CN117321141A

CN117321141A - Solvent-free composition

Info

Publication number: CN117321141A
Application number: CN202280030290.7A
Authority: CN
Inventors: 中家直树; 古川智规; 田中智惠; 渡边勇树
Original assignee: Nissan Chemical Corp
Current assignee: Nissan Chemical Corp
Priority date: 2021-04-23
Filing date: 2022-04-21
Publication date: 2023-12-29
Also published as: WO2022225017A1; KR20230174249A; TW202311330A; JPWO2022225017A1

Abstract

A solvent-free composition comprising a triazine ring-containing polymer, a crosslinking agent, and inorganic fine particles, and being free of an organic solvent, the triazine ring-containing polymer comprising a repeating unit structure represented by the following formula (1) having at least one triazine ring terminal, at least a part of the triazine ring terminal being blocked with an amino group having a crosslinking group. Wherein R and R' independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or an aralkyl group, and Q represents a divalent group having 3 to 30 carbon atoms and having a ring structure. * Represents a chemical bond and is used to form a bond,

Description

Solvent-free composition

Technical Field

The present invention relates to solvent-free compositions.

Background

In recent years, in the development of electronic devices such as liquid crystal displays, organic Electroluminescence (EL) devices (organic EL displays or organic EL illumination), touch panels, optical semiconductor (light emitting diode (LED) devices, etc.), solid-state imaging devices, organic thin-film solar cells, dye-sensitized solar cells, and organic thin-film transistors (TFTs), high-functional polymer materials have been demanded.

Specific characteristics required include 1) heat resistance, 2) transparency, 3) high refractive index, 4) high solubility, 5) low volume shrinkage, 6) high temperature and high humidity resistance, 7) high film hardness, and the like.

In view of this, the present applicant has found that a polymer containing a repeating unit having a triazine ring and an aromatic ring has a high refractive index, and the polymer alone can achieve high heat resistance, high transparency, high refractive index, high solubility and low volume shrinkage, and is suitable as a film-forming composition in the production of electronic devices (patent document 1).

In addition, in the planarization layer, the light scattering layer, and the like in the organic EL lighting, a composition in which a high refractive index material is dissolved in an organic solvent is generally used and a thin film is produced by a coating method, but depending on the kind of transparent conductive film, a solvent having high polarity may not be used.

In view of this, the present applicant has found that a composition for a solvent-free photocurable adhesive comprising a triazine ring-containing polymer is suitable for use as a refractive index adjusting material (patent document 2).

However, there is room for improvement in solvent resistance.

Prior art literature

Patent literature

Patent document 1: international publication No. 2010/128661.

Patent document 2: international publication No. 2016/194920.

Disclosure of Invention

Problems to be solved by the invention

The present invention has been made in view of the above circumstances, and an object thereof is to provide a solvent-free composition which can form a cured film having a high refractive index, which can maintain a high solvent resistance even when the film thickness is large, which can maintain a high transmittance and a low haze, and which can reduce the viscosity.

Means for solving the problems

As a result of intensive studies to achieve the above object, the present inventors have found that by using a triazine ring-containing polymer having at least one triazine ring end and at least a part of the triazine ring end being blocked with an amino group having a crosslinking group, a crosslinking agent, and inorganic fine particles in a solvent-free composition, a cured film having a high refractive index, capable of maintaining high solvent resistance even when the film thickness is thick, and capable of maintaining high transmittance and low haze can be formed, and further by including inorganic fine particles in a solvent-free composition containing a triazine ring-containing polymer, the high refractive index can be maintained and the viscosity can be reduced, and completed the present invention.

Namely, the present invention provides the following solvent-free composition.

[1] A solvent-free composition comprising a triazine ring-containing polymer, a crosslinking agent, and inorganic fine particles, and being free of an organic solvent, the triazine ring-containing polymer comprising a repeating unit structure represented by the following formula (1) having at least one triazine ring terminal, at least a part of the triazine ring terminal being blocked with an amino group having a crosslinking group.

Chemical formula 1

( In the formula (1), R and R' independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or an aralkyl group, and Q represents a divalent group having 3 to 30 carbon atoms and having a ring structure. * Representing a chemical bond. )

[2] The solvent-free composition according to [1], wherein Q in the formula (1) represents at least one selected from the group consisting of formulas (2) to (13) and formulas (102) to (115).

