JP6693116B2 - Light-scattering film forming composition and light-scattering film - Google Patents

Description

  The present invention relates to a composition for forming a light scattering film and a light scattering film.

  Until now, various attempts have been made to improve the functionality of polymer compounds. For example, attempts have been made to introduce an aromatic ring, a halogen atom or a sulfur atom as a method for increasing the refractive index of a polymer compound. Among them, episulfide polymer compounds and thiourethane polymer compounds having a sulfur atom introduced are put to practical use as high refractive index lenses for spectacles.

  In addition, a method using an inorganic metal oxide is known as the most effective method for achieving a higher refractive index of a polymer compound. For example, a method of increasing the refractive index by using a hybrid material obtained by mixing a siloxane polymer and a fine particle dispersion material in which zirconia, titania, or the like is dispersed has been reported (Patent Document 1). Furthermore, a method of introducing a condensed ring skeleton having a high refractive index into a part of a siloxane polymer has also been reported (Patent Document 2).

  In addition, many attempts have been made to impart heat resistance to polymer compounds, and it is well known that the heat resistance of polymer compounds can be improved by introducing an aromatic ring. .. For example, a polyarylene copolymer having a substituted arylene repeating unit in its main chain has been reported (Patent Document 3), and this polyarylene copolymer is expected to be applied mainly to heat-resistant plastics.

  Melamine resin is well known as a triazine-based resin, but has a far lower decomposition temperature than heat-resistant materials such as graphite. Up to now, aromatic polyimides and aromatic polyamides have been mainly used as heat-resistant organic materials composed of carbon and nitrogen, but since these materials have a linear structure, the heat-resistant temperature is not so high. A triazine-based condensation material has also been reported as a nitrogen-containing polymer material having heat resistance (Patent Document 4).

  By the way, in recent years, when developing electronic devices such as a liquid crystal display, an organic electroluminescence (EL) display, an optical semiconductor (LED) element, a solid-state image sensor, an organic thin film solar cell, a dye-sensitized solar cell, and an organic thin film transistor (TFT). In addition, high-performance polymer materials have been required. Specific properties required include 1) heat resistance, 2) transparency, 3) high refractive index, 4) high solubility, and 5) low volume shrinkage.

  In view of this point, the present inventors have found that the hyperbranched 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 it is suitable as a film-forming composition for producing an electronic device, since it can achieve high properties and low volume shrinkage (Patent Document 5). However, when the cured film produced from the composition is applied to the light extraction layer of an organic EL device or a light emitting diode, further improvement of the light extraction efficiency (light diffusion efficiency) is required.

JP, 2007-246877, A JP, 2008-24832, A US Pat. No. 5,886,130 JP, 2000-53659, A International Publication No. 2010/128661

  The present invention has been made in view of the above circumstances, and includes a triazine ring-containing polymer capable of achieving high heat resistance, high transparency, high refractive index, high solubility, and low volume shrinkage by itself, and light diffusion. An object of the present invention is to provide a composition for forming a light-scattering film, which can give a cured film having good efficiency and light extraction efficiency.

  The present inventors have conducted extensive studies in order to achieve the above-mentioned object, and as a result, a composition containing a predetermined triazine ring-containing polymer, a cross-linking agent, and a light diffusing agent containing barium titanate has a light diffusion property. The inventors have found that a cured film having good efficiency and light extraction efficiency can be provided, and completed the present invention.

［式中、Ｒ及び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、又はアラルキル基を表し、
Ａｒは、下記式（２）〜（１３）で表される基からな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の直鎖状若しくは分岐状のアルキル基、又は炭素数１〜１０の直鎖状若しくは分岐状のアルコキシ基を表し、
Ｒ⁹³及びＲ⁹⁴は、水素原子、又は炭素数１〜１０の直鎖状若しくは分岐状のアルキル基を表し、
Ｗ¹及びＷ²は、互いに独立して、単結合、−ＣＲ⁹⁵Ｒ⁹⁶−、−Ｃ(＝Ｏ)−、−Ｏ−、−Ｓ−、−Ｓ(＝Ｏ)−、−ＳＯ₂−又は−ＮＲ⁹⁷−を表し、Ｒ⁹⁵及びＲ⁹⁶は、互いに独立して、水素原子、又は炭素数１〜１０の直鎖状若しくは分岐状のアルキル基を表し、これらは互いに結合してこれらが結合する炭素原子と共に環を形成していてもよく、Ｒ⁹⁷は、水素原子、又は炭素数１〜１０の直鎖状若しくは分岐状のアルキル基を表し、
Ｘ¹及びＸ²は、互いに独立して、単結合、炭素数１〜１０の直鎖状若しくは分岐状のアルキレン基、又は下記式（１４）で表される基を表す。

（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の直鎖状若しくは分岐状のアルキル基、又は炭素数１〜１０の直鎖状若しくは分岐状のアルコキシ基を表し、Ｙ¹及びＹ²は、互いに独立して、単結合、又は炭素数１〜１０の直鎖状若しくは分岐状のアルキレン基を表す。）｝］
２．前記チタン酸バリウム粒子の平均一次粒子径が、５０ｎｍ〜３μｍである１の光散乱膜形成用組成物。
３．更に、溶媒を含む１又は２の光散乱膜形成用組成物。
４．１〜３のいずれかの光散乱膜形成用組成物を硬化させて得られる光散乱膜。
５．ヘーズ値が３０〜７５である４の光散乱膜。
６．４又は５の光散乱膜の上に平坦化膜を積層させた光散乱膜。
７．ヘーズ値が２５〜７０である６の光散乱膜。
８．４〜７のいずれかの光散乱膜を備える有機ＥＬ素子。
９．４〜７のいずれかの光散乱膜を備える発光ダイオード。
１０．４〜７のいずれかの光散乱膜を備える誘電材料。 Therefore, the present invention provides the following composition for forming a light-scattering film and a light-scattering film.
1. A composition for forming a light-scattering film, comprising a triazine ring-containing polymer containing a repeating unit represented by the following formula (1), a crosslinking agent, and a light diffusing agent containing barium titanate particles.

[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,
Ar represents at least one selected from the group consisting of groups represented by the following formulas (2) to (13).

{In the formula, R ^{1 to} R ⁹² are each independently a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, a linear or branched alkyl group having 1 to 10 carbon atoms, or 1 to 10 carbon atoms. Represents a linear or branched alkoxy group of
R ⁹³ and R ⁹⁴ represent a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms,
W ¹ and W ² are independently of each other, a single ^{bond, -CR 95 R 96 -, -} C (= O) -, - O -, - S -, - S (= O) -, - SO 2 - Or —NR ⁹⁷ —, R ⁹⁵ and R ⁹⁶ each independently represent a hydrogen atom, or a linear or branched alkyl group having 1 to 10 carbon atoms, which are bonded to each other to form A ring may be formed together with the carbon atom to be bonded, R ⁹⁷ represents a hydrogen atom, or a linear or branched alkyl group having 1 to 10 carbon atoms,
X ¹ and X ² each independently represent a single bond, a linear or branched alkylene group having 1 to 10 carbon atoms, or a group represented by the following formula (14).

(In the formula, R ^{98 to} R ¹⁰¹ are each independently a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, a linear or branched alkyl group having 1 to 10 carbon atoms, or 1 to 10 carbon atoms. Represents a linear or branched alkoxy group, and Y ¹ and Y ² independently of each other represent a single bond or a linear or branched alkylene group having 1 to 10 carbon atoms.)}]
2. 1. The light-scattering film-forming composition 1, wherein the barium titanate particles have an average primary particle diameter of 50 nm to 3 μm.
3. Furthermore, 1 or 2 composition for light-scattering film formation containing a solvent.
A light-scattering film obtained by curing the composition for forming a light-scattering film of any one of 4.1 to 3.
5. 4. A light-scattering film having a haze value of 30 to 75.
A light-scattering film having a flattening film laminated on the light-scattering film 6.4 or 5.
7. 6. A light-scattering film having a haze value of 25 to 70.
An organic EL device comprising the light scattering film according to any one of 8.4 to 7.
A light emitting diode comprising the light scattering film according to any one of 9.4 to 7.
A dielectric material comprising the light-scattering film of any of 10.4 to 7.

  The light-scattering film-forming composition of the present invention contains a predetermined triazine ring-containing polymer, a cross-linking agent, and barium titanate as a light diffusing agent. Therefore, by using this composition, good light diffusing property can be obtained. The light scattering film can be efficiently manufactured. Generally, in order to improve the light diffusibility of the cured film, it is necessary to disperse a large amount of the light diffusing agent to increase the haze value of the film, but barium titanate having a sharp particle size distribution and a nearly spherical shape is used. This makes it possible to obtain a light-scattering film having good light extraction efficiency even when the amount of filling in the cured film is small and the haze value is not increased.

  The light-scattering film obtained from the composition of the present invention is a liquid crystal display, an organic EL device (organic EL display or organic EL lighting), an LED device, a solid-state imaging device, an organic thin film solar cell, a dye-sensitized solar cell, a TFT, or the like. Can be suitably used as a dielectric material for a ceramic capacitor, a ceramic multilayer capacitor, a PCT thermistor, a piezoelectric element, etc. when manufacturing an electronic device of the above. Especially, since it has excellent light diffusivity, it can be used as an organic EL element or an LED element. It can be suitably used as a material for the light scattering layer.

FIG. 3 is a ¹ H-NMR spectrum diagram of a triazine ring-containing hyperbranched polymer HB-TmDA40 obtained in Synthesis Example 1. It is a figure which shows the TG-DTA measurement result of the triazine ring containing hyperbranched polymer HB-TmDA40 obtained in Synthesis Example 1. 9 is a graph showing the incident angle dependence of the total radiant flux in the light-scattering film of Example 40 (solid line) and the light-scattering film of Comparative Example 6 (dotted line). 9 is a graph showing the incident angle dependence of the total radiant flux in the light-scattering film of Comparative Example 8 (solid line) and the light-scattering film of Comparative Example 6 (dotted line).

  The composition for forming a light-scattering film of the present invention contains a predetermined triazine ring-containing polymer, a crosslinking agent, and a light diffusing agent containing barium titanate particles.

[Polyazine containing triazine ring]
The triazine ring-containing polymer contains a repeating unit represented by the following formula (1).

  In formula (1), R and R ′ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group, but both are hydrogen atoms from the viewpoint of further increasing the refractive index. Preferably.

  The number of carbon atoms of the alkyl group is not particularly limited, but is preferably 1 to 20, more preferably 1 to 10 and even more preferably 1 to 3 in consideration of further improving the heat resistance of the polymer. The structure may be linear, branched or cyclic.

  Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, cyclobutyl group, 1-methyl group. -Cyclopropyl group, 2-methyl-cyclopropyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl -N-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, cyclopentyl group, 1-methyl-cyclobutyl group, 2-methyl -Cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group, 2-ethyl-cycloalkyl group Rhopropyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl- n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3 , 3-Dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n -Propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, cyclohexyl group, 1-methyl-cyclopentyl group, 2-methyl-cyclopentyl group, 3-methyl -Cyclopentyl group, 1-ethyl-cyclobutyl , 2-ethyl-cyclobutyl group, 3-ethyl-cyclobutyl group, 1,2-dimethyl-cyclobutyl group, 1,3-dimethyl-cyclobutyl group, 2,2-dimethyl-cyclobutyl group, 2,3-dimethyl-cyclobutyl group 2,4-dimethyl-cyclobutyl group, 3,3-dimethyl-cyclobutyl group, 1-n-propyl-cyclopropyl group, 2-n-propyl-cyclopropyl group, 1-isopropyl-cyclopropyl group, 2-isopropyl -Cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, 1,2,3-trimethyl-cyclopropyl group, 2,2,3-trimethyl-cyclopropyl group, 1-ethyl-2-methyl-cyclo Propyl group, 2-ethyl-1-methyl-cyclopropyl group, 2-ethyl-2-methyl-cyclopropyl group, 2-ethyl-3-methyl- A cyclopropyl group etc. are mentioned.

  The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably 1 to 20, more preferably 1 to 10 and even more preferably 1 to 3 in consideration of further increasing the heat resistance of the polymer. The structure of the alkyl moiety may be linear, branched or cyclic.

  Specific examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, s-butoxy group, t-butoxy group, n-pentyloxy group, 1-methyl group. -N-butoxy group, 2-methyl-n-butoxy group, 3-methyl-n-butoxy group, 1,1-dimethyl-n-propoxy group, 1,2-dimethyl-n-propoxy group, 2,2- Dimethyl-n-propoxy group, 1-ethyl-n-propoxy group, n-hexyloxy group, 1-methyl-n-pentyloxy group, 2-methyl-n-pentyloxy group, 3-methyl-n-pentyloxy group Group, 4-methyl-n-pentyloxy group, 1,1-dimethyl-n-butoxy group, 1,2-dimethyl-n-butoxy group, 1,3-dimethyl-n-butoxy group, 2,2-dimethyl − n-butoxy group, 2,3-dimethyl-n-butoxy group, 3,3-dimethyl-n-butoxy group, 1-ethyl-n-butoxy group, 2-ethyl-n-butoxy group, 1,1,2 -Trimethyl-n-propoxy group, 1,2,2-trimethyl-n-propoxy group, 1-ethyl-1-methyl-n-propoxy group, 1-ethyl-2-methyl-n-propoxy group and the like. ..

  The number of carbon atoms in the aryl group is not particularly limited, but is preferably 6 to 40, more preferably 6 to 16 and even more preferably 6 to 13 in consideration of further increasing the heat resistance of the polymer.

  Specific examples of the aryl group include phenyl group, o-chlorophenyl group, m-chlorophenyl group, p-chlorophenyl group, o-fluorophenyl group, p-fluorophenyl group, o-methoxyphenyl group, p-methoxyphenyl group, p-nitrophenyl group, p-cyanophenyl group, α-naphthyl group, β-naphthyl group, o-biphenylyl group, m-biphenylyl group, p-biphenylyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group Group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group and the like.

  The carbon number of the aralkyl group is not particularly limited, but is preferably 7 to 20, and the alkyl portion thereof may be linear, branched or cyclic.

  Specific examples of the aralkyl group include benzyl group, p-methylphenylmethyl group, m-methylphenylmethyl group, o-ethylphenylmethyl group, m-ethylphenylmethyl group, p-ethylphenylmethyl group, 2-propylphenyl group. Examples thereof include a methyl group, a 4-isopropylphenylmethyl group, a 4-isobutylphenylmethyl group and an α-naphthylmethyl group.

  In the formula (1), Ar represents at least one selected from the group consisting of groups represented by the following formulas (2) to (13).

In the formula, R ^{1 to} R ⁹² each independently represent a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, a linear or branched alkyl group having 1 to 10 carbon atoms, or a C ^{1 to} 10 carbon atom. It represents a straight-chain or branched alkoxy group.

R ⁹³ and R ⁹⁴ represent a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms.

W ¹ and W ² are independently of each other, a single ^{bond, -CR 95 R 96 -, -} C (= O) -, - O -, - S -, - S (= O) -, - SO 2 - or -NR ⁹⁷ - represents a. R ⁹⁵ and R ⁹⁶ each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms, which are bonded to each other to form a ring with the carbon atom to which they are bonded. You may have. R ⁹⁷ represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms.

X ¹ and X ² each independently represent a single bond, a linear or branched alkylene group having 1 to 10 carbon atoms, or a group represented by the following formula (14).

In the formula, R ^{98 to} R ¹⁰¹ are independently of each other a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, a linear or branched alkyl group having 1 to 10 carbon atoms, or a C 1 to 10 carbon atom. It represents a linear or branched alkoxy group, and Y ¹ and Y ² independently of each other represent a single bond or a linear or branched alkylene group having 1 to 10 carbon atoms.

  Here, 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 the alkoxy group are the same as above. Examples of the linear or branched alkylene group having 1 to 10 carbon atoms include methylene group, ethylene group, propylene group, trimethylene group, tetramethylene group, pentamethylene group and the like.

Among these, R ^{1 to} R ⁹² and R ^{98 to} R ¹⁰¹ are each a hydrogen atom, a halogen atom, a sulfo group, a linear or branched alkyl group having 1 to 5 carbon atoms, or a C ^{1 to} 5 carbon atom. A linear or branched alkoxy group is preferable, and a hydrogen atom is more preferable.

  In particular, as Ar, at least one selected from the group consisting of groups represented by formulas (2) and (5) to (13) is preferable, and formulas (2), (5), (7), (8) ) And (11) to (13), at least one selected from the group consisting of groups is more preferable. Specific examples of the aryl group represented by the formulas (2) to (13) include, but are not limited to, those shown below.

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

  The triazine ring-containing polymer preferably contains the repeating unit represented by the formula (15) in view of further increasing the solubility in a highly safe solvent such as a resist solvent.

（式中、Ｒ、Ｒ'及びＲ¹〜Ｒ⁴は、前記と同じ。）

(In the formula, R, R ′ and R ^{1 to} R ⁴ are the same as above.)

  From this point of view, as a particularly preferable repeating unit, a unit represented by the following formula (16) can be mentioned, and a unit represented by the following formula (17) is most suitable.

（式中、Ｒ及びＲ'は、前記と同じ。）

(In the formula, R and R ′ are the same as above.)

  The weight average molecular weight (Mw) of the triazine ring-containing polymer is not particularly limited, but is preferably 500 to 500,000. From the viewpoint of further improving the heat resistance and lowering the shrinkage ratio, Mw is preferably 1,000 or more, more preferably 2,000 or more, and further increases the solubility and lowers the viscosity of the obtained solution. Therefore, Mw is preferably 100,000 or less, more preferably 50,000 or less, even more preferably 30,000 or less, still more preferably 10,000 or less. The Mw in the present invention is an average molecular weight obtained by gel permeation chromatography (GPC) analysis in terms of standard polystyrene.

  The triazine ring-containing polymer used in the present invention can be produced by the method disclosed in Patent Document 5. For example, as shown in Scheme 1 below, a hyperbranched polymer containing a repeating unit (17 ′) can be obtained by reacting a cyanuric halide (18) and an m-phenylenediamine compound (19) in a suitable organic solvent. be able to.

（式中、Ｒは、前記と同じ。Ｘは、互いに独立して、ハロゲン原子を表す。）

(In the formula, R is the same as the above. X's each independently represent a halogen atom.)

  In addition, as shown in Scheme 2 below, a hyperbranched polymer containing a repeating unit (17 ′) is prepared by using cyanuric halide (18) and m-phenylenediamine compound (19) in an equal amount in a suitable organic solvent. It can also be synthesized from the compound (20) obtained by the reaction.

（式中、Ｘ及びＲは、前記と同じ。）

(In the formula, X and R are the same as above.)

  The amount of each raw material charged in the methods of Schemes 1 and 2 is arbitrary as long as the intended polymer can be obtained, but with respect to 1 equivalent of cyanuric halide (18), m-phenylenediamine compound (19). 01 to 10 equivalents are preferred. However, in the method of Scheme 1, it is preferable to avoid using 3 equivalents of the m-phenylenediamine compound (19) with respect to 2 equivalents of the cyanuric halide (18). By shifting the equivalent amount of the functional group, it is possible to prevent the formation of a gelled product. In order to obtain a hyperbranched polymer containing various triazine ring terminals of various molecular weights, it is preferable to use the m-phenylenediamine compound (19) in an amount of less than 3 equivalents based on 2 equivalents of the cyanuric halide (18).

  On the other hand, in order to obtain a hyperbranched polymer containing many amine terminals of various molecular weights, it is preferable to use the cyanuric halide (18) in an amount of less than 2 equivalents to 3 equivalents of the m-phenylenediamine compound (19). .. For example, a hyperbranched polymer containing many triazine ring terminals is preferable in that it has excellent transparency and light resistance when a thin film is produced.

  Thus, by appropriately adjusting the amounts of the m-phenylenediamine compound (19) and cyanuric halide (18), the molecular weight of the obtained hyperbranched polymer can be easily adjusted.

  As the organic solvent, various solvents usually used in this type 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-dimethylpropionamide, N, N-dimethylisobutyramide, N-methylformamide, N, N'-dimethylpropylene. Examples thereof include amide solvents such as urea, and mixed solvents thereof. Among them, N, N-dimethylformamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, and a mixed system thereof are preferable, and particularly, N, N-dimethylacetamide and N-methyl-2-pyrrolidone. Is preferred.

  In the reaction of the second step of Scheme 1 and Scheme 2, the reaction temperature may be appropriately set within the range from the melting point to the boiling point of the solvent used, but it is particularly preferably about 0 to 150 ° C, more preferably 60 to 100 ° C. preferable. In particular, in the reaction of Scheme 1, the reaction temperature is preferably 60 to 150 ° C., more preferably 80 to 150 ° C., further preferably 80 to 120 ° C., from the viewpoint of suppressing linearity and increasing branching degree.

  In the reaction of the first step of Scheme 2, the reaction temperature may be appropriately set within the range from the melting point of the solvent used to the boiling point of the solvent, but particularly preferably about -50 to 50 ° C, and about -20 to 50 ° C. Is more preferable, about -10 to 50 ° C is even more preferable, and -10 to 10 ° C is further preferable. In particular, in the method of Scheme 2, it is preferable to employ a two-step process comprising a first step of reacting at -50 to 50 ° C and a second step of reacting at 60 to 150 ° C following this step.

