JP6515811B2 - Triazine polymer-containing composition - Google Patents

Description

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

In recent years, we develop electronic devices such as liquid crystal displays, organic electroluminescence (EL) displays, touch panels, optical semiconductor (LED) elements, solid-state imaging devices, organic thin film solar cells, dye-sensitized solar cells, and organic thin film transistors (TFTs) At the same time, high functional polymer materials have come to be required.
Specific characteristics required are 1) heat resistance, 2) transparency, 3) high refractive index, 4) high solubility, 5) low volume shrinkage, 6) high temperature and high humidity resistance, 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 low volume shrinkage can be achieved and it is suitable as a composition for film formation when producing an electronic device (Patent Document 1).

By the way, pattern formation using a transparent material is performed in 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 use so far.
In particular, in recent years, with the increasing demand for high definition liquid crystal displays and displays for mobile phones, small patterns having a diameter of 10 μm or less are required.
Moreover, in the touch panel, the need for a high refractive index layer is increasing to improve the visibility of the transparent electrode, but the presence of the insulating film in the electrode wiring portion affects the response, so the wiring portion It is necessary to remove the insulating layer with a width of 100 to 1000 μm.
The existing materials used for the application 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 respect, although the polymer of Patent Document 1 can meet the requirements in terms of refractive index, there is room for improvement in terms of fine pattern formation.

  In addition, although the composition for pattern formation containing a triazine ring containing polymer is disclosed by patent document 2, this polymer is less than 1.7 refractive index, and the said high refractive index is requested | required. Not suitable for use.

  In addition, with the trend of thinning and reducing the weight of devices in recent years, the use of materials with low heat resistance such as plastic film substrates is also increasing, and there is a demand for the design of materials and compositions that can be fired at low temperatures when producing thin films. Is rising.

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

  The present invention has been made in view of the above-mentioned circumstances, and it is possible to form a thin film having high refractive index and excellent transparency by low temperature baking, and to form a triazine series weight which can also form a fine pattern of high refractive index. It is an object to provide a united containing composition.

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

｛式中、ＲおよびＲ′は、互いに独立して、水素原子、アルキル基、アルコキシ基、アリール基、またはアラルキル基を表し、Ａｒ¹は、水酸基、カルボキシル基および／またはマレイミド基を有するアリール基を表し、Ａｒ²は、式（２）〜（１３）で示される群から選ばれる少なくとも１種を表す。

〔式中、Ｒ¹〜Ｒ⁹²は、互いに独立して、水素原子、ハロゲン原子、カルボキシル基、スルホ基、炭素数１〜１０の分岐構造を有していてもよいアルキル基、または炭素数１〜１０の分岐構造を有していてもよいアルコキシ基を表し、Ｒ⁹³およびＲ⁹⁴は、水素原子または炭素数１〜１０の分岐構造を有していてもよいアルキル基を表し、Ｗ¹およびＷ²は、互いに独立して、単結合、ＣＲ⁹⁵Ｒ⁹⁶（Ｒ⁹⁵およびＲ⁹⁶は、互いに独立して、水素原子または炭素数１〜１０の分岐構造を有していてもよいアルキル基（ただし、これらは一緒になって環を形成していてもよい。）を表す。）、Ｃ＝Ｏ、Ｏ、Ｓ、ＳＯ、ＳＯ₂、またはＮＲ⁹⁷（Ｒ⁹⁷は、水素原子または炭素数１〜１０の分岐構造を有していてもよいアルキル基を表す。）を表し、Ｘ¹およびＸ²は、互いに独立して、単結合、炭素数１〜１０の分岐構造を有していてもよいアルキレン基、または式（１４）

（式中、Ｒ⁹⁸〜Ｒ¹⁰¹は、互いに独立して、水素原子、ハロゲン原子、カルボキシル基、スルホ基、炭素数１〜１０の分岐構造を有していてもよいアルキル基、または炭素数１〜１０の分岐構造を有していてもよいアルコキシ基を表し、Ｙ¹およびＹ²は、互いに独立して、単結合または炭素数１〜１０の分岐構造を有していてもよいアルキレン基を表す。）で示される基を表す。〕｝
２． 前記架橋剤が、多官能（メタ）アクリル化合物と多官能エポキシ化合物との組み合わせである１のトリアジン系重合体含有組成物、
３． 前記多官能（メタ）アクリル化合物と多官能エポキシ化合物との含有量が、質量比で１：１〜３：１である２のトリアジン系重合体含有組成物、
４． 前記重合体が、下記式（１８）で示される繰り返し単位構造を含む１〜３のいずれかのトリアジン系重合体含有組成物、

（式中、Ｒ、Ｒ′およびＡｒ²は、前記と同じ意味を表す。）
５． 下記式（１９）で示される繰り返し単位構造を含む４のトリアジン系重合体含有組成物、

（式中、Ｒ、Ｒ′およびＡｒ²は、前記と同じ意味を表す。）
６． 下記式（２３）で示される繰り返し単位構造を含む５のトリアジン系重合体含有組成物、

７． さらに、オキシラン環含有化合物と、光硬化型触媒とを含有する１〜６のいずれかのトリアジン系重合体含有組成物、
８． さらにアジド化合物を含有する１〜６のいずれかのトリアジン系重合体含有組成物、
９． パターン形成用である１〜８のいずれかのトリアジン系重合体含有組成物、
１０． １〜８のいずれかのトリアジン系重合体含有組成物を硬化させて得られる硬化膜、
１１． ９のトリアジン系重合体含有組成物から作製されたパターン、
１２． 基材と、この基材上に形成された１０の硬化膜とを備える電子デバイス、
１３． 基材と、この基材上に形成された１０の硬化膜とを備える光学部材、
１４． 基材と、この基材上に形成された１１のパターンとを備える電子デバイス
を提供する。That is, the present invention
1. A triazine-based polymer-containing composition comprising a polymer having a repeating unit structure represented by the following formula (1), and at least two types of crosslinking agents,