Chemical formula 2

[ in the formulae (2) to (13), R ¹ ～R ⁹² Independently of each other, a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.

R ⁹³ And R is ⁹⁴ Represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

W ¹ And W is ² Independently of each other, represent a single bond, CR ⁹⁵ R ⁹⁶ (R ⁹⁵ And R is ⁹⁶ Independently of one another, represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms (wherein these may form a ring together) or a haloalkyl group having 1 to 10 carbon atoms), c= O, O, S, SO, SO ₂ Or NR (NR) ⁹⁷ (R ⁹⁷ Represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a phenyl group).

X ¹ And X ² Independently of each other, represents a single bond, an alkylene group having 1 to 10 carbon atoms, or a group represented by the formula (14).

Chemical formula 3

(in the formula (14), R ⁹⁸ ～R ¹⁰¹ Independently of one another, represents a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, Y ¹ And Y ² Independently of each other, represents a single bond or an alkylene group having 1 to 10 carbon atoms).

* Representing a chemical bond. A kind of electronic device

Chemical formula 4

(in the formulae (102) to (115), R ¹ And R is ² Independently of each other, represents an alkylene group having 1 to 5 carbon atoms which may have a branched structure. * Representing a chemical bond. )

[3]Such as [1]]Or [2 ]]The solvent-free composition, wherein the R in the formulas (2) to (13) ¹ ～R ⁹² And R is ⁹⁸ ～R ¹⁰¹ Independently of one another, a hydrogen atom, a halogen atom or a haloalkyl group having 1 to 10 carbon atoms.

[4] The solvent-free composition according to any one of [1] to [3], wherein the arylamino group having a crosslinking group is represented by formula (15).

Chemical formula 5

(in the formula (15), R ¹⁰² Represents a crosslinking group. * Representing a chemical bond. )

[5] The solvent-free composition according to [4], wherein the amino group having a crosslinking group is represented by formula (16).

Chemical formula 6

(in the formula (16), R ¹⁰² The same meaning as described above is indicated. * Representing a chemical bond. )

[6]Such as [4]]Or [5]]The solvent-free composition, wherein R is ¹⁰² Is a hydroxyl-containing group or a (meth) acryloyl-containing group.

[7]Such as [6 ]]The solvent-free composition, wherein R is ¹⁰² Is a hydroxyalkyl group, (meth) acryloyloxyalkyl group or a group represented by the following formula (i).

Chemical formula 7

(in the formula (i), A ¹ Represents an alkylene group having 1 to 10 carbon atoms, A ² Represents a single bond or a group represented by the following formula (j),

chemical formula 8

A ³ Represents an (a+1) -valent aliphatic hydrocarbon group which may be substituted with a hydroxyl group, A ⁴ Represents a hydrogen atom or a methyl group, a represents 1 or 2, and a represents a bond. )

[8]Such as [7 ]]The solvent-free composition, wherein R is ¹⁰² Is a group selected from the group consisting of hydroxymethyl, 2-hydroxyethyl, (meth) acryloyloxymethyl, (meth) acryloyloxyethyl and groups represented by the following formulas (i-2) to (i-5).

Chemical formula 9

(in the formulae (i-2) to (i-5): represent a bond.)

[9] The solvent-free composition according to any one of [2] to [8], wherein at least one aromatic ring in Q in the formula (1) contains at least one halogen atom or a halogenated alkyl group having 1 to 10 carbon atoms.

[10] The solvent-free composition of any one of [1] to [9], wherein a portion of the triazine ring ends are further capped with an unsubstituted arylamino group.

[11] The solvent-free composition of any one of [1] to [10], wherein the unsubstituted arylamino group is represented by formula (33).

Chemical formula 10

(in formula (33): represents a chemical bond.)

[12] The solvent-free composition according to any one of [1] to [11], wherein Q in the formula (1) is represented by the formula (17).

Chemical formula 11

(in formula (17): represents a chemical bond.)

[13] The solvent-free composition according to any one of [1] to [12], wherein Q in the formula (1) is represented by the formula (20).

Chemical formula 12

(in formula (20): represents a chemical bond.)

[14] The solvent-free composition of any one of [1] to [13], wherein the crosslinking agent is a polyfunctional (meth) acryl compound.