  In each of the above reactions, the mixing order of each component is arbitrary, but in the reaction of Scheme 1, a solution containing a cyanuric halide (18) or m-phenylenediamine compound (19) and an organic solvent is added at 60 to 150 ° C. The method of heating at 80 to 150 ° C. and adding the m-phenylenediamine compound (19) or cyanuric halide (18) to the solution at this temperature is the most suitable. In this case, either the component dissolved in the solvent in advance or the component added later may be used, but the method of adding the cyanuric halide (18) to the heated solution of the m-phenylenediamine compound (19) is preferable.

  Further, in the reaction of Scheme 2, the component dissolved in the solvent in advance or the component added later may be either, but a method of adding the m-phenylenediamine compound (19) to the cooling solution of the cyanuric halide (18). Is preferred. 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 reaction. Is. Further, the addition may be carried out gradually by dropping or the like, or the whole amount may be added all at once.

  In the reaction of Scheme 1, after the both compounds are mixed in a heated state, even if the reaction is carried out in one step (without stepwise raising the temperature), the target triazine ring-containing compound does not gel and does not undergo gelation. You can get coalesced.

  Further, in the second-step reaction of the schemes 1 and 2, various bases usually used during or after the 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, and oxidation. Calcium, barium hydroxide, trilithium phosphate, trisodium phosphate, tripotassium phosphate, cesium fluoride, aluminum oxide, ammonia, trimethylamine, triethylamine, diisopropylamine, diisopropylethylamine, N-methylpiperidine, 2,2,6 Examples include 6,6-tetramethyl-N-methylpiperidine, pyridine, 4-dimethylaminopyridine, N-methylmorpholine and the like.

  The addition amount of the base is preferably 1 to 100 equivalents, and more preferably 1 to 10 equivalents, relative to 1 equivalent of cyanuric halide (18). In addition, these bases may be used as an aqueous solution. In any of the schemes, the product can be easily purified by a reprecipitation method or the like after completion of the reaction.

  In the present invention, a part of the halogen atom of at least one terminal triazine ring is replaced with an alkyl group, an aralkyl group, an aryl group, an alkylamino group, an alkoxysilyl group-containing alkylamino group, an aralkylamino group, an arylamino group, You may cap with an alkoxy group, an aralkyloxy group, an aryloxy group, an ester group, etc. Among these, an alkylamino group, an alkoxysilyl group-containing alkylamino group, an aralkylamino group, an arylamino group and the like are preferable, an alkylamino group and an arylamino group are more preferable, and an arylamino group is further preferable.

  Examples of the alkyl group, alkoxy group, aryl group and aralkyl group include the same ones as described above. Specific examples of the ester group include a methoxycarbonyl group and an ethoxycarbonyl group.

  Specific examples of the alkylamino group include methylamino group, ethylamino group, n-propylamino group, isopropylamino group, n-butylamino group, isobutylamino group, s-butylamino group, t-butylamino group, n. -Pentylamino group, 1-methyl-n-butylamino group, 2-methyl-n-butylamino group, 3-methyl-n-butylamino group, 1,1-dimethyl-n-propylamino group, 1,2 -Dimethyl-n-propylamino group, 2,2-dimethyl-n-propylamino group, 1-ethyl-n-propylamino group, n-hexylamino group, 1-methyl-n-pentylamino group, 2-methyl -N-pentylamino group, 3-methyl-n-pentylamino group, 4-methyl-n-pentylamino group, 1,1-dimethyl-n-butylamino group, 1,2-dimethyl -N-butylamino group, 1,3-dimethyl-n-butylamino group, 2,2-dimethyl-n-butylamino group, 2,3-dimethyl-n-butylamino group, 3,3-dimethyl-n -Butylamino group, 1-ethyl-n-butylamino group, 2-ethyl-n-butylamino group, 1,1,2-trimethyl-n-propylamino group, 1,2,2-trimethyl-n-propyl An amino group, a 1-ethyl-1-methyl-n-propylamino group, a 1-ethyl-2-methyl-n-propylamino group and the like can be mentioned.

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

  Specific examples of the aralkylamino group include benzylamino group, methoxycarbonylphenylmethylamino group, ethoxycarbonylphenylmethylamino group, p-methylphenylmethylamino group, m-methylphenylmethylamino group, o-ethylphenylmethylamino group. , M-ethylphenylmethylamino group, p-ethylphenylmethylamino group, 2-propylphenylmethylamino group, 4-isopropylphenylmethylamino group, 4-isobutylphenylmethylamino group, naphthylmethylamino group, methoxycarbonylnaphthylmethyl group Examples thereof include an amino group and an ethoxycarbonylnaphthylmethylamino group.

  Specific examples of the arylamino group include phenylamino group, methoxycarbonylphenylamino group, ethoxycarbonylphenylamino group, naphthylamino group, methoxycarbonylnaphthylamino group, ethoxycarbonylnaphthylamino group, anthranylamino group, pyrenylamino group, biphenylamino group. Group, terphenylamino group, fluorenylamino group and the like.

  Specific examples of the aryloxy group include a phenoxy group, a naphthoxy group, an anthranyloxy group, a pyrenyloxy group, a biphenyloxy group, a terphenyloxy group and a fluorenyloxy group.

  Specific examples of the aralkyloxy group include benzyloxy group, p-methylphenylmethyloxy group, m-methylphenylmethyloxy group, o-ethylphenylmethyloxy group, m-ethylphenylmethyloxy group, p-ethylphenylmethyl group. Examples thereof include an oxy group, a 2-propylphenylmethyloxy group, a 4-isopropylphenylmethyloxy group, a 4-isobutylphenylmethyloxy group and an α-naphthylmethyloxy group.

  These groups can be easily introduced by substituting the halogen atom on the triazine ring with a compound giving a corresponding substituent. At this time, a compound which gives a corresponding substituent may be charged at the same time as another monomer. That is, by reacting a cyanuric halide compound and an aromatic diamine compound in the presence of a compound giving a corresponding substituent, the rigidity of the hyperbranched polymer is relaxed, and a soft hyperbranched polymer with a low degree of branching. Can be obtained. The hyperbranched polymer obtained by this method has excellent solubility in a solvent (suppression of aggregation) and excellent crosslinkability with a crosslinking agent, and therefore is particularly useful when used as a composition in combination with a crosslinking agent described below. It is advantageous.

  Examples of the compound giving the corresponding substituent include organic monoamines. As the organic monoamine, any of alkyl monoamine, aralkyl monoamine, and aryl monoamine can be used.

  Examples of the alkylmonoamine 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-butylamine 1,2,2-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-ethylhexylamine and the like can be 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 the aryl monoamine include aniline, p-methoxycarbonylaniline, p-ethoxycarbonylaniline, p-methoxyaniline, 1-naphthylamine, 2-naphthylamine, anthranylamine, 1-aminopyrene, 4-biphenylylamine, o-. Phenylaniline, 4-amino-p-terphenyl, 2-aminofluorene and the like can be mentioned.

  For example, as shown in scheme 3 below, a hyperbranched polymer (21) having a phenylamino group at at least one terminal is obtained by adding an aniline derivative and reacting it.

（式中、Ｘ及びＲは、前記と同じ。）

(In the formula, X and R are the same as above.)

  In the reaction of Scheme 3, the amount of the organic monoamine used is preferably 0.05 to 500 equivalents, more preferably 0.05 to 120 equivalents, still more preferably 0.05 to 50 equivalents, relative to 1 equivalent of the cyanuric halide compound. preferable.

  The reaction temperature in this case is also preferably 60 to 150 ° C, more preferably 80 to 150 ° C, and even more preferably 80 to 120 ° C from the viewpoint of suppressing linearity and increasing the degree of branching. However, the mixing of the three components of the organic monoamine, the cyanuric halide compound and the aromatic diamine compound may be carried out at a low temperature, and in that case, the temperature is preferably about -50 to 50 ° C, and -20 to 50 ° C. The degree is more preferable, and −20 to 10 ° C. is further preferable. After charging at a low temperature, it is preferable to raise the temperature all at once (in one stage) to the temperature at which the polymerization is carried out to carry out the reaction.

  Further, the mixing of the two components of the cyanuric halide compound and the aromatic diamine compound may be carried out at a low temperature, and in that case, the temperature is preferably about -50 to 50 ° C, more preferably about -20 to 50 ° C. Preferably, -20-10 degreeC is more preferable. After charging at a low temperature, it is preferable to add an organic monoamine and raise the temperature to a temperature for polymerization at once (in one step) to carry out the reaction. The reaction of reacting the cyanuric halide compound with the aromatic diamine compound in the presence of such an organic monoamine may be carried out using the same organic solvent as described above.

[Crosslinking agent]
The crosslinking agent contained in the composition of the present invention is not particularly limited as long as it is a compound containing a substituent capable of reacting with the above-mentioned triazine ring-containing polymer. Examples of such a compound include a methylol group, a melamine compound containing a cross-linking substituent such as a methoxymethyl group, a substituted urea compound, an epoxy group, a compound containing a cross-linking substituent such as an oxetane group, and a blocked isocyanate group. Examples thereof include compounds containing an acid anhydride, compounds containing an acid anhydride, compounds containing a (meth) acryl group, and phenoplast compounds. Of these, from the viewpoint of heat resistance and storage stability, an epoxy group, a blocked isocyanate group, a compound containing a (meth) acrylic group is preferable, and in particular, a compound containing a blocked isocyanate group and without using an initiator. Polyfunctional epoxy compounds and / or polyfunctional (meth) acrylic compounds that provide photocurable compositions are preferred. It should be noted that these compounds may contain at least one cross-linking substituent when they are used for the terminal treatment of a polymer, and at least two cross-linking substituents when they are used for the cross-linking treatment of polymers. Must be included.

  The polyfunctional epoxy compound is not particularly limited as long as it contains 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-diglycidylaniline), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, trimethylolethane triglycidyl ether, bisphenol A diglycidyl ether, pentaerythritol polyglycidyl ether, etc. And the like.