[Wherein, 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 is 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 each independently a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group optionally having a carbon number of 1 to 10, or a carbon number of 1 represents an alkoxy group which may have a branched structure to 10, R ⁹³ and R ⁹⁴ represents an alkyl group which may have a hydrogen atom or a branched structure having 1 to 10 carbon atoms, W ¹ and W ² is, independently of each other, a single bond, CR ⁹⁵ R ⁹⁶ (R ⁹⁵ and R ⁹⁶ are each independently a hydrogen atom or an alkyl group having a branched structure of 1 to 10 carbon atoms ( Provided that they may together form a ring))), C = O, O, S, SO, SO ₂ or NR ⁹⁷ (R ⁹⁷ is a hydrogen atom or 1 carbon atom represents an alkyl group which may have a branched structure 10.) represents, X ¹ Contact Fine X ² independently of one another, a single bond, an alkylene group which may have a branched structure of 1 to 10 carbon atoms, or the formula, (14)

(Wherein, R ^{98 to} R ¹⁰¹ each independently represent a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group having 1 to 10 carbon atoms, or a branched structure, or 1 carbon atom) And an alkoxy group which may have a branched structure of 10 to 10, and Y ¹ and Y ² independently of each other are a single bond or an alkylene group which may have a branched structure of 1 to 10 carbon atoms Represents a group represented by ]}
2. 1. The triazine-based polymer-containing composition according to 1, wherein the crosslinking agent is a combination of a polyfunctional (meth) acrylic compound and a polyfunctional epoxy compound.
3. 2. The triazine polymer-containing composition according to 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 comprises 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. A triazine-based polymer-containing composition of 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. 5. A triazine-based polymer-containing composition of 5 comprising a repeating unit structure represented by the following formula (23):

7. Furthermore, the triazine polymer-containing composition according to any one of 1 to 6, which comprises an oxirane ring-containing compound and a photocurable catalyst,
8. Furthermore, the triazine type polymer containing composition in any one of 1-6 containing an azide compound,
9. A composition containing a triazine polymer according to any one of 1 to 8 for pattern formation,
10. A cured film obtained by curing a triazine polymer-containing composition according to any one of 1 to 8,
11. A pattern prepared from the triazine polymer containing composition of 9,
12. An electronic device comprising a substrate and 10 cured films formed on the substrate,
13. An optical member comprising a substrate and 10 cured films formed on the substrate,
14. Provided is an electronic device comprising a substrate and 11 patterns formed on the substrate.

According to the present invention, a thin film having high refractive index and excellent transparency can be formed, and after exposure and curing by masking, a fine pattern can be formed by alkali development or the like.
In particular, since two types of crosslinking agents are used in combination, it has an advantage that thin film formation is possible by low temperature baking.
A cured film or a fine pattern produced from the composition of the present invention can exhibit the properties of high heat resistance, high refractive index, and low volume shrinkage due to the crosslinked triazine ring-containing polymer, and thus liquid crystal displays, organic electro Luminescent (EL) display, touch panel, optical semiconductor (LED) element, solid-state image sensor, 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 when producing
Moreover, the high refractive index pattern produced from the composition of the present invention is required to prevent the appearance of the transparent electrode such as the touch panel described above, and the light extraction application and the black matrix application of the organic EL display. It can be used suitably for the use.

FIG. 2 is a ¹ H-NMR spectrum diagram of the polymer compound [4] obtained in Example 1. FIG. 5 is a graph showing the results of TG-DTA measurement 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 comprises a polymer having a repeating unit structure represented by the following formula (1) and at least two types of crosslinking agents.

In the above formulas, R and R ′ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or an aralkyl group, but from the viewpoint of further increasing the refractive index, both are hydrogen atoms preferable.
In the present invention, the carbon number of the alkyl group is not particularly limited, but is preferably 1 to 20, and in view of further enhancing the heat resistance of the polymer, the carbon number is preferably 1 to 10, more preferably 1 to 3. Is even more preferred. In addition, the structure may be linear, branched or cyclic.

  Specific examples of the alkyl group are methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-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-pen , 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 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-cyclo , 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, 2,2,2, 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 carbon number of the above alkoxy group is not particularly limited, but is preferably 1 to 20, and in view of further enhancing the heat resistance of the polymer, the carbon number is preferably 1 to 10, more preferably 1 to 3 preferable. In addition, the structure of the alkyl moiety may be linear, branched or cyclic.

  Specific examples of the alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-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-butyl 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 above aryl group is not particularly limited, but is preferably 6 to 40, and in view of further enhancing the heat resistance of the polymer, the carbon number is preferably 6 to 16 and more preferably 6 to 13 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 etc. are mentioned.

The carbon number of the aralkyl group is not particularly limited, but is preferably 7 to 20 carbon atoms, and the alkyl moiety thereof 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, 4-isobutylphenyl methyl, an alpha-naphthyl methyl group, etc. are mentioned.

Although said Ar ¹ will not be specifically limited if it is an aryl group which has a hydroxyl group, a carboxyl group, and / or a maleimide group, What is shown by following formula (15)-(17) is preferable.

（式中、Ｒ¹⁰²〜Ｒ¹¹⁰は、互いに独立して、上記Ｒ¹と同様の意味を表す。）

(Wherein, R ^{102 to} R ¹¹⁰ independently of each other represent the same meaning as the above R ¹ ).

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

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

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

（式中、Ｒ、Ｒ′およびＡｒ²は、上記と同じ意味を表す。）

(Wherein R, R ′ and Ar ² represent the same meaning as described above)

（式中、Ｒ、Ｒ′およびＡｒ²は、上記と同じ意味を表す。）

(Wherein R, R ′ and Ar ² represent the same meaning as described above)

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

The R ^{1 to} R ⁹² are each independently a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group having 1 to 10 carbon atoms which may have a branched structure, or 1 to 10 carbon atoms R ¹ represents an alkoxy group which may have a branched structure, and W ¹ and W ² each independently represent a single bond, CR ⁹⁵ R ⁹⁶ (R ⁹⁵ and R ⁹⁶ independently of each other, a hydrogen atom or carbon C ア ル キ ル O, O, S, SO, an alkyl group which may have a branched structure of the number 1 to 10 (provided that they may together form a ring), C = O, O, S, SO, SO ₂ or NR ⁹⁷ (R ⁹⁷ represents a hydrogen atom or an alkyl group optionally having 1 to 10 carbon atoms and having a branched structure), and R ⁹³ and R ^{94 each} represent a hydrogen atom or a carbon number Represents an alkyl group which may have a branched structure of 1 to 10;
The halogen atom includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Examples of the alkyl group and the alkoxy group include the same as described above.
Moreover, X ¹ and X ² each independently represent a single bond, an alkylene group optionally having a carbon number of 1 to 10, and a group represented by the formula (14).