[15] The solvent-free composition of any one of [1] to [14], wherein the inorganic fine particles comprise a metal oxide, a metal sulfide or a metal nitride.

[16] The solvent-free composition of any one of [1] to [15], wherein the solvent-free composition further comprises a reactive diluent.

[17] The solvent-free composition of [16], wherein the reactive diluent is a compound having one radical polymerizable group.

[18] The solvent-free composition according to any one of [1] to [17], wherein the solvent-free composition is a photocurable composition.

[19] A film, wherein the film is obtained from the solvent-free composition of any one of [1] to [18 ].

[20] An electronic device, wherein the electronic device has a substrate and the film of [19] formed on the substrate.

[21] An optical member, wherein the optical member has a substrate and the film of [19] formed on the substrate.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, a solvent-free composition which can form a cured film having a high refractive index, can maintain a high solvent resistance even when the film thickness is large, can maintain a high transmittance and a low haze, and can further reduce the viscosity can be provided.

The film made of the solvent-free composition of the present invention can exhibit characteristics such as high heat resistance, high refractive index, low volume shrinkage, solvent resistance (crack resistance), and the like, and therefore can be suitably used in the field of electronic devices or optical materials for manufacturing one member such as a liquid crystal display, an organic EL element (organic EL display or organic EL illumination), a touch panel, an optical semiconductor element, a solid-state imaging element, an organic thin film solar cell, a dye-sensitized solar cell, an organic thin film transistor, a lens, a prism, a camera, a binoculars, a microscope, a semiconductor exposure device, and the like.

In particular, the film made of the solvent-free composition of the present invention is high in transparency and also high in refractive index, solvent resistance (crack resistance), and therefore by being used as a planarizing layer, a light scattering layer, a sealing material for organic EL illumination, the light extraction efficiency (light diffusion efficiency) thereof can be improved and the durability thereof can be improved.

Drawings

FIG. 1 shows the compound P-1 (polymer compound [5 ]]) A kind of electronic device ¹ H-NMR spectrum.

FIG. 2 is a schematic diagram of the compound P-2 (Polymer [7 ]]) A kind of electronic device ¹ H-NMR spectrum.

FIG. 3 is an optical micrograph of the solvent-exposed surface of the cured film obtained in example 3-1-1.

FIG. 4 is an optical micrograph of the solvent-exposed surface of the cured film obtained in example 3-1-2.

FIG. 5 is an optical micrograph of the solvent-exposed surface of the cured film obtained in example 3-1-3.

FIG. 6 is an optical micrograph of the solvent-exposed surface of the cured film obtained in example 3-2-1.

FIG. 7 is an optical micrograph of the solvent-exposed surface of the cured film obtained in example 3-2-2.

FIG. 8 is an optical micrograph of the solvent-exposed surface of the cured film obtained in example 3-2-3.

FIG. 9 is an optical micrograph of the solvent-exposed surface of the cured film obtained in example 3-3-1.

FIG. 10 is an optical micrograph of the solvent-exposed surface of the cured film obtained in example 3-3-2.

FIG. 11 is an optical micrograph of the solvent-exposed surface of the cured film obtained in example 3-3-3.

FIG. 12 is an optical micrograph of the solvent-exposed surface of the cured film obtained in example 3-4-1.

FIG. 13 is an optical micrograph of the solvent-exposed surface of the cured film obtained in example 3-4-2.

FIG. 14 is an optical micrograph of the solvent-exposed surface of the cured film obtained in example 3-4-3.

FIG. 15 is an optical micrograph of the solvent-exposed surface of the cured film obtained in example 3-5-1.

FIG. 16 is an optical micrograph of the solvent-exposed surface of the cured film obtained in example 3-5-2.

FIG. 17 is an optical micrograph of the solvent-exposed surface of the cured film obtained in example 3-5-3.

FIG. 18 is an optical micrograph of the solvent-exposed surface of the cured film obtained in example 3-6-1.

FIG. 19 is an optical micrograph of the solvent-exposed surface of the cured film obtained in example 3-6-2.

FIG. 20 is an optical micrograph of the solvent-exposed surface of the cured film obtained in example 3-6-3.

Detailed Description

The present invention will be described in further detail below.