  The polyfunctional epoxy compound is also available as a commercial product, and specific examples thereof include epoxy resins containing at least two epoxy groups, YH-434, YH-434L (above, Nippon Steel & Sumikin Chemical Co., Ltd. Co., Ltd.), an epoxy resin containing a cyclohexene oxide structure, Epolide (registered trademark) GT-401, GT-403, GT-301, GT-302, Celoxide (registered trademark) 2021, 3000 (above, ) Daicel), bisphenol A type epoxy resin, jER (registered trademark) 1001, 1002, 1003, 1004, 1007, 1009, 1010, 828 (above, Mitsubishi Chemical Corporation), bisphenol F type epoxy resin JER 807 (manufactured by Mitsubishi Chemical Co., Ltd.), phenol novolac type epoxy resin, jER 152, 154 (manufactured by Mitsubishi Chemical Co., Ltd.), EPPN201, 202 (manufactured by Nippon Kayaku Co., Ltd.) , Cresol novolac type epoxy resin, EOCN-102, E OCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, EOCN-1027 (Nippon Kayaku Co., Ltd.), jER 180S75 (Mitsubishi Chemical Co., Ltd.), alicyclic epoxy resin, Denacol (registered trademark) EX-252 (manufactured by Nagase Chemtex Corp.), Araldite (registered trademark) CY-175, CY-177, CY-179, CY-182, CY-192, CY-184 (above, Huntsman -Advanced Materials Co., Ltd., EPICLON (registered trademark) 200, 400 (above, DIC Corporation), jER 871, 872 (above, Mitsubishi Chemical Corporation), ED-5661, ED-5662 ( As above, Denacol (registered trademark) EX-611, EX-612, EX-614, EX-622, EX-411, EX-512, EX- which is an aliphatic polyglycidyl ether manufactured by Celanese Coating Co., Ltd. 522, EX-421, EX-313, EX-314, EX-321 (above, manufactured by Nagase Chemtex Co., Ltd.) and the like can also be used.

  The polyfunctional (meth) acrylic compound is not particularly limited as long as it contains two or more (meth) acrylic groups in one molecule. Specific examples thereof include ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, ethoxylated glycerin tri (meth) acrylate. Acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, polyglycerin monoethylene oxide poly (meth) acrylate, polyglycerin polyethylene glycol poly (meth) acrylate, dipentaerythritol hexa (meth) ) Acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, Rodez Kanji dimethanol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, polybasic acid-modified acryl oligomers, and the like.

  Further, polyfunctional (meth) acrylic compound is also available as a commercial product, as specific examples thereof, NK ester A-200, A-400, A-600, A-1000, A-9300, 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-TMPT-9EO, AT-20E, ATM-4E, ATM-35E, A-DPH, A-DCP, A-HD-N, TMPT, DCP, NPG, HD-N , NK oligo U-15HA, vanaresin GH-1203 (above, Shin Nakamura Chemical Co., Ltd.), KAYARAD (registered trademark) DPEA-12, PEG400DA, THE-330, RP-1040 (above, Nippon Kayaku Co., Ltd. )), Aronix (registered trademark) M-210, M-350 (above, manufactured by Toagosei Co., Ltd.), KAYARAD DPHA, NPGDA, PET30, DN-0075 (manufactured by Nippon Kayaku Co., Ltd.) and the like. ..

  A polybasic acid-modified acrylic oligomer is also available as a commercial product, and specific examples thereof include Aronix (registered trademark) M-510 and 520 (all manufactured by Toagosei Co., Ltd.).

  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, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadic anhydride, methylnadic acid anhydride, maleic anhydride, succinic anhydride, Those containing one acid anhydride group in the molecule such as octyl succinic anhydride and dodecenyl succinic anhydride; 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-Dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, 1,2,3,4-butanetetracarboxylic acid dianhydride 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) Examples include hexafluoropropane dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride and the like containing two acid anhydride groups in the molecule.

  As a compound containing a blocked isocyanate group, an isocyanate group (-NCO) contains two or more blocked isocyanate groups in one molecule which are blocked by a suitable protective group, and when exposed to a high temperature during heat curing, There is no particular limitation as long as the protective group (block portion) is thermally dissociated and removed, and the resulting isocyanate group causes a crosslinking reaction with the resin. Examples of such a compound include compounds containing two or more groups represented by the following formulas in one molecule (these groups may be the same or different from each other).

（式中、Ｒ_bは、保護基を表す。）

(In the formula, R _b represents a protecting group.)

  Such a compound can be obtained, for example, by reacting a compound containing two or more isocyanate groups in one molecule with a suitable blocking agent.

  Examples of the compound containing two or more isocyanate groups in one molecule include polyisocyanates such as isophorone diisocyanate, 1,6-hexamethylene diisocyanate, methylene bis (4-cyclohexyl isocyanate), 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, 1-butanol, 2-ethoxyhexanol, 2-N, N-dimethylaminoethanol, 2-ethoxyethanol and cyclohexanol; 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, benzophenone oxime and the like oximes. Examples thereof include 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, and specific examples thereof include Takenate (registered trademark) B-830, B-815N, B-842N, B-870N, B-874N, B -882N, B-7005, B-7030, B-7075, B-5010 (above, Mitsui Chemicals, Inc.), Duranate (registered trademark) 17B-60PX, TPA-B80E, MF-B60X, MF-K60X, E402-B80T (above, Asahi Kasei Chemicals Corporation), Karens MOI-BM (registered trademark) (Showa Denko Corporation), BI-7950, BI-7951, BI-7960, BI-7961, BI-7963 , BI-7982, BI-7991, BI-7992 (manufactured by Baxenden chemicals) and the like.

  The aminoplast compound is not particularly limited as long as it contains two or more methoxymethylene groups in one molecule, and examples thereof include CYMEL (registered trademark) 303 (hexamethoxymethylmelamine), 1170 (tetrabutoxymethylglycoluril). , 1123 (Tetramethoxymethylbenzoguanamine) (above, Ornex Co.) Cymel series, methylated melamine resin Nicalac (registered trademark) MW-30HM, MW-390, MW-100LM, MX-750LM, methylated Melamine-based compounds such as the Nikalac series such as Nikalac (registered trademark) MX-270, MX-280, MX-290 (above, manufactured by Sanwa Chemical Co., Ltd.) which is a urea resin can be mentioned.

  The oxetane compound is not particularly limited as long as it contains two or more oxetanyl groups in one molecule, and examples thereof include Alone Oxetane (registered trademark) OXT-221, OX-SQ-H, OX-SC (above, Toagosei Co., Ltd.). Co., Ltd.) and the like.

  The phenoplast compound contains 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 there.

  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 (all manufactured by Asahi Organic Materials Co., Ltd.) and the like.

  Among these, a polyfunctional (meth) acrylic compound is preferable because it can suppress the decrease in refractive index due to the incorporation of a crosslinking agent, and the curing reaction proceeds rapidly, and among them, with a triazine ring-containing polymer. A polyfunctional (meth) acrylic compound containing the following isocyanuric acid skeleton is more preferable because it has excellent compatibility. Examples of the polyfunctional (meth) acrylic compound having such a skeleton include NK ester A-9300 and A-9300-1CL (all manufactured by Shin-Nakamura Chemical Co., Ltd.).

（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)アクリル基を含む１価の有機基である。）

(In the formula, R ^{111 to} R ¹¹³ are, independently of each other, a monovalent organic group containing at least one (meth) acrylic group at the terminal.)

  Further, from the viewpoint of further improving the curing rate and enhancing the solvent resistance, acid resistance, and alkali resistance of the obtained cured film, it is a liquid at 25 ° C. and its viscosity is 5,000 mPa · s or less, preferably Is 1 to 3,000 mPa · s, more preferably 1 to 1,000 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). It is preferable to use them singly or in combination of two or more or in combination with the polyfunctional (meth) acrylic compound containing the isocyanuric acid skeleton.

  Such a low-viscosity crosslinking agent is also available as a commercial product. For example, among the above-mentioned polyfunctional (meth) acrylic compounds, 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-4E (150 mPa ·) s, 25 ° C.), ATM-35E (350 mPa · s, 25 ° C.) (above, manufactured by Shin-Nakamura Chemical Co., Ltd.) and the like, and cross-linking agents having a relatively long chain length between (meth) acrylic groups.

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

  The crosslinking agents may be used alone or in combination of two or more. The amount of the cross-linking agent used is preferably 1 to 100 parts by mass with respect to 100 parts by mass of the triazine ring-containing polymer, but considering solvent resistance, the lower limit is preferably 2 parts by mass, more preferably 5 parts by mass. In consideration of controlling the refractive index, the upper limit is preferably 50 parts by mass, more preferably 20 parts by mass.

  The light-scattering film forming composition of the present invention may contain an initiator corresponding to each crosslinking agent. As described above, when a polyfunctional epoxy compound and / or a polyfunctional (meth) acrylic compound is used as a crosslinking agent, photocuring proceeds to give a cured film without using an initiator, but in that case, You can use the agent.

  When a polyfunctional epoxy compound is used as a crosslinking agent, a photoacid generator or a photobase generator can be used.

  The photo-acid 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, and 4-methylphenyldiazonium hexafluorophosphate; diphenyliodonium hexafluoroantimonate, di (4-methylphenyl). Diaryl iodonium salts such as iodonium hexafluorophosphate and di (4-t-butylphenyl) iodonium hexafluorophosphate; triphenylsulfonium hexafluoroantimonate, tris (4-methoxyphenyl) sulfonium hexafluorophosphate, diphenyl-4-thiophenoxy Phenylsulfonium hexafluoroantimonate, diphenyl-4-thiophenoxyphenylsulfo Umhexafluorophosphate, 4,4'-bis (diphenylsulfonio) phenyl sulfide-bishexafluoroantimonate, 4,4'-bis (diphenylsulfonio) 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- Such as [4 ′-(benzoyl) phenylthio] phenyl-di (4-fluorophenyl) sulfonium hexafluoroantimonate and 4- [4 ′-(benzoyl) phenylthio] phenyl-di (4-fluorophenyl) sulfonium hexafluorophosphate Triarylsulfonium salt Etc.

  The photo-acid generator may be a commercially available product, and specific examples thereof include San-Aid (registered trademark) SI-60, SI-80, SI-100, SI-60l, SI-80l, SI-100l, SI- L145, SI-L150, SI-L160, SI-L110, SI-L147 (above, Sanshin Chemical Industry Co., Ltd.), UVI-6950, UVI-6970, UVI-6974, UVI-6990, UVI-6992 ( As above, manufactured by Union Carbide Co., CPI (registered trademark) -100P, 100A, 200K, 200S (above, manufactured by San-Apro Co., Ltd.), ADEKA OPTOMER SP-150, SP-151, SP-170, SP-171 ( Above, ADEKA Corporation, Irgacure (registered trademark) 261 (manufactured by BASF), CI-2481, CI-2624, CI-2639, CI-2064 (all manufactured by Nippon Soda Co., Ltd.), CD-1010 , CD-1011, CD-1012 (above, manufactured 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, MBZ-101, MBZ-301, PYR-100, PYR-200, DNB-101, NB-101, NB-201, BBI-101, BBI-1 02, BBI-103, BBI-109 (above, Midori Chemical Co., Ltd.), PCI-061T, PCI-062T, PCI-020T, PCI-022T (above, Nippon Kayaku Co., Ltd.), 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 and used, for example, Co-amine complex type, oxime carboxylic acid ester type, carbamic acid ester type, quaternary ammonium salt type photobase generating agent. Etc. can be used.

  Specific examples thereof include 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-carbamoylhydroxyamine, 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-diacetyl-4- (2'-nitrophenyl) -1,4 Dihydropyridine, 2,6-dimethyl-3,5-diacetyl-4- (2 ', 4'-dinitrophenyl) -1,4-dihydropyridine and the like.