The R ^{98 to} R ¹⁰¹ are, independently of one another, a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group having 1 to 10 carbon atoms which may have a branched structure, or 1 to 10 carbon atoms Y represents an alkoxy group which may have a branched structure, and Y ¹ and Y ² each independently represent a single bond or an alkylene group which may have a C 1-10 branched structure. Examples of the halogen atom, the alkyl group and the alkoxy group include the same as described above.
As an alkylene group which may have a C1-C10 branched structure, a methylene, ethylene, a propylene, a trimethylene, tetramethylene, a pentamethylene group etc. are mentioned.

  In particular, as Ar, at least one selected from Formulas (2) and (5) to (13) is preferable, and Formulas (2), (5), (7), (8), and (11) to (13) are preferable. More preferred is at least one of the groups shown in Although the thing shown by a following formula is mentioned as a specific example of the aryl group represented by said Formula (2)-(13), It is not limited to these.

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

  In particular, in consideration of enhancing the solubility in a highly safe solvent such as a resist solvent, it is preferable to include a repeating unit structure represented by the following formula (20), and a repeating unit structure represented by the following formula (21) More preferably,

（式中、Ｒ、Ｒ′およびＲ¹〜Ｒ⁴は、上記と同じ意味を表す。）

(Wherein, R, R ′ and R ^{1 to} R ⁴ have the same meaning as described above)

（式中、Ｒ、Ｒ′およびＲ¹〜Ｒ⁴は、上記と同じ意味を表す。）

(Wherein, R, R ′ and R ^{1 to} R ⁴ have the same meaning as described above)

  From such a point of view, particularly preferable repeating unit structures include those represented by the following formula (22), and those represented by the following formula (23) are more preferable.

（式中、ＲおよびＲ′は、上記と同じ意味を表す。）

(Wherein R and R ′ represent 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, and from the viewpoint of improving heat resistance and lowering shrinkage rate, 2000 or more is preferable, 50000 or less is preferable, 30000 or less is more preferable, and 10000 or less is more preferable from the point of raising solubility more and reducing 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 method disclosed in Patent Document 1 mentioned above.
For example, as shown in the following scheme 1, a triazine ring-containing polymer having a repeating structure (26) is produced by reacting a triazine compound (24) having a phenylamino group and a diamino compound (25) in an appropriate organic solvent Can be obtained.
In addition, the compound represented by the said Formula (24) can be manufactured by a well-known method from halogenated cyanuric and 3-aminophenol. Alternatively, the reaction may be carried out by adding a diamino compound in the reaction system of cyanuric halide and 3-aminophenol.

（式中、Ｘは、互いに独立してハロゲン原子を表す。ＲおよびＲ′は、上記と同じ意味を表す。）

(Wherein, X's each independently represent a halogen atom. R and R 'have the same meaning as described above.)

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

As the organic solvent, various solvents commonly used in this type of reaction can be used, for example, tetrahydrofuran, dioxane, dimethyl sulfoxide; N, N-dimethylformamide, N-methyl-2-pyrrolidone, tetramethyl urea, Hexamethylphosphoramide, N, N-dimethylacetamide, N-methyl-2-piperidone, N, N-dimethylethyleneurea, N, N, N ', N'-tetramethylmalonamide, N-methylcaprolactam, N-acetyl pyrrolidine, N, N-diethylacetamide, N-ethyl-2-pyrrolidone, N, N-dimethylpropionic acid amide, N, N-dimethylisobutyramide, N-methyl formamide, N, N'-dimethylpropylene urea Amide solvents such as H, and mixed solvents thereof
Among them, N, N-dimethylformamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, and a mixture thereof are preferable, and in particular, N, N-dimethylacetamide, N-methyl-2-pyrrolidone Is preferred.

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

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

In the present invention, a part of the halogen atoms of at least one terminal triazine ring is 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, an alkylamino, an alkoxysilyl group-containing alkylamino, an aralkylamino, and an arylamino group are preferable, an alkylamino and an arylamino group are more preferable, and an arylamino group is more preferable.
Examples of the above-mentioned alkyl group and alkoxy group include the same as described above.

Specific examples of the ester group include methoxycarbonyl, ethoxycarbonyl group and the like.
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 etc. are mentioned.
Specific examples of the aralkyl group include benzyl, p-methylphenylmethyl, m-methylphenylmethyl, o-ethylphenylmethyl, m-ethylphenylmethyl, p-ethylphenylmethyl, 2-propylphenylmethyl, 4-isopropylphenyl Methyl, 4-isobutylphenyl methyl, an alpha-naphthyl methyl group, etc. are mentioned.

  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-2 And -methyl-n-propylamino and the like.

Specific examples of the aralkylamino group include benzylamino, methoxycarbonylphenylmethylamino, ethoxycarbonylphenylmethylamino, p-methylphenylmethylamino, m-methylphenylmethylamino, o-ethylphenylmethylamino, m-ethylphenylmethylamino Amino, p-ethylphenylmethylamino, 2-propylphenylmethylamino, 4-isopropylphenylmethylamino, 4-isobutylphenylmethylamino, naphthylmethylamino, methoxycarbonylnaphthylmethylamino, ethoxycarbonylnaphthylmethylamino and the like. .
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, and 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- (2-aminoethyl) Aminoethyl) -3-methyldimethoxysilylpropylamino, N- (2-aminoethyl) -3-trimethoxysilylpropylamino and the like.

Specific examples of the aryloxy group include phenoxy, naphthoxy, anthranyloxy, pyrenyloxy, biphenyloxy, terphenyloxy, fluorenyloxy and the like.
Specific examples of the aralkyloxy group include benzyloxy, p-methylphenylmethyloxy, m-methylphenylmethyloxy, o-ethylphenylmethyloxy, m-ethylphenylmethyloxy, p-ethylphenylmethyloxy, 2-propyl A phenyl methyloxy, 4-isopropylphenyl methyloxy, 4-isobutylphenyl methyloxy, the (alpha) -naphthyl methyloxy group etc. are mentioned.

