prepared in Example 2, polyfunctional acrylate (AT-20E, manufactured by Shin-Nakamura Chemical Co., Ltd.) 0.74 g, polyfunctional epoxy (Epolide GT-401, Daicel Chemical Industries ( Co., Ltd.) 0.37 g, photo radical initiator (Irgacure OXE02, manufactured by BASF) 0.52 g, photoacid generator (CPI-210S, manufactured by San Apro Co., Ltd.) 0.45 g, and PGME 24.0 g were added to form a solid. 45 g of a composition (LP-W) having a content of 20% by mass was prepared.
This composition was filtered using a 0.45 μm filter and then applied onto a silicon wafer substrate using a spin coater. A coating film was formed by baking (soft baking) on a hot plate at 100 ° C. for 30 seconds. This coating film was irradiated with ultraviolet rays having an irradiation amount of 365 m at 200 mJ / cm ² by an ultraviolet irradiation device MA6 (manufactured by SUSS). Thereafter, post-baking was performed on a hot plate at 100 ° C. for 25 minutes to produce a cured film.
About the obtained cured film, when the refractive index in 550 nm was measured with the ellipsometer, it was refractive index 1.711 (@ 550 nm). Moreover, when the transmittance | permeability of 400 nm was measured about the obtained cured film, the transmittance | permeability was 75%.

Claims (14)

1. The triazine type polymer containing composition characterized by including the polymer containing the repeating unit structure represented by following formula (1), and at least 2 types of crosslinking agent.
   

   

   {In the formula, R and R 'each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group, and Ar ¹ represents an aryl group having a hydroxyl group, a carboxyl group, and / or a maleimide group. Ar ² represents at least one selected from the group represented by formulas (2) to (13).
   

   

   [Wherein R ¹ to R ⁹² are independently of each other a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group which may have a branched structure having 1 to 10 carbon atoms, or a carbon number of 1 Represents an alkoxy group which may have a branched structure of ˜10, R ⁹³ and R ⁹⁴ represent a hydrogen atom or an alkyl group which may have a branched structure of 1 to 10 carbon atoms, W ¹ and W ² is independently a single bond, CR ⁹⁵ R ⁹⁶ (R ⁹⁵ and R ⁹⁶ are each independently a hydrogen atom or an alkyl group optionally having a branched structure of 1 to 10 carbon atoms ( However, these may be combined to form a ring.))), C═O, O, S, SO, SO ₂ , or NR ⁹⁷ (R ⁹⁷ is a hydrogen atom or a carbon number of 1). have a branched structure to 10 represent also alkyl groups.) represents, X ¹ Contact Fine X ² are independently of each other a single bond, an alkylene group which may have a branched structure having 1 to 10 carbon atoms, or the formula, (14)
   

   

   (Wherein R ⁹⁸ to R ¹⁰¹ are each independently a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group which may have a branched structure having 1 to 10 carbon atoms, or 1 carbon atom) Represents an alkoxy group which may have a branched structure of ˜10, and Y ¹ and Y ² each independently represent an alkylene group which may have a single bond or a branched structure of 1 to 10 carbon atoms. Represents a group represented by: ]}
2. The triazine polymer-containing composition according to claim 1, wherein the crosslinking agent is a combination of a polyfunctional (meth) acrylic compound and a polyfunctional epoxy compound.
3. 3. The triazine polymer-containing composition according to claim 2, wherein the content of the polyfunctional (meth) acrylic compound and the polyfunctional epoxy compound is 1: 1 to 3: 1 by mass ratio.
4. The triazine polymer-containing composition according to any one of claims 1 to 3, wherein the polymer contains a repeating unit structure represented by the following formula (18).
   

   

   (Wherein R, R ′ and Ar ² represent the same meaning as described above.)
5. The triazine polymer-containing composition according to claim 4, comprising a repeating unit structure represented by the following formula (19).
   

   

   (Wherein R, R ′ and Ar ² represent the same meaning as described above.)
6. The triazine polymer-containing composition according to claim 5, comprising a repeating unit structure represented by the following formula (23).
   

   
7. The triazine polymer-containing composition according to any one of claims 1 to 6, further comprising an oxirane ring-containing compound and a photocurable catalyst.
8. The triazine polymer-containing composition according to any one of claims 1 to 6, further comprising an azide compound.
9. The triazine polymer-containing composition according to any one of claims 1 to 8, which is used for pattern formation.
10. A cured film obtained by curing the triazine polymer-containing composition according to any one of claims 1 to 8.
11. A pattern produced from the triazine-based polymer-containing composition according to claim 9.
12. An electronic device comprising a base material and the cured film according to claim 10 formed on the base material.
13. An optical member comprising a substrate and the cured film according to claim 10 formed on the substrate.
14. An electronic device comprising a base material and the pattern according to claim 11 formed on the base material.

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