The solvent-free composition of the invention comprises a triazine ring-containing polymer, a cross-linking agent and inorganic particles. The solventless composition does not contain an organic solvent.

The term "free of an organic solvent" means substantially free of an organic solvent, and specifically means that the content of the organic solvent is 10 mass% or less.

(1) Triazine ring-containing polymers

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

The triazine ring-containing polymer is, for example, a so-called hyperbranched polymer. Hyperbranched polymers refer to highly branched polymers having an irregular branched structure. The term "irregular" as used herein means that the branched structure of the dendrimer is more irregular than that of the hyperbranched polymer having a regular branched structure.

For example, the triazine ring-containing polymer as the hyperbranched polymer includes, as a structure larger than the repeating unit structure represented by the formula (1), a structure (structure X) in which three chemical bonds of the repeating unit structure represented by the formula (1) are bonded to the repeating unit structure represented by the formula (1), respectively. In the triazine ring-containing polymer as the hyperbranched polymer, the structure X is distributed throughout the whole of the triazine ring-containing polymer except for the terminal.

In the triazine ring-containing polymer as the hyperbranched polymer, the repeating unit structure may be essentially constituted of only the repeating unit structure represented by the formula (1).

Chemical formula 13

* Representing a chemical bond.

R and R' >, and a process for preparing the same

In the above formula, R and R' independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or an aralkyl group, but from the viewpoint of further improving the refractive index, hydrogen atoms are preferable.

In the present invention, the number of carbon atoms of the alkyl group is not particularly limited, but is preferably 1 to 20, and in view of further improving the heat resistance of the polymer, the number of carbon atoms of the alkyl group is more preferably 1 to 10, and still more preferably 1 to 3. The structure of the alkyl group is not particularly limited, and may be, for example, any of linear, branched, cyclic, and a combination of two or more of these.

As a specific example of the alkyl group, examples thereof include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1-dimethyl-n-propyl, 1, 2-dimethyl-n-propyl, 2-dimethyl-n-propyl, 1-ethyl-n-propyl, cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclobutyl, 1, 2-dimethyl-cyclopropyl, 2, 3-dimethyl-cyclopropyl 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1-dimethyl-n-butyl, 1, 2-dimethyl-n-butyl, 1, 3-dimethyl-n-butyl, 2-dimethyl-n-butyl, 2, 3-dimethyl-n-butyl, 3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1, 2-trimethyl-n-propyl, 1, 2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1, 2-dimethyl-cyclobutyl, 1, 3-dimethyl-cyclobutyl, 2-dimethyl-cyclobutyl, 2, 3-dimethyl-cyclobutyl, 2, 4-dimethyl-cyclobutyl, 3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-isopropyl-cyclopropyl, 2-isopropyl-cyclopropyl, 1, 2-trimethyl-cyclopropyl, 1,2, 3-trimethyl-cyclopropyl, 2, 3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl, 2-ethyl-3-methyl-cyclopropyl, and the like.

The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably 1 to 20, and in view of further improving the heat resistance of the polymer, the number of carbon atoms of the alkoxy group is more preferably 1 to 10, and still more preferably 1 to 3. The structure of the alkyl moiety is not particularly limited, and may be, for example, any of linear, branched, cyclic, and combinations of two or more of these.

As a specific example of the alkoxy group, examples thereof include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, 1-methyl-n-butoxy, 2-methyl-n-butoxy, 3-methyl-n-butoxy, 1-dimethyl-n-propoxy, 1, 2-dimethyl-n-propoxy, 2-dimethyl-n-propoxy, 1-ethyl-n-propoxy, n-hexyloxy, 1-methyl-n-pentoxy, 2-methyl-n-pentoxy, 3-methyl-n-pentoxy 4-methyl-n-pentyloxy, 1-dimethyl-n-butyloxy, 1, 2-dimethyl-n-butyloxy, 1, 3-dimethyl-n-butyloxy, 2-dimethyl-n-butyloxy, 2, 3-dimethyl-n-butyloxy, 3-dimethyl-n-butyloxy, 1-ethyl-n-butyloxy, 2-ethyl-n-butyloxy, 1, 2-trimethyl-n-propyloxy, 1, 2-trimethyl-n-propyloxy, 1-ethyl-1-methyl-n-propyloxy, 1-ethyl-2-methyl-n-propyloxy, and the like.