  These groups can be easily introduced by substituting a halogen atom on the triazine ring with a compound giving the corresponding substituent, and, for example, as shown in the following scheme 2, such as aniline (derivative) etc. The organic monoamine is added and reacted to obtain a triazine ring-containing polymer (27) having a phenylamino group at at least one end.

（式中、Ｘ、ＲおよびＲ′は上記と同じ意味を表す。）

(Wherein, X, R and R ′ represent the same meaning as described above)

As the organic monoamine, any of an alkyl monoamine, an aralkyl monoamine, and an aryl monoamine can be used.
As alkyl monoamines, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-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, 2-ethylhexyl amine etc. are mentioned.

Specific examples of the aralkyl monoamine include benzylamine, p-methoxycarbonylbenzylamine, p-ethoxycarbonylbenzylamine, p-methylbenzylamine, m-methylbenzylamine, o-methoxybenzylamine and the like.
Specific examples of aryl monoamines include aniline, p-methoxycarbonylaniline, p-ethoxycarbonylaniline, p-methoxyaniline, 1-naphthylamine, 2-naphthylamine, anthranylamine, 1-aminopyrene, 4-biphenylylamine, o- Examples include phenyl aniline, 4-amino-p-terphenyl, 2-amino fluorene 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 still more preferably 0.05 to 50 equivalents relative to the cyanuric halide compound. .
60-150 degreeC is preferable, 80-150 degreeC is more preferable, and 80-120 degreeC of the reaction temperature is still more preferable.
However, the mixing of the three components of the organic monoamine, halogenated cyanuric compound and diaminoaryl compound may be carried out at low temperature, and the temperature in that case 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 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, mixing of the two components of the halogenated cyanuric compound and the diaminoaryl compound may be performed at low temperature, and the temperature in that case is preferably about -50 to 50 ° C, and more preferably about -20 to 50 ° C, -20-10 degreeC is further more preferable. After charging at a low temperature, it is preferable to add an organic monoamine and raise the temperature to the polymerization temperature in one step (in one step) to carry out the reaction.
In addition, the reaction of reacting a cyanuric halide compound and a diaminoaryl compound in the presence of such an organic monoamine may be performed using the same organic solvent as described above.

In the composition of the present invention, at least two 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 triazine ring-containing polymer described above.
As such a compound, a melamine compound having a crosslink forming substituent such as methylol group or methoxymethyl group, a substituted urea compound, a compound having a crosslink forming substituent such as an epoxy group or an oxetane group, blocked isocyanate Compounds containing an acid anhydride, compounds containing an acid anhydride, compounds containing an (meth) acrylic group, phenoplast compounds, etc., but from the viewpoint of heat resistance and storage stability, epoxy groups, blocked isocyanate groups, (meth) acrylics The compound containing a group is preferable, and in particular, two compounds selected from a compound having a blocked isocyanate group and a polyfunctional epoxy compound and a polyfunctional (meth) acrylic compound which give a photocurable composition without using an initiator Preferably, a polyfunctional epoxy compound and a polyfunctional (meth) acrylic compound Seen together is more preferable.
In addition, these compounds should just have at least 1 bridge formation substituent, when using for the terminal treatment of a polymer, and when using for the crosslinking process of polymers mutually, at least 2 bridge formation substituents 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 thereof include tris (2,3-epoxypropyl) isocyanurate, 1,4-butanediol diglycidyl ether, 1,2-epoxy-4- (epoxyethyl) cyclohexane, glycerol triglycidyl ether, diethylene glycol diglycidyl Ether, 2,6-diglycidyl phenyl glycidyl ether, 1,1,3-tris [p- (2,3-epoxypropoxy) phenyl] propane, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, 4,4'- Methylenebis (N, N-diglycidyl aniline), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, trimethylolethane triglycidyl ether, bisphenol-A-diglycidyl ether, pentaerythyl Ritol polyglycidyl ether etc. are mentioned.

  In addition, YH-434 and YH434L (made by Tohto Kasei Co., Ltd.), which are epoxy resins having at least two epoxy groups, and Eporide GT-401, which are epoxy resins having a cyclohexene oxide structure are commercially available products. -403, GT-301, GT-302, Celoxide 2021, 3000 (manufactured by Daicel Chemical Industries, Ltd.), bisphenol A epoxy resin, Epicoat (now jER) 1001, 1002, 1003, 1004, 1007, 1009, 1010, 828 (above, made by Japan Epoxy Resins Co., Ltd.), Epicoat (now jER) 807 (made by Japan Epoxy Resins, Inc.) which is a bisphenol F-type epoxy resin Epikote (now a phenol novolac epoxy resin) jER) 152, 154 (above, Japan Epoxy Resins Co., Ltd.), EPPN 201, 202 (above, Nippon Kayaku Co., Ltd.), cresol novolac epoxy resin, EOCN-102, 103S, 104 S, 1020, 1025, 1027 (above, Nippon Kayaku Co., Ltd. product), Epicoat (now, jER) 180 S 75 (Japan Epoxy Resins Co., Ltd. product), an epoxy epoxy resin, Denacol EX- 252 (manufactured by Nagase ChemteX Co., Ltd.), CY175, CY177, CY179 (manufactured by CIBA-GEIGY A.G), Araldite CY-182, the same CY-192, and the same CY-184 (manufactured by CIBA-GEIGY A. G), Epiclon 200, 400 (all manufactured by DIC Corporation), Epicoat (now jER) 87 872 (above, made by Japan Epoxy Resins Co., Ltd.), ED-5661, ED-5662 (above, made by Celanese Coatings Co., Ltd.), aliphatic polyglycidyl ether, Denacol EX-611, EX- 612, EX-614, EX-622, EX-411, EX-512, EX-522, EX-421, EX-313, EX-314, EX-321 (Nagase Chemex) (Made by KK) etc. 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 thereof include ethylene glycol diacrylate, ethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, ethoxylated bisphenol A diacrylate, ethoxylated bisphenol A dimethacrylate, ethoxylated trimethylolpropane triacrylate, and ethoxylated Trimethylolpropane trimethacrylate, ethoxylated glycerin triacrylate, ethoxylated glycerin trimethacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetramethacrylate, ethoxylated dipentaerythritol hexaacrylate, polyglycerin monoethylene oxide polyacrylate, polyglycerin Polyethylene Glycol polyacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, Tricyclodecane dimethanol diacrylate, tricyclodecane dimethanol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate and the like can be mentioned.