  A commercially available product may be used as the photobase generator, and specific examples thereof include TPS-OH, NBC-101, ANC-101 (above, manufactured by Midori Kagaku Co., Ltd.) and the like.

  When using a photo-acid or a base generator, the usage-amount is 0.1-15 mass parts with respect to 100 mass parts of polyfunctional epoxy compounds, and 1-10 mass parts is more preferable. In addition, you may mix | blend an epoxy resin hardener with the quantity of 1-100 mass parts with respect to 100 mass parts of polyfunctional epoxy compounds as needed.

  On the other hand, when a polyfunctional (meth) acrylic compound is used, a photo radical polymerization initiator can be used. The photo-radical polymerization initiator may be appropriately selected and used from known ones, and examples thereof include acetophenones, benzophenones, Michler's benzoylbenzoate, amyloxime esters, oxime esters, tetramethylthiuram monosulfide, and thioxanthones. Can be mentioned.

  In particular, a photocleavable photoradical polymerization initiator is preferable. The photocleavable photoradical polymerization initiator is described in the latest UV curing technology (page 159, publisher: Kazuhiro Takahashi, publisher: Technical Information Institute Co., Ltd., 1991).

  Examples of commercially available photoradical polymerization initiators include Irgacure 127, 184, 369, 379, 379EG, 651, 500, 754, 819, 903, 907, 784, 2959, CGI1700, CGI1750, CGI1850, CG24-61, OXE01. , OXE02, Darocur (registered trademark) 1116, 1173, MBF, Lucillin TPO (above, manufactured by BASF), UVECRYL (registered trademark) P36 (manufactured by Cytec Surface Specialties), ESACURE (registered trademark) KIP150, KIP65LT, KIP100F, Examples include KT37, KT55, KTO46, KIP75 / B (manufactured by Lamberty).

  When a photoradical polymerization initiator is used, the amount thereof used is preferably 0.1 to 200 parts by mass, more preferably 1 to 150 parts by mass, relative to 100 parts by mass of the polyfunctional (meth) acrylate compound.

[Light scattering agent]
The light scattering agent contained in the composition of the present invention contains barium titanate particles. The barium titanate particles may be appropriately selected and used from publicly known ones in order to enhance the light-scattering property, light-transmitting property and dielectric property of the obtained cured film. The barium titanate particles may be used alone or in combination of two or more.

  The barium titanate particles are synthesized by a liquid phase method or a solid phase method such as an oxalic acid method, a hydrothermal method, a sol-gel method, and a spray pyrolysis method, but may be obtained by any method. Among these, the liquid phase method is preferable to the solid phase method from the viewpoint of atomizing the particles and sharpening the particle size distribution. In addition, the build-up method, which allows monodispersion with a relatively weak crushing and tends to have a sharp particle size distribution, rather than the breakdown method, which requires strong mechanical crushing and has a large amount of contamination from the equipment and the particle size distribution tends to be broad. Synthesized barium titanate is preferred.

The average primary particle diameter of the barium titanate particles is not particularly limited, but it is preferably 3 μm or less from the viewpoint of further improving the dispersibility, making the obtained cured film thinner, and further improving the flatness of the cured film. 2 μm or less is more preferable, and 1 μm or less is even more preferable. Further, from the viewpoint of exhibiting sufficient light diffusibility in the obtained cured film, it is preferably 50 nm or more, more preferably 100 nm or more, still more preferably 150 nm or more. In the present invention, the average primary particle diameter is a 50% cumulative volume diameter (median diameter, D ₅₀ ) obtained by a laser diffraction / scattering method based on Mie theory.

  The sharp particle size distribution means that the primary particle size of 100 barium titanate particles is measured with a scanning electron microscope and the average thereof is calculated, and the CV value calculated from standard deviation / average diameter × 100 is , 20% or less, preferably 15% or less, and more preferably 10% or less.

  Regarding the particle shape, the ratio of the major axis and the minor axis (major axis / minor axis) measured by observation with a scanning electron microscope or the like is preferably 3 or less, more preferably 2 or less, and more preferably 1.5 or less. More preferable.

  As the barium titanate particles, commercially available products can be used, for example, barium titanate BT series (manufactured by Sakai Chemical Industry Co., Ltd.), BT-HP9DX (particle size: 100, 150, 200, 250, 300, 400 nm) (manufactured by Kyoritsu Material Co., Ltd.), Parcelam (registered trademark) BT (particle size: 0.3, 0.6, 2.0 μm) (manufactured by Nippon Kagaku Kogyo Co., Ltd.), barium titanate BT-series, HP-Series (Fuji Titanium Industry Co., Ltd.), TFP-NA-E, TFP-NB-E, TFP-NC-E, TFP-ND-E, TFP-NE-E, TFP-NF-E, TFP -NJ-R (above, manufactured by Toda Kogyo Co., Ltd.) and the like.

  The light-scattering agent may contain other light-scattering agent other than the barium titanate particles as long as the effect of the present invention is not impaired. Other light scattering agents include inorganic fine particles, organic fine particles, organic-inorganic composite fine particles, and the like. The other light scattering agents may be used alone or in combination of two or more kinds.

  The inorganic fine particles are not particularly limited, but in the present invention, Be, Al, Si, Ca, Ti, V, Fe, Cu, Zn, Y, Zr, Nb, Mo, In, Sn, Sb, Ta, Preference is given to oxides, sulfides or nitrides of one or more metals selected from the group consisting of W, Pb, Bi and Ce, and particularly preferred are these metal oxides.

Specific examples of the metal oxide include Al ₂ O ₃ , ZnO, TiO ₂ , ZrO ₂ , Fe ₂ O ₃ , Sb ₂ O ₅ , BeO, ZnO, SnO ₂ , CeO ₂ , SiO ₂ , WO _{3 and the} like. Be done. Alternatively, a composite oxide obtained from a plurality of metal oxides may be used. The complex oxide is obtained by mixing two or more kinds of inorganic oxides at the stage of producing fine particles. For example, a composite oxide of TiO ₂ and ZrO ₂ , TiO ₂ , ZrO ₂ and SnO ₂ , ZrO ₂ and SnO ₂ and the like can be mentioned. Furthermore, it is also possible to use a _{ZnSb 2 O 6, SrTiO 3,} SrSnO 3 and the like.

  The inorganic fine particles may be treated with silicon oxide, an organosilicon compound, an organometallic compound, or the like. The treatment with silicon oxide is to grow silicon oxide fine particles on the surface of the fine particles in a dispersion containing inorganic fine particles by a known method. The treatment with an organosilicon compound or an organometallic compound is to add these compounds to a dispersion containing inorganic fine particles and stir with heating.

  Examples of the organosilicon compound include a silane coupling agent and silane. Specific examples of the silane coupling agent include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane and 3 -Glycidoxypropylmethylditriethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyl Methyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-Aminopropylmethyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl- N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, Examples thereof include bis (triethoxysilylpropyl) tetrasulfide and 3-isocyanatopropyltriethoxysilane.

  Further, specific examples of silane include methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, methyltriethoxysilane, and dimethyldichlorosilane. Ethoxysilane Phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, decyltrimethoxysilane, trifluoropropyltrimethoxysilane, hexamethyldisilazane and the like. Be done.

  Examples of the organometallic compound include titanate-based coupling agents and aluminum-based coupling agents, and specific examples of the titanate-based coupling agents include Planeact (registered trademark) KR TTS, KR 46B, KR 38B, KR 138S, KR238S, 338X, KR 44, KR 9SA, KR ET5, KR ET (manufactured by Ajinomoto Fine-Techno Co., Ltd.), specific examples of aluminum-based coupling agents include Planeact AL-M (manufactured by Ajinomoto Fine-Techno Co., Ltd.), etc. Is mentioned.

  The amount of the organosilicon compound or organometallic compound used is preferably 2 to 100 parts by mass with respect to 100 parts by mass of the inorganic fine particles.

  The metal oxide fine particles can be produced by a known method, for example, an ion exchange method, a peptization method, a hydrolysis method, or a reaction method. Examples of the ion exchange method include a method of treating the acidic salt of the metal with a hydrogen ion exchange resin, a method of treating the basic salt of the metal with a hydroxyl group anion exchange resin, and the like. Examples of the peptization method include a method of neutralizing the acid salt of the metal with a base. Examples of the hydrolysis method include a method of hydrolyzing the metal alkoxide, a method of hydrolyzing the basic salt of the metal under heating, and a method of removing unnecessary acid. Examples of the reaction method include a method of reacting the metal powder with an acid.

  Examples of the organic fine particles include crosslinked polymethylmethacrylate (PMMA) particles, crosslinked polymethylacrylate particles, crosslinked polystyrene particles, crosslinked styrene-acrylic copolymer particles, melamine-formaldehyde particles, silicone resin particles, silica-acrylic composite particles, nylon particles, Examples thereof include benzoguanamine-formaldehyde particles, benzoguanamine / melamine / formaldehyde particles, fluororesin particles, epoxy resin particles, polyphenylene sulfide resin particles, polyethersulfone resin particles, polyacrylonitrile particles, and polyurethane particles. As such organic fine particles, commercially available products can be used. For example, crosslinked PMMA particles MX-150 (manufactured by Soken Chemical Industry Co., Ltd.), Techpolymer (registered trademark) SSX series (Sekisui Plastics Co., Ltd. )), Tuftic (registered trademark) FH-S series (manufactured by Toyobo Co., Ltd.), crosslinked styrene-acrylic hollow particles Nanotex (registered trademark) (manufactured by JSR Corporation), and silicone resin particles Tospearl (Registered trademark) series (manufactured by Momentive Co., Ltd.), KMP series (manufactured by Shin-Etsu Chemical Co., Ltd.), polystyrene-based and polymethacrylate-based particles Gants Pearl (registered trademark) series (manufactured by Gantz Kasei Co., Ltd.) Soliostar (registered trademark) RA and SP (manufactured by Nippon Shokubai Co., Ltd.) which are silica-acrylic composite particles, Amylan (registered trademark) (manufactured by Toray Industries, Inc.) which is nylon particles, and benzoguanamine Formaldehyde particles Epostor (registered trademark) MS, M05, l15 (manufactured by Nippon Shokubai Co., Ltd.), benzoguanamine / melamine formaldehyde particles Eposter M30 (manufactured by Nippon Shokubai Co., Ltd.), fluororesin particles Fluon (registered trademark) Trademark) PTFE dispersion (manufactured by Asahi Glass Co., Ltd.), epoxy resin particles Trepal (registered trademark) EP (manufactured by Toray Co., Ltd.), polyphenylene sulfide resin particles Trepal PPS (manufactured by Toray Co., Ltd.), polyether Terepearl PES (manufactured by Toray Industries, Inc.) which is a sulfone resin particle, Toughtic F series F-120 (manufactured by Toyobo Co., Ltd.) which is polyacrylonitrile particles, Art Pearl (registered trademark) which is a polyurethane particle (crosslinked urethane beads MM, Negami Industry Co., Ltd.) and the like.