  Also, polyfunctional (meth) acrylic compounds are commercially available, and specific examples thereof include NK esters A-200, A-400, A-600, A-1000, and 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, A-T PT-9EO, AT-20E, ATM-4E, ATM-35E (above, Shin-Nakamura Chemical Co., Ltd. product), KAYARAD (registered trademark) DPEA-12, PEG400DA, THE-330, and RP -104 (above, Nippon Kayaku Co., Ltd. product), M-210, M-350 (above, Toagosei Co., Ltd. product), KAYARAD (registered trademark) DPHA, NPGDA, PET 30 (above, Nippon Kayaku) NK Ester A-DPH, A-TMPT, A-DCP, A-HD-N, TMPT, DCP, NPG, HD-N (all, Shin-Nakamura Chemical Co., Ltd. And NK Oligo U-15 HA (manufactured by Shin-Nakamura Chemical Co., Ltd.), NK Polymer Vanaresin 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, and specific examples thereof include phthalic anhydride, tetrahydrophthalic anhydride, hexahydroanhydride One per molecule of phthalic acid, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, maleic anhydride, maleic anhydride, succinic anhydride, octyl succinic anhydride, dodecenyl succinic anhydride, etc. With an acid anhydride group; 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, pyromellitic acid anhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene Succinic acid dianhydride, bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic acid dianhydride, 5- (2,5-dicarboxylic acid dianhydride, Xotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 1,2,3,4-butanetetracarboxylic acid dianhydride, 3,3 ′, 4,4 ′ Benzophenone tetracarboxylic acid dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic acid dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 1, Those having two acid anhydride groups in the molecule such as 3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride and the like can be mentioned.

  As a compound containing a blocked isocyanate, when an isocyanate group (-NCO) has two or more blocked isocyanate groups blocked by a suitable protecting group in one molecule, and is exposed to a high temperature during heat curing It is not particularly limited as long as the protective group (block portion) is thermally dissociated and the resulting isocyanate group causes a cross-linking reaction with the resin. For example, one group represented by the following formula is The compound which has 2 or more in the molecule (note that these groups may be the same or different) may be mentioned.

（式中、Ｒ_bはブロック部の有機基を表す。）

(Wherein, R _b represents an organic group of a 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 isophorone diisocyanate, 1,6-hexamethylene diisocyanate, methylenebis (4-cyclohexylisocyanate), polyisocyanate of trimethylhexamethylene diisocyanate, and dimers thereof And trimers and reaction products thereof with diols, triols, diamines, or triamines.
As the blocking agent, for example, alcohols such as methanol, ethanol, isopropanol, n-butanol, 2-ethoxyhexanol, 2-N, N-dimethylaminoethanol, 2-ethoxyethanol, cyclohexanol and the like; phenol, o-nitrophenol Phenols such as p-chlorophenol, o-, m- or p-cresol; lactams such as ε-caprolactam; acetone oxime, methyl ethyl ketone oxime, methyl isobutyl ketone oxime, cyclohexanone oxime, acetophenone oxime, oximes such as benzophenone oxime And pyrazoles such as pyrazole, 3,5-dimethylpyrazole and 3-methylpyrazole; and thiols such as dodecanethiol and benzenethiol.

  Compounds containing blocked isocyanates are commercially available, and specific examples thereof include B-830, B-815N, B-842N, B-870N, B-874N, B-882N, B. -7005, B-7030, B-7075, B-5010 (above, Mitsui Chemicals Polyurethanes Co., Ltd.), Duranate (registered trademark) 17B-60PX, TPA-B80E, MF-B60X, MF-K60X, The same E402-B80T (above, Asahi Kasei Chemicals Co., Ltd. product), Kalens MOI-BM (trademark) (above, Showa Denko Co., Ltd. product), etc. are mentioned.

The aminoplast compound is not particularly limited as long as it has two or more methoxymethylene groups in one molecule, and, for example, hexamethoxymethylmelamine CYMEL (registered trademark) 303, tetrabutoxymethyl glycoluril 1170 Cymer series such as tetramethoxymethyl benzoguanamine 1123 (all manufactured by Nippon Cytech Industries, Ltd.), methylated melamine resin Nikalac (registered trademark) MW-30HM, MW-390, MW-100LM, and the like Examples include melamine based compounds such as Nicalac series such as MX-750LM, methylated urea resin, MX-270 and MX-280, MX-290 (above, Sanwa Chemical Co., Ltd.).
The oxetane compound is not particularly limited as long as it has two or more oxetanyl groups in one molecule, and, for example, OXT-221, OX-SQ-H, OX-SC (containing one or more oxetanyl groups) And Toagosei Co., Ltd.).

As a phenoplast compound, it has two or more hydroxymethylene groups in one molecule, and when exposed to a high temperature during heat curing, the crosslinking reaction proceeds by the dehydration condensation reaction with the polymer of the present invention It is a thing.
As the phenoplast compound, for example, 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 And 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 as specific examples, 26DMPC, 46DMOC, DM-BIPC-F, DM-BIOC-F, TM-BIP-A, BISA-F, BI25X-DF And BI25X-TPA (all manufactured by Asahi Organic Materials Co., Ltd.) and the like.

Among these, polyfunctional (meth) acrylic compounds are preferable in that they can suppress the decrease in refractive index due to the addition of a crosslinking agent and the curing reaction proceeds rapidly, and among them, triazine ring-containing polymers are preferable. The following polyfunctional (meth) acrylic compounds having an isocyanuric acid skeleton are more preferable because they are excellent in compatibility.
As a polyfunctional (meth) acrylic compound which has such frame | skeleton, NK ester A-9300 and the same A-93000-1CL (all are Shin-Nakamura Chemical Co., Ltd. product) are mentioned, for example.

（式中、Ｒ¹¹¹〜Ｒ¹¹³は、互いに独立して、末端に少なくとも１つの（メタ）アクリル基を有する一価の有機基である。）

(Wherein, each of R ^{111 to} R ¹¹³ independently of each other is a monovalent organic group having at least one (meth) acrylic group at its terminal).

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

  Furthermore, in consideration of improving the alkali resistance of the obtained cured film, NK ester A-GLY-20E (manufactured by Shin-Nakamura Chemical Co., Ltd.) and ATM-35E (manufactured by Shin-Nakamura Chemical Co., Ltd.) It is preferable to use it in combination with the polyfunctional (meth) acrylic compound having the above-mentioned isocyanuric acid skeleton, and at least one of them.

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 in view of solvent resistance, the lower limit is preferably 2 parts by mass, more preferably 5 parts The upper limit is preferably 20 parts by mass, more preferably 15 parts by mass, in consideration of controlling the refractive index.
The use ratio of the two or more crosslinking agents is not particularly limited, but in the case where the multifunctional (meth) acrylic compound and the multifunctional epoxy compound which are the preferable combination 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 in mass ratio, preferably 1: 1 to 5: 1, and more preferably 1: 1 to 3: It is 1.

  In the composition of the present invention, an initiator corresponding to each crosslinking agent can also be blended. In addition, as above-mentioned, when using a polyfunctional epoxy compound and a polyfunctional (meth) acrylic compound as a crosslinking agent, although photocuring advances without using an initiator, a cured film is given, but in that case It is safe to use an initiator.

When using a polyfunctional epoxy compound as a crosslinking agent, a photo-acid generator and a photo-base generator can be used.
The photoacid generator may be appropriately selected from known ones and used. For example, onium salt derivatives such as diazonium salts, sulfonium salts and iodonium salts can be used.
Specific examples thereof include aryldiazonium salts such as phenyldiazonium hexafluorophosphate, 4-methoxyphenyldiazonium hexafluoroantimonate, 4-methylphenyldiazonium hexafluorophosphate and the like; diphenyliodonium hexafluoroantimonate, di (4-methylphenyl) Diaryl iodonium salts such as iodonium hexafluorophosphate, di (4-tert-butylphenyl) iodonium hexafluorophosphate; triphenylsulfonium hexafluoroantimonate, tris (4-methoxyphenyl) sulfonium hexafluorophosphate, diphenyl-4-thiophenoxy Phenyl sulfonium hexafluoroantimonate, diphenyl-4-thiophenoxy Henylsulfonium hexafluorophosphate, 4,4'-bis (diphenylsulfonylo) phenyl sulfide-bishexafluoroantimonate, 4,4'-bis (diphenylsulfonylio) phenyl sulfide-bishexafluorophosphate, 4,4 '-Bis [di (β-hydroxyethoxy) phenylsulfonio] phenyl sulfide-bishexafluoroantimonate, 4,4'-bis [di (β-hydroxyethoxy) phenylsulfonio] phenyl sulfide-bis-hexafluorophosphate , 4- [4 '-(Benzoyl) phenylthio] phenyl-di (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- [4'-(benzoyl) phenylthio] phenyl-di (4-fluorophenyl) sul Triarylsulfonium salts such as triphenylsulfonium hexafluorophosphate and the like.

  As these onium salts, commercially available products may be used, and as specific examples thereof, Sanaid SI-60, SI-80, SI-100, SI-60L, SI-80L, SI-100L, SI-L145, SI- L150, SI-L160, SI-L110, SI-L147 (above, made by Sanshin Chemical Industry Co., Ltd.), UVI-6950, UVI-6970, UVI-6974, UVI-6990, UVI-6992 (above, union carbide) CPI-100P, CPI-100A, CPI-200K, CPI-200S (above, San-Apro Ltd.), Adeka Optomer SP-150, SP-151, SP-170, SP-171 (above, Asahi Denka Kogyo Co., Ltd. product, Irgacure 261 (manufactured by BASF Corporation), CI-2481, CI-2624, CI-26 9, CI-2064 (above, Nippon Soda Co., Ltd. product), CD-1010, CD-1011, CD-1012 (above, Sartmar company), 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 ( The above, Midori Chemical Co., Ltd. product), PCI-061 T, PCI-062 T, PCI-020 T, P I-022T (manufactured by Nippon Kayaku Co., Ltd.), it can be mentioned IBPF, IBCF (manufactured by Sanwa Chemical Co., Ltd.), and the like.

On the other hand, the photo base generator may be appropriately selected from known ones and used, for example, Co-amine complex type, oxime carboxylate type, carbamate type, quaternary ammonium salt type photo base generator, etc. 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 (triphenylmethyl borate), 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, etc. It can be mentioned.
Moreover, a commercial item may be used for a photobase generator, As a specific example, TPS-OH, NBC-101, ANC-101 (all are a product name, Midori Chemical Co., Ltd. product) etc. are mentioned.

When a photoacid or base generator is used, it is preferably used in an amount of 0.1 to 15 parts by mass, more preferably 1 to 10 parts by mass, with respect to 100 parts by mass of the polyfunctional epoxy compound.
In addition, you may mix | blend the epoxy resin hardening | curing agent in the quantity of 1-100 mass parts with respect to 100 mass parts of polyfunctional epoxy compounds as needed.

On the other hand, when using a polyfunctional (meth) acrylic compound, a radical photopolymerization initiator can be used.
The photo radical polymerization initiator may be appropriately selected from known ones and used. For example, acetophenones, benzophenones, Michler's benzoyl benzoate, amiloxym esters, oxime esters, tetramethylthiuram monosulfide and thioxanthones, etc. Can be mentioned.
In particular, photocleavage type photo radical polymerization initiators are preferred. The photocleavage type photo radical polymerization initiator is described in the latest UV curing technology (p. 159, Issuer: Kazuhiro Takata, Publisher: Institute of Technology Information, published in 1991).
As a commercially available radical photopolymerization initiator, for example, BASF Corp. trade name: Irgacure 127, 184, 369, 379, 379 EG, 651, 500, 754, 819, 903, 907, 784, 2959, CGI 1700, CGI 1750, CGI 1850 CG24-61, OXE01, OXE02, Darocure 1116, 1173, MBF, manufactured by BASF Trade name: Lucirin TPO, manufactured by UCB Trade name: Yubekrill P36, manufactured by Fratetris-Lamberty Trade name: Ezacure KIP150, KIP65LT, KIP100F, KT37, KT55, KTO46, KIP75 / B etc. are mentioned.
When using a radical photopolymerization initiator, it is preferable to use in the range of 0.1 to 200 parts by mass and use in the range of 1 to 150 parts by mass with respect to 100 parts by mass of the polyfunctional (meth) acrylate compound. Is more preferred.