  Examples of the organic-inorganic composite fine particles include melamine resin / silica composite particles. As such an organic-inorganic composite fine particle, a commercially available product can be used, and examples thereof include Optobeads (registered trademark) 500S (manufactured by Nissan Chemical Industries, Ltd.) which is a melamine resin / silica composite particle. The organic-inorganic composite fine particles are preferably treated with a surface modifier. In this case, the surface modifier is not particularly limited as long as it can improve the compatibility between the matrix resin and the light diffusing agent, but considering that the matrix resin is a triazine ring-containing polymer, silane coupling It is preferable to use two components, an agent and a compound having a (meth) acrylic group and an isocyanate group.

  The average primary particle diameter, particle size distribution and shape of the other light scattering agent are not particularly limited, but are preferably the same as those of the barium titanate particles.

  The light-scattering agent may or may not be treated with a surface modifier as long as the compatibility with the triazine ring-containing polymer which is the matrix resin and the dispersibility in the solvent are enhanced. Good.

  The surface modifier is not particularly limited, and examples thereof include inorganic oxides such as silicon oxide, zirconium oxide, and aluminum oxide, polyhydric alcohols, alkanolamines, silicone oils, silane coupling agents, titanium coupling agents, and the like. Be done.

  The amount of the light-scattering agent is not particularly limited, but in consideration of further increasing the light-scattering efficiency of the obtained light-scattering film, the lower limit thereof is preferably 1 mass with respect to 100 parts by mass of the triazine ring-containing polymer. Part, more preferably 5 parts by mass, still more preferably 30 parts by mass, and considering the suppression of the decrease in the light transmittance of the cured film and the suppression of the decrease in the film-forming property, the upper limit thereof is preferably 500 parts by mass, It is more preferably 300 parts by mass, and even more preferably 100 parts by mass.

  The content of barium titanate particles in the light-scattering agent is preferably 1% by mass or more, more preferably 20% by mass or more, still more preferably 50% by mass or more, in the total light-scattering agent. It is even more preferably 100% by mass.

[solvent]
It is preferable to add various solvents to the composition of the present invention to dissolve the triazine ring-containing polymer before use. The solvent is not particularly limited as long as the compatibility with the polymer is not impaired, but a solvent having a light scattering agent dispersing ability is preferable. Examples of such a 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 Glycol monomethyl ether, diethylene glycol monomethyl ether, dipropylene glycol monoethyl ether, diethylene glycol monoethyl ether, triethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol, 1-octanol, ethylene glycol, hexylene glycol, trimethylene glycol, 1- Methoxy-2-butanol, cyclohexanol, diacetone alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, propylene glycol, benzyl alcohol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, γ -Butyrolactone, acetone, methyl ethyl ketone, methyl isopropyl ketone, die Tyl ketone, methyl isobutyl ketone, methyl n-butyl ketone, cyclohexanone, cyclopentanone, ethyl acetate, isopropyl acetate, n-propyl acetate, isobutyl acetate, n-butyl acetate, ethyl lactate, methanol, ethanol, 1-propanol, 2-propanol , T-butyl alcohol, allyl alcohol, 2-methyl-2-butanol, isobutyl alcohol, 1-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-imidazolidinone , Dimethylsul Examples include phoxide and N-cyclohexyl-2-pyrrolidinone. These may be used alone or in combination of two or more. The solvent may be the same as or different from the solvent used during the polymerization of the triazine ring-containing polymer.

[Other ingredients]
The composition of the present invention may contain other components other than the components described above, for example, additives such as a leveling agent and a surfactant, as long as the effects of the present invention are not impaired.

  Examples of the surfactant include nonionic surfactants, fluorine-based surfactants and organosiloxane polymers.

  Nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, and other polyoxyethylene alkyl ethers; 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 Fatty acid esters of sorbitan such as polyoxyethylene sorbitan monolaurate, polyoxyethylene Sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan tristearate, and the like.

  As the fluorine-based surfactant, Ftop (registered trademark) EF301, EF303, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Megafac (registered trademark) F171, F173, R-08, R-30, R- 40, F-553, F-554, RS-75, RS-72-K (manufactured by DIC Corporation), FLUORAD (registered trademark) FC430, FC431 (manufactured by 3M Company), trade name Asahi Guard (registered trademark) AG710 (Manufactured by Asahi Glass Co., Ltd.), Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (AGC Seimi Chemical Co., Ltd.) and the like.

  As the organosiloxane polymer, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), BYK-302, BYK-307, BYK-322, BYK-323, BYK-330, BYK-333, BYK-370, BYK-375, BYK. -378 (above, manufactured by BYK-Chemie) and the like.

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

[Composition for forming light-scattering film]
The light-scattering film-forming composition of the present invention may be prepared by mixing the triazine ring-containing polymer, the cross-linking agent, the light-scattering agent, and optionally a solvent and other components in any order. it can. For example, it can be prepared by dissolving the triazine ring-containing polymer in a solvent, adding a light scattering agent to disperse the triazine ring-containing polymer, and then adding a crosslinking agent and, if necessary, other components. ..

  The dispersion treatment method of the light scattering agent is not particularly limited, and ultrasonic treatment, a wet jet mill, a ball mill, a bead mill, a paint shaker, a basket mill, a dyno mill, an ultra visco mill, an annular disperser, or the like can be used. Further, the composition for forming a light-scattering film obtained by these may be further treated with a known filter or separator, if necessary.

  The solid content concentration in the composition of the present invention 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, 0.1 to 50 mass% is preferable, and 0.1 to 40 mass% is more preferable. The solid content means the components of the composition excluding the solvent.

[Light scattering film]
It is possible to obtain a desired light-scattering film by applying the composition for forming a light-scattering film of the present invention to a substrate, and then heating as necessary to evaporate the solvent, followed by heating or light irradiation. it can.

  The method of applying the composition is arbitrary, for example, spin coating method, dipping method, flow coating method, inkjet method, jet dispenser method, spray method, bar coating method, gravure coating method, slit coating method, roll coating method, transfer A printing method, a brush coating method, a blade coating method, an air knife coating method, a screen printing method and the like can be adopted.

  As the base material, silicon, glass on which indium tin oxide (ITO) is formed, glass on which indium zinc oxide (IZO) is formed, metal nanowire, sapphire glass, glass, quartz, ceramics, or the like is used. And a plastic such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), and polyimide. A flexible base material having flexibility can also be used.

  The firing temperature is not particularly limited for the purpose of evaporating the solvent, and may be 40 to 400 ° C., for example.

  The firing method is not particularly limited, and for example, a hot plate or an oven may be used to evaporate in a suitable atmosphere such as the atmosphere, an inert gas such as nitrogen, or a vacuum.

  The firing temperature and the firing time may be selected under conditions suitable for the intended process step of the 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 light irradiation are not particularly limited, and appropriate irradiation energy and time may be adopted depending on the triazine ring-containing polymer and the crosslinking agent used.

  The light scattering film of the present invention thus obtained has excellent light diffusion efficiency and light extraction efficiency without increasing the haze value. The haze value of the light-scattering film of the present invention is usually 30 to 75, preferably 35 to 70, more preferably 45 to 65. When the haze value is within the above range, the light diffusion efficiency and the light extraction efficiency are excellent without increasing the haze value. The haze value in the present invention is a value measured according to JIS K 7136.

  Since the light-scattering film of the present invention can achieve high heat resistance, high transparency, high refractive index, high solubility and low volume shrinkage, liquid crystal displays, organic EL devices (organic EL displays and organic EL lighting), LED devices. , Solid-state image sensor, organic thin-film solar cell, dye-sensitized solar cell, one member for manufacturing electronic devices such as TFT, ceramic capacitor, ceramic multilayer capacitor, PCT thermistor, can be suitably used as a dielectric material for piezoelectric element, etc. Especially, since it has excellent light diffusivity, it can be suitably used as a material for a light scattering layer of an organic EL element or an LED element.

  In order to further enhance the flatness of the obtained light-scattering film, a composition obtained by removing the light-diffusing agent from the composition for forming a light-scattering film described above is used as a planarizing material, and using this, on the light-scattering film You may further laminate | stack a planarization film. In this flattening material, specific examples of the triazine ring-containing polymer, the cross-linking agent, etc., their compounding amounts, and the film forming method are as described above.

  The haze value of the light-scattering film on which the planarizing film is laminated is usually 25 to 70, preferably 30 to 65, and more preferably 40 to 60. When the haze value is within the above range, the light diffusion efficiency and the light extraction efficiency are excellent without increasing the haze value.

  Hereinafter, the present invention will be specifically described with reference to synthesis examples, examples and comparative examples, but the present invention is not limited to the following examples. The measuring devices and reagents used in the examples are as follows.

[ ¹ H-NMR]
Equipment: Varian NMR System 400NB (400 MHz)
JEOL-ECA700 (700 MHz)
Measurement solvent: DMSO-d6
Reference substance: tetramethylsilane (TMS) (δ 0.0 ppm)
[GPC]
Equipment: Tosoh Corp. HLC-8200 GPC
Column: Shodex KF-804L + KF-805l
Column temperature: 40 ° C
Solvent: Tetrahydrofuran (THF)
Detector: UV (254 nm)
Calibration curve: Standard polystyrene [ball mill]
Universal ball mill UB-32 manufactured by Yamato Scientific Co., Ltd.
[Vertical batch bead mill]
RMB manufactured by IMEX Co., Ltd., container capacity: 800 mL
[Sputtering device]
Sanyu Electronics Co., Ltd. SRS-700T / LL
[Ellipsometer]
Equipment: JA Woollam Japan multi-incidence angle spectroscopic ellipsometer VASE
[Differential thermal balance (TG-DTA)]
Equipment: Rigaku TG-8120
Temperature rising rate: 10 ° C / min Measuring temperature: 25-750 ° C
[Measurement of light scattering film thickness]
Equipment: Kosaka Laboratory Ltd. ET-4000
[Measurement of particle size distribution]
Equipment: Nikkiso Co., Ltd., Microtrac ultrafine particle size analyzer UPA-EX150
[Measurement of total light transmittance (TT), haze value, parallel light transmittance (PT) and diffuse light transmittance (DIF)]
Equipment: NDH5000 manufactured by Nippon Denshoku Industries Co., Ltd.
[Measurement of light transmission and scattering characteristics]
Device: integrating sphere type transmission fluorescence measuring device manufactured by Spectrometer Co., Ltd. A device equivalent to that described in Institute of Electronics, Information and Communication Engineers EID2011-16 (2012-01), pp. 5-8 was prepared and measured. (Commercial device: Spectrometer)
[Calculation of light extraction index]
Calculations were made using software equivalent to that described in The Institute of Electronics, Information and Communication Engineers EID2011-16 (2012-01), pp. 5-8.
[Barium titanate particles]
Toda Kogyo Co., Ltd. barium titanate powder TFP-NJ-R, average primary particle size: 175 nm
[Titanium oxide particles]
TAYCA Corporation rutile titanium oxide JR-600A, average primary particle size: 0.25 μm
[F-477]
DIC Corporation surfactant Megafac (registered trademark) F-477
[3-methacryloxypropyltriethoxysilane]
Shin-Etsu Chemical Co., Ltd.KBE-503
[Crosslinking agent]
BI-7992 manufactured by Baxenden chemicals
B-882N manufactured by Mitsui Chemicals, Inc.