It is preferable that various solvents be added to the composition of the present invention, and the triazine ring-containing polymer be dissolved and used.
As the solvent, for example, 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.

  Under the present circumstances, solid content concentration in a composition will not be specifically limited if it is a range which does not affect storage stability, What is necessary is just to set suitably according to the thickness of the target film | membrane. Specifically, in view 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.

In the composition of the present invention, as long as the effects of the present invention are not impaired, addition of triazine ring-containing polymer, crosslinking agent and other components other than solvent, such as leveling agent, surfactant, silane coupling agent, etc. An agent may be included.
Examples of surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, etc .; polyoxyethylene octyl phenol ether, polyoxyethylene nonyl phenol 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, polyoxyethylene so Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as bitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, etc. EF303, EF352 (Mitsubishi Materials Electronics Kasei Co., Ltd. (old) manufactured by Gemco), trade names Megafac F171, F173, R-08, R-30, R-40, F-40, F-553, F-554, RS-75, RS-72-K (made by DIC Corporation), Florard FC430, FC431 (made by Sumitomo 3M Co., Ltd.), trade name Asahi Guard AG710, Surfron S-382, SC101, SC101, SC102, SC103, SC104, SC105 , SC 106 (Asahi Fluorine-based surfactants such as Shikko Co., Ltd., organosiloxane polymer KP 341 (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 KK), and the like.

These surfactants may be used alone or in combination of two or more. The amount of surfactant used is preferably 0.0001 to 5 parts by mass, more preferably 0.001 to 1 parts 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.
The above-mentioned other components can be added at any step in preparing the composition of the present invention.

The composition of the present invention can be applied to a substrate and then heated as required to evaporate the solvent, and then heated or irradiated with light to form a desired cured film.
The composition may be applied by any method, such as spin coating, dipping, flow coating, inkjet, jet dispenser, spraying, bar coating, gravure coating, slit coating, roll coating, transfer, etc. Methods such as printing, brush coating, blade coating, air knife coating and the like can be employed.

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

In the case of forming a negative pattern forming composition, the above composition may further contain an oxirane ring-containing compound and a photocurable catalyst.
Examples of the oxirane ring-containing compound include compounds having one or more, preferably two or more oxirane rings in the molecule, and specific examples thereof include glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, alicyclic epoxy resin Resin, epoxy modified polybutadiene resin, oxetane compound etc. are mentioned. These may be used alone or in combination of two or more.
Although the compounding quantity of an oxirane containing compound is not specifically limited, It can be about 10-400 mass parts with respect to 100 mass parts of triazine ring containing polymers.

The photocurable catalyst includes a photocation generator. Specific examples of the photocation generator include triarylsulfonium salts such as triphenylsulfonium hexafluorophosphate and triphenylsulfonium hexafluoroantimonate; triarylselenium salts; diphenyliodonium hexafluorophosphate and diphenyliodonium hexafluoroantimonate Diaryl iodonium salts and the like can be mentioned. These may be used alone or in combination of two or more.
The compounding 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 composition for negative pattern formation is not specifically limited, What is necessary is to mix | blend and prepare each component in arbitrary order. At this time, the above-mentioned solvent may be used.
The composition described above can be cured by, for example, irradiating ultraviolet light or the like at 1 to 4000 mJ / cm ² after application according to the above-described method. 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 a laser beam.
In addition, as needed, when using a low heat resistant base material etc. about 80-180 degreeC before and after exposure, you may heat at preferably 80 degreeC or more and less than 150 degreeC, More preferably, it is 80-130 degreeC.
The development after exposure can be carried out by immersing the exposure resin in the above-described organic solvent developer or aqueous developer.

On the other hand, when it is set as a positive pattern forming composition, 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. As a specific example thereof, 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 and the like.
Although the compounding quantity of an oxirane containing compound is not specifically limited, It can be about 4-60 mass parts with respect to 100 mass parts of triazine ring containing polymers.

The preparation method of the composition for forming a positive pattern is also not particularly limited, and the components may be mixed and prepared in an arbitrary order. At this time, the above-mentioned solvent may be used.
The composition described above can be applied by the above-described method, and then cured by, for example, irradiating ultraviolet light or the like at 1 to 2000 mJ / cm ² by the above-described light irradiation method. Also in this case, when using a low heat resistant substrate or the like at about 80 to 180 ° C. before and after exposure, heating may be preferably performed at 80 ° C. or more and less than 150 ° C., more preferably 80 to 130 ° C. .
The development after exposure can be carried out by immersing the exposure resin in the above-described organic solvent developer or aqueous developer.

  Various additives may be added to the above-mentioned each composition for pattern formation if needed. Additives include thermal cation generators such as benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 1-naphthylmethyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 4-hydroxyphenyldimethylsulfonium methyl sulfate; 2 Photosensitizers, such as 5-diethyl thioxanthone, anthracene, 9, 10- ethoxy anthracene, etc., the additive illustrated in the composition for film formation, etc. are mentioned.

  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, and thus, liquid crystal display, organic electroluminescence (EL) display, touch panel, optical semiconductor (LED) elements, solid-state imaging elements, organic thin-film solar cells, dye-sensitized solar cells, organic thin-film transistors (TFTs), lenses, prism cameras, binoculars, microscopes, semiconductor exposure devices, etc. And optical materials can be suitably used.

EXAMPLES The present invention will be more specifically described below with reference to examples and comparative examples, but the present invention is not limited to the following examples. In addition, each measuring device used in the Example is as follows.
[ ¹ H-NMR]
Equipment: Varian NMR System 400NB (400 MHz)
) JEOL-ECA 700 (700 MHz)
Measurement solvent: DMSO-d6
Reference material: tetramethylsilane (TMS) (δ 0.0 ppm)
[GPC]
Device: Remodeled 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]
Device: SHIMADSU UV-3600 manufactured by Shimadzu Corporation
[Ellipsometer]
Device: JA A. Woolam Japan multi-incidence spectroscopy ellipsometer VASE
[Differential thermal balance (TG-DTA)]
Device: TG-8120 manufactured by Rigaku Corporation
Heating rate: 10 ° C / min Measurement temperature: 25 ° C-750 ° C
[electronic microscope]
Nippon Denshi Co., Ltd. electron microscope S-4800

[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.) is added to a 500 mL four-necked flask, and 104.14 g of N-methyl-2-pyrrolidone (NMP) is added. Melted and cooled to 0 ° C. or less. Thereafter, 2,4,6-trichloro-1,3,5-triazine [1] (18.34 g, 0.1 mol, made by Evonik Degussa) was added and stirred for 1 hour, then dissolved in 154.96 g of NMP. -Phenylenediamine [3] (16.14g, 0.15moL) was dropped so that internal temperature was maintained at 30 degrees C or less. After dropping, the mixture was heated to 90 ° C. and allowed to react for 3 hours, and 50.34 g of triethylamine was added to terminate the polymerization.
The formed triethylamine hydrochloride was removed by filtration, and the filtrate was dropped into 1290 g of ion exchanged water to carry out reprecipitation. The resulting precipitate was filtered, and 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 compound [4] (hereinafter referred to as L-TmDA-100).
The measurement result of the ¹ H-NMR spectrum of L-TmDA-100 is shown in FIG. Moreover, the weight average molecular weight Mw measured by polystyrene conversion by GPC of L-TmDA-100 was 8,200, and polydispersion degree 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 measurement was performed at a temperature rising rate of 15 ° C./min by TG-DTA, the 5% weight loss was 392 ° C. The The results are 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, 18.00 g of propylene glycol monomethyl ether (PGME) was added as a solvent, and a 40% by mass polymer solution (hereinafter referred to as 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, which was 1.7494 (@ 550 nm).

[3] Preparation of fine pattern [Example 3]
L-TmDA-100-M 18.95 g prepared in Example 2, 0.74 g of a multifunctional acrylate (AT-20E, Shin-Nakamura Chemical Co., Ltd. product), a multifunctional epoxy (Epolide GT-401, Daicel Chemical Industries, Ltd. Add 0.37 g of Photonics Co., Ltd.), 0.52 g of photo radical initiator (IRGACURE OXE02, manufactured by BASF), 0.45 g of a photoacid generator (CPI-210S, manufactured by San-Apro Co., Ltd.), and 24.0 g of PGME. 45 g of composition (LP-W) of 20% by mass was prepared.
The composition was filtered using a 0.45 μm filter and then coated on a glass substrate using a spin coater. The coating film was formed by baking (soft baking) on a hot plate at 100 ° C. for 30 seconds. The coating film was irradiated with ultraviolet light at an irradiation amount of 365 nm of 200 mJ / cm ² by an ultraviolet irradiation device MA6 (manufactured by SUSS). Then, it is post-baked on a hot plate at 100 ° C. for 25 minutes, developed by immersion in a 23 ° C. NMD-3 developer (manufactured by Tokyo Ohka Kogyo Co., Ltd.) for a certain period of time, and developed. went. After development, 10/10 μm, 7/7 μm, 5/5 μm lines / spaces 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 the electron microscope observation was performed, the foreign material was not seen on the cured film.

[4] Preparation of Cured Film [Example 4]
L-TmDA-100-M 18.95 g prepared in Example 2, 0.74 g of a multifunctional acrylate (AT-20E, Shin-Nakamura Chemical Co., Ltd. product), a multifunctional epoxy (Epolide GT-401, Daicel Chemical Industries, Ltd. Add 0.37 g of Photonics Co., Ltd.), 0.52 g of photo radical initiator (IRGACURE OXE02, manufactured by BASF), 0.45 g of a photoacid generator (CPI-210S, manufactured by San-Apro Co., Ltd.), and 24.0 g of PGME. 45 g of composition (LP-W) of 20% by mass was prepared.
The composition was filtered using a 0.45 μm filter and then coated on a silicon wafer substrate using a spin coater. The coating film was formed by baking (soft baking) on a hot plate at 100 ° C. for 30 seconds. The coating film was irradiated with ultraviolet light at an irradiation amount of 365 nm of 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 prepare 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 (10)

A triazine-based polymer-containing composition for pattern formation, which comprises a polymer having a repeating unit structure represented by the following formula (1) and at least two types of photocurable crosslinking agents.

[Wherein, 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 is 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 each independently a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group optionally having a carbon number of 1 to 10, or a carbon number of 1 represents an alkoxy group which may have a branched structure to 10, R ⁹³ and R ⁹⁴ represents an alkyl group which may have a hydrogen atom or a branched structure having 1 to 10 carbon atoms, W ¹ and W ² is, independently of each other, a single bond, CR ⁹⁵ R ⁹⁶ (R ⁹⁵ and R ⁹⁶ are each independently a hydrogen atom or an alkyl group having a branched structure of 1 to 10 carbon atoms ( Provided that they may together form a ring))), C = O, O, S, SO, SO ₂ or NR ⁹⁷ (R ⁹⁷ is a hydrogen atom or 1 carbon atom represents an alkyl group which may have a branched structure 10.) represents, X ¹ Contact Fine X ² independently of one another, a single bond, an alkylene group which may have a branched structure of 1 to 10 carbon atoms, or the formula, (14)

(Wherein, R ^{98 to} R ¹⁰¹ each independently represent a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group having 1 to 10 carbon atoms, or a branched structure, or 1 carbon atom) And an alkoxy group which may have a branched structure of 10 to 10, and Y ¹ and Y ² independently of each other are a single bond or an alkylene group which may have a branched structure of 1 to 10 carbon atoms Represents a group represented by ]}   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.   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. The triazine type-polymer containing composition of any one of Claims 1-3 in which the said polymer contains the repeating unit structure shown by following formula (18).

(Wherein, R, R ′ and Ar ² represent the same meaning as described above) The triazine type polymer containing composition of Claim 4 containing the repeating unit structure shown by following formula (19).

(Wherein, R, R ′ and Ar ² represent the same meaning as described above) The triazine type polymer containing composition of Claim 5 containing the repeating unit structure shown by following formula (23).

  The triazine polymer-containing composition according to any one of claims 1 to 6, further comprising an azide compound.   A pattern produced from the triazine polymer-containing composition according to any one of claims 1 to 7.   An optical member comprising a substrate and the pattern according to claim 8 formed on the substrate.   An electronic device comprising a substrate and the pattern according to claim 8 formed on the substrate.

Images