[1] Synthesis of triazine ring-containing hyperbranched polymer [Synthesis example 1] Synthesis of triazine ring-containing hyperbranched polymer HB-TmDA

DMAc 456.02 g was added to a 1,000 mL four-necked flask under a nitrogen atmosphere, and the mixture was cooled to −10 ° C. with an acetone-dry ice bath, and 2,4,6-trichloro-1,3,5-triazine (84.83 g, 0.460 mol, manufactured by Eponic Degussa Co., Ltd.) was added and dissolved. Then, m-phenylenediamine (62.18 g, 0.575 mol) and aniline (14.57 g, 0.156 mol) dissolved in 304.01 g of DMAc were added dropwise. After the dropping, the mixture was stirred for 30 minutes, and 1.85 g of DMAc62.85 g was added to a 2,000 mL four-necked flask in advance, and the solution was dropped into a tank heated to 85 ° C. in an oil bath over 1 hour by a liquid feeding pump. Polymerization was carried out by stirring for an hour.
Then, aniline (113.95 g, 1.224 mol) was added and the reaction was completed by stirring for 1 hour. After cooling to room temperature with an ice bath, triethylamine (116.36 g, 1.15 mol) was added dropwise and stirred for 30 minutes to quench hydrochloric acid. Then, the precipitated hydrochloride was removed by filtration. The filtered reaction solution was reprecipitated into a mixed solution of 28% aqueous ammonia solution (279.29 g) and deionized water (8,820 g). The precipitate was filtered, dried in a vacuum dryer at 150 ° C. for 8 hours, redissolved in THF (3.13.1 g), and reprecipitated in ion-exchanged water (6,665 g). The obtained precipitate was filtered and dried in a vacuum dryer at 150 ° C. for 25 hours to obtain 118.0 g of a target triazine ring-containing hyperbranched polymer HB-TmDA40.
The measurement result of the ¹ H-NMR spectrum of HB-TmDA40 is shown in FIG. The obtained HB-TmDA40 is a compound containing a repeating unit represented by the following formula. HB-TmDA40 had an Mw of 4,300 and a dispersity (Mw / Mn) of 3.44.

(1) Heat resistance test The HB-TmDA40 obtained in Synthesis Example 1 was subjected to TG-DTA measurement, and the 5% weight loss was 419 ° C. The result is shown in FIG.
(2) Measurement of Refractive Index 0.5 g of HB-TmDA40 obtained in Synthesis Example 1 was dissolved in 4.5 g of cyclohexanone to obtain a pale yellow transparent solution. The polymer varnish thus obtained was spin-coated on a glass substrate using a spin coater at 200 rpm for 5 seconds and 2,000 rpm for 30 seconds, and heated at 150 ° C. for 1 minute and 250 ° C. for 5 minutes to remove the solvent to form a film. Got When the refractive index of the obtained coating film was measured, the refractive index at 550 nm was 1.790.

[2] Preparation of composition for forming light-scattering film [Production Example 1]
40 g of HB-TmDA40 obtained in Synthesis Example 1 was dissolved in a mixed solvent of 153.6 g of cyclohexanone and 6.4 g of ion-exchanged water to prepare a 20 mass% solution (HB-TmDA40V).

[Production Example 2] Preparation of light diffusion particle dispersion liquid TFP-NJ-R-D75 In a 300 mL glass bottle filled with 720 g of media (zirconia beads having an average particle diameter of 0.5 mm), 36.0 g of barium titanate particles, Production Example 60.0 g of HB-TmDA40V prepared in 1 and 24.0 g of cyclopentanone / ion-exchanged water (96/4 (mass ratio)) were added and dispersed in a ball mill for 22 hours to obtain a dispersion liquid having a solid content of 40% by mass (TFP -NJ-R-D75) was prepared. Barium titanate: HB-TmDA = 75: 25 (mass ratio). The particle size distribution of this dispersion was measured and found to be 0.24 μm (D ₅₀ ) and 0.31 μm (D ₉₀ ).

[Production Example 3] Preparation of light diffusion particle dispersion liquid TFP-NJ-R-D50 To 20.0 g of TFP-NJ-R-D75 prepared in Production Example 2 was added HB-TmDA40V 20.0 g, and the solid content was 30% by mass. A dispersion liquid (TFP-NJ-R-D50) was prepared. Barium titanate: HB-TmDA = 50: 50 (mass ratio).

[Production Example 4] Preparation of light diffusing particle dispersion liquid TFP-NJ-R-D30 To 10.0 g of TFP-NJ-R-D75 prepared in Production Example 2 was added HB-TmDA40V 30.0 g to obtain a solid content of 25% by mass. A dispersion liquid (TFP-NJ-R-D30) was prepared. Barium titanate: HB-TmDA = 30: 70 (mass ratio).

[Production Example 5] Preparation of film-forming composition HB-TmDA40-VF In a 2 L eggplant flask, 874.6 g of HB-TmDA40V prepared in Production Example 1, 50.1 g of crosslinking agent B-882N and 5 of F-477 were prepared. Mass% cyclopentanone / ion-exchanged water (96/4 (mass ratio)) solution 1.75 g and cyclopentanone / ion-exchanged water (96/4 (mass ratio)) 473.5 g were added, and the dispersion liquid (HB -TmDA40-VF) was prepared.

[Production Example 6] Preparation of light diffusion particle dispersion liquid JR600A-D In a 500 mL round-bottomed flask, titanium oxide particles 50 g, cyclopentanone 194.5 g, 3-methacryloxypropyltriethoxysilane 5.0 g, and ion-exchanged water 0 0.5 g was added and the mixture was stirred at 60 ° C. for 3 hours. A vertical batch type bead mill in which HB-TmDA40V66.67g prepared in Production Example 1 was added to 233.33g of this dispersion and 1,160g of media (φ1.0 mm zirconia beads (YTZ ball, manufactured by Nikkato)) was filled. Then, the medium was removed by stirring at 200 rpm for 5 minutes and 1500 rpm for 2 hours to obtain a dispersion (JR600A-D).

[Example 1] Preparation of composition TFP-NJ-R-D75-40 for forming light-scattering film TFP-NJ-R-D75 38.10 g prepared in Production Example 2, crosslinking agent BI-7992 1.10 g, F 0.17 g of a 1 mass% cyclopentanone / ion exchanged water (96/4 (mass ratio)) solution of -477 and 0.63 g of cyclopentanone / ion exchanged water (96/4 (mass ratio)), A dispersion liquid (TFP-NJ-R-D75-40) having a solid content of 40 mass% was prepared.

[Example 2] Preparation of composition for forming light-scattering film TFP-NJ-R-D75-30 6.0 g of TFP-NJ-R-D75-40 prepared in Example 1, cyclopentanone / ion-exchanged water ( 96/4 (mass ratio)) 2.0 g was added to prepare a dispersion liquid (TFP-NJ-R-D75-30) having a solid content of 30% by mass.

[Example 3] Preparation of light-scattering film forming composition TFP-NJ-R-D50-30 36.36 g of TFP-NJ-R-D50 prepared in Production Example 3, 1.57 g of F-7-992, F -277% of 1 mass% cyclopentanone / ion-exchanged water (96/4 (mass ratio)) solution and 0.27 g of cyclopentanone / ion-exchanged water (96/4 (mass ratio)) 1.81 g were added, A dispersion liquid (TFP-NJ-R-D50-30) having a solid content of 30 mass% was prepared.

[Example 4] Preparation of composition for forming light-scattering film TFP-NJ-R-D50-20 4.0 g of TFP-NJ-R-D50-30 prepared in Example 3 and cyclopentanone / ion-exchanged water (96/4 (mass ratio)) 2.0 g was added to prepare a dispersion liquid (TFP-NJ-R-D50-20) having a solid content of 20 mass%.

[Example 5] Preparation of composition TFP-NJ-R-D30-25 for forming light-scattering film 35.10 g of TFP-NJ-R-D30 prepared in Production Example 4, 1.75 g of crosslinking agent BI-7992, F 0.37 g of a 1 mass% cyclopentanone / ion exchanged water (96/4 (mass ratio)) solution of -477 and 2.87 g of cyclopentanone / ion exchanged water (96/4 (mass ratio)), A dispersion liquid (TFP-NJ-R-D30-25) having a solid content of 25 mass% was prepared.

[Example 6] Preparation of composition for forming light scattering film TFP-NJ-R-D30-15 3.0 g of TFP-NJ-R-D30-25 prepared in Example 5 and cyclopentanone / ion-exchanged water (96/4 (mass ratio)) 2.0 g was added to prepare a dispersion liquid (TFP-NJ-R-D30-15) having a solid content of 15% by mass.

[Example 7] Production of light scattering film TFP-NJ-RD-75-T25 Using TFP-NJ-R-D75-40 prepared in Example 1, spin coating was performed at 200 rpm for 5 seconds and 650 rpm for 30 seconds. The film was formed under the condition of second. Then, it was dried at 100 ° C. for 1 minute and at 200 ° C. for 5 minutes to obtain a light scattering film TFP-NJ-RD-75-T25. The film thickness of this light scattering film was measured and found to be 2.5 μm.

[Example 8] Production of light scattering film TFP-NJ-RD-75-T20 The same as Example 7 except that the film was formed by spin coating at 200 rpm for 5 seconds and 1,000 rpm for 30 seconds. Thus, a light scattering film TFP-NJ-RD-75-T20 was obtained. The film thickness of this light scattering film was measured and found to be 2.0 μm.

[Example 9] Production of light scattering film TFP-NJ-RD-75-T15 Same as Example 7 except that the film was formed by spin coating at 200 rpm for 5 seconds and 1700 rpm for 30 seconds. Thus, a light scattering film TFP-NJ-RD-75-T15 was obtained. The film thickness of this light scattering film was measured and found to be 1.5 μm.

[Example 10] Preparation of light scattering film TFP-NJ-RD-75-T10 Using the TFP-NJ-R-D75-30 prepared in Example 2, spin coating was performed at 200 rpm for 5 seconds and at 900 rpm for 30 seconds. The film was formed under the condition of second. Then, it was dried at 100 ° C. for 1 minute and at 200 ° C. for 5 minutes to obtain a light scattering film TFP-NJ-RD-75-T10. The film thickness of this light scattering film was measured and found to be 1.0 μm.

[Example 11] Production of light scattering film FP-NJ-RD-50-T25 Using the TFP-NJ-R-D50-30 prepared in Example 3, spin coating was performed at 200 rpm for 5 seconds and at 800 rpm for 30 seconds. The film was formed under the condition of second. Then, it was dried at 100 ° C. for 1 minute and at 200 ° C. for 5 minutes to obtain a light scattering film TFP-NJ-RD-50-T25. The film thickness of this light scattering film was measured and found to be 2.5 μm.

[Example 12] Production of light scattering film TFP-NJ-RD-50-T20 The same as Example 11 except that the film was formed by spin coating at 200 rpm for 5 seconds and 1200 rpm for 30 seconds. Thus, a light scattering film TFP-NJ-RD-50-T20 was obtained. The film thickness of this light scattering film was measured and found to be 2.0 μm.

[Example 13] Production of light scattering film TFP-NJ-RD-50-T15 Same as Example 11 except that the film was formed by spin coating at 200 rpm for 5 seconds and 1,950 rpm for 30 seconds. Thus, a light scattering film TFP-NJ-RD-50-T15 was obtained. The film thickness of this light scattering film was measured and found to be 1.5 μm.

[Example 14] Production of light-scattering film TFP-NJ-RD-50-T10 Using TFP-NJ-R-D50-20 prepared in Example 4, spin coating was performed at 200 rpm for 5 seconds and 650 rpm for 30 seconds. The film was formed under the condition of second. Then, it was dried at 100 ° C. for 1 minute and at 200 ° C. for 5 minutes to obtain a light scattering film TFP-NJ-RD-50-T10. The film thickness of this light scattering film was measured and found to be 1.0 μm.

[Example 15] Production of light scattering film TFP-NJ-RD-30-T25 Using the TFP-NJ-R-D30-25 prepared in Example 5, spin coating was performed at 200 rpm for 5 seconds and 1,050 rpm. A film was formed under the conditions of 30 seconds. Then, it was dried at 100 ° C. for 1 minute and at 200 ° C. for 5 minutes to obtain a light scattering film TFP-NJ-RD-30-T25. The film thickness of this light scattering film was measured and found to be 2.5 μm.

[Example 16] Production of light scattering film TFP-NJ-RD-30-T20 The same as Example 15 except that the film was formed by spin coating at 200 rpm for 5 seconds and 1500 rpm for 30 seconds. As a result, a light scattering film TFP-NJ-RD-30-T20 was obtained. The film thickness of this light scattering film was measured and found to be 2.0 μm.

[Example 17] Production of light scattering film TFP-NJ-RD-30-T15 In the same manner as in Example 15 except that the film was formed by spin coating at 200 rpm for 5 seconds and 2,700 rpm for 30 seconds. Thus, a light scattering film TFP-NJ-RD-30-T15 was obtained. The film thickness of this light scattering film was measured and found to be 1.5 μm.

[Example 18] Production of light-scattering film TFP-NJ-RD-30-T10 Using TFP-NJ-R-D30-15 prepared in Example 6, by spin coating method, 200 rpm for 5 seconds, and 500 rpm for 30 seconds. The film was formed under the condition of second. Then, it was dried at 100 ° C. for 1 minute and at 200 ° C. for 5 minutes to obtain a light scattering film TFP-NJ-RD-30-T10. The film thickness of this light scattering film was measured and found to be 1.0 μm.

[Comparative Example 1] Preparation of light scattering film forming composition JR600A-D-20 223.10 g of HB-TmDA40V prepared in Production Example 6, 250.99 g of JR600A-D prepared in Production Example 14, crosslinking agent BI-7992 15.94 g, 2.79 g of a 5 mass% cyclopentanone / ion-exchanged water (96/4 (mass ratio)) solution of F-477, and cyclopentanone / ion-exchanged water (96/4 (mass ratio)) 37 .19 g was added to prepare a dispersion liquid (JR600A-D-20) having a solid content of 20% by mass.

[Comparative Example 2] Production of light scattering film JR600A-D-20-T15 Using the JR600A-D-20 prepared in Comparative Example 1, a film was formed by spin coating at 200 rpm for 5 seconds and 500 rpm for 30 seconds. did. Then, it was dried at 100 ° C. for 1 minute and at 200 ° C. for 5 minutes to obtain a light scattering film JR600A-D-20-T15.

[Comparative Example 3] Production of light scattering film JR600A-D-20-T10 Light was produced in the same manner as in Example 76 except that the film was formed by spin coating at 200 rpm for 5 seconds and 1,000 rpm for 30 seconds. A scattering film JR600A-D-20-T10 was obtained.

  The TT, haze value, PT, and DIF of each light-scattering film produced in Examples 7 to 18 and Comparative Examples 2 to 3 were measured using a turbidimeter. The results are shown in Table 1.

  As shown in Table 1, the light diffusion performance is improved by blending barium titanate as the light diffusing particles, and as the blending ratio of the light diffusing particles is increased, the haze value, the total light transmittance and the diffuse light transmittance are increased. The rate has risen.

[Examples 19 to 30 and Comparative Examples 4 to 5] Flattened light-scattering film The HB-TmDA40-VF prepared in Production Example 5 was placed on the substrates obtained in Examples 7 to 18 and Comparative Examples 2 to 3. A film was formed by spin coating under the conditions of 200 rpm for 5 seconds and 1,000 rpm for 30 seconds. Then, it was dried at 100 ° C. for 1 minute and at 200 ° C. for 1 hour to obtain a flattened light-scattering film. When the film thickness of the flattened light-scattering film was measured, the film thickness was increased by 1.0 μm.

  The TT, haze value, PT, and DIF of the flattened light-scattering films produced in Examples 19 to 30 and Comparative Examples 4 to 5 were measured using a turbidimeter. The results are shown in Table 2.

  As shown in Table 2, by laminating HB-TmDA40-V-F as the flattening layer, the haze value and diffused light transmittance decreased, and the total light transmittance increased.

[3] Measurement of light transmission / scattering characteristics [Examples 31 to 42]
RF sputtering was performed on the flattening light-scattering films produced in Examples 19 to 30 and Comparative Examples 4 to 5 at 22 ° C. for 7 minutes at an output of 350 W by using a sputtering apparatus, and ITO was laminated to a thickness of 250 nm. It was

[Comparative Example 6]
RF sputtering was performed on a non-alkali glass substrate at 22 ° C. for 7 minutes at an output of 350 W on a non-alkali glass substrate to deposit ITO with a thickness of 250 nm.

[Comparative Examples 7 to 8]
RF sputtering was performed on the flattened light-scattering film produced in Comparative Examples 4 to 5 using a sputtering device at 22 ° C. and an output of 350 W for 7 minutes to stack ITO with a thickness of 250 nm.

  The light transmission / scattering characteristics of the films produced in Examples 31 to 42 and Comparative Examples 6 to 8 were measured using an integrating sphere type transmission fluorescence measuring device. Table 3 shows the results of the respective light extraction indexes when Comparative Example 6 was used as the reference (1.00).

  As shown in Table 3, in Comparative Examples 7 to 8, the light extraction index was 1.29 times by introducing the light scattering layer using titanium oxide between ITO and the alkali-free glass. When the light-scattering layer using barium titanate was introduced, the light extraction index was improved to 1.27 to 1.45 times.

  Further, a graph showing the incident angle dependence of the total radiant flux in the light-scattering film of Example 40 (solid line) and the light-scattering film of Comparative Example 6 (dotted line) is shown in FIG. 3, and the light-scattering film of Comparative Example 8 (solid line). 4) and the light scattering film of Comparative Example 6 (dotted line), the graph showing the incident angle dependence of the total radiant flux is shown in FIG.

Claims (11)

Light-scattering film formation comprising a triazine ring-containing polymer containing a repeating unit represented by the following formula (1), a cross-linking agent, and a light diffusing agent containing barium titanate particles having an average primary particle diameter of 50 nm to 3 μm. a use composition,
The barium titanate particles measure the primary particle diameter of 100 barium titanate particles with a scanning electron microscope and calculate the average thereof, and the CV value calculated from standard deviation / average diameter × 100 is 20%. The following composition for forming a light-scattering film .

[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,
Ar represents at least one selected from the group consisting of groups represented by the following formulas (2) to (13).

{In the formula, R ^{1 to} R ⁹² are each independently a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, a linear or branched alkyl group having 1 to 10 carbon atoms, or 1 to 10 carbon atoms. Represents a linear or branched alkoxy group of
R ⁹³ and R ⁹⁴ represent a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms,
W ¹ and W ² are independently of each other, a single ^{bond, -CR 95 R 96 -, -} C (= O) -, - O -, - S -, - S (= O) -, - SO 2 - Or —NR ⁹⁷ —, R ⁹⁵ and R ⁹⁶ each independently represent a hydrogen atom, or a linear or branched alkyl group having 1 to 10 carbon atoms, which are bonded to each other to form A ring may be formed together with the carbon atom to be bonded, R ⁹⁷ represents a hydrogen atom, or a linear or branched alkyl group having 1 to 10 carbon atoms,
X ¹ and X ² each independently represent a single bond, a linear or branched alkylene group having 1 to 10 carbon atoms, or a group represented by the following formula (14).

(In the formula, R ^{98 to} R ¹⁰¹ are each independently a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, a linear or branched alkyl group having 1 to 10 carbon atoms, or 1 to 10 carbon atoms. Represents a linear or branched alkoxy group, and Y ¹ and Y ² independently of each other represent a single bond or a linear or branched alkylene group having 1 to 10 carbon atoms.)}] The light-scattering film-forming composition according to claim 1 , wherein the barium titanate particles have an average primary particle diameter of 150 nm to 1 μm. The composition for forming a light-scattering film according to claim 1 or 2, wherein the barium titanate particles have a ratio of major axis to minor axis (major axis / minor axis) of 3 or less measured by observation with a scanning electron microscope. Furthermore, the light scattering film forming composition according to any one of claims 1 to 3 containing a solvent. Light-scattering film obtained by curing the claims 1 to light scattering film forming composition according to any one of the 4. The light scattering film according to claim 5 , having a haze value of 30 to 75. Light scattering film formed by laminating a planarizing film on the light scattering film according to claim 5 or 6. The light scattering film according to claim 7 , which has a haze value of 25 to 70. An organic electroluminescent device comprising a light-scattering film of any one of claims 5-8. Emitting diode comprising a light-scattering film of any one of claims 5-8. Dielectric material with a light-scattering film of any one of claims 5-8.

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