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

In the present invention, the above aryl group includes an aryl group having a substituent. Examples of the substituent include a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a nitro group, and a cyano group.

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-nitrophenyl group, p-cyanophenyl group, α -naphthyl group, β -naphthyl group, o-biphenyl group, m-biphenyl group, p-biphenyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group and the like.

The number of carbon atoms of the aralkyl group is not particularly limited, and the number of carbon atoms is preferably 7 to 20, and the structure of the alkyl moiety is not particularly limited, and for example, it may be any of straight chain, branched, cyclic, and a combination of two or more of these.

In the present invention, the aralkyl group includes an aralkyl group having a substituent. Examples of the substituent include a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a nitro group, and a cyano group.

Specific examples thereof include benzyl, p-methylphenyl methyl, m-methylphenyl methyl, o-ethylphenyl methyl, m-ethylphenyl methyl, p-ethylphenyl methyl, 2-propylphenyl methyl, 4-isopropylphenyl methyl, 4-isobutylphenyl methyl, and α -naphthylmethyl.

＜＜Q＞＞

Q in the formula (1) is not particularly limited as long as it is a divalent group having 3 to 30 carbon atoms in a ring structure.

The ring structure may be an aromatic ring structure or an alicyclic ring structure.

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

Chemical formula 14

* Representing a chemical bond.

R is as described above ¹ ～R ⁹² Independently of each other, a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.

W ¹ And W is ² Independently of each other, represent a single bond, CR ⁹⁵ R ⁹⁶ (R ⁹⁵ And R is ⁹⁶ Independently of each other, represent a hydrogen atom, a carbon atomAlkyl of 1 to 10 (wherein these may form a ring together) or haloalkyl of 1 to 10 carbon atoms), c= O, O, S, SO, SO ₂ Or NR (NR) ⁹⁷ (R ⁹⁷ Represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a phenyl group).

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The alkyl group and the alkoxy group may be the same groups as described above.

Examples of the alkyl group and the alkoxy group include the same groups as the alkyl group and the alkoxy group in R, R'.

The haloalkyl group having 1 to 10 carbon atoms is obtained by substituting at least one hydrogen atom in the alkyl group having 1 to 10 carbon atoms with a halogen atom, and as a specific example thereof, for example, examples thereof include trifluoromethyl, 2-trifluoroethyl, perfluoroethyl, 3-trifluoropropyl, 2, 3-pentafluoropropyl, 2, 3-tetrafluoropropyl 2, 2-trifluoro-1- (trifluoromethyl) ethyl, perfluoropropyl, 4-trifluorobutyl, 3, 4-pentafluorobutyl 2, 2-trifluoro-1- (trifluoromethyl) ethyl, perfluoropropyl 4, 4-trifluorobutyl, 3, 4-pentafluorobutyl. In the present invention, from the viewpoint of improving the solubility of the triazine ring-containing polymer in a low-polarity solvent or the like while maintaining the refractive index, a perfluoroalkyl group having 1 to 10 carbon atoms is preferable, a perfluoroalkyl group having 1 to 5 carbon atoms is particularly preferable, and a trifluoromethyl group is still more preferable.

In addition, X ¹ And X ² Independently of each other, represents a single bond, an alkylene group having 1 to 10 carbon atoms, or a group represented by the formula (14).

The structures of these alkyl groups, haloalkyl groups, alkoxy groups, and alkylene groups are not particularly limited, and may be, for example, any of straight-chain, branched, cyclic, and combinations of two or more of these.

Chemical formula 15

* Representing a chemical bond.

R is as described above ⁹⁸ ～R ¹⁰¹ Independently of each other, a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.

Y ¹ And Y ² Independently of each other, represents a single bond or an alkylene group having 1 to 10 carbon atoms.

Examples of the halogen atom, alkyl group, haloalkyl group and alkoxy group include R ¹ ～R ⁹² The halogen atom, alkyl group, haloalkyl group and alkoxy group are the same.

Examples of the alkylene group having 1 to 10 carbon atoms include methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene and the like.

The structure of the alkylene group is not particularly limited, and may be, for example, any of linear, branched, cyclic, and a combination of two or more of these.

Wherein R is as R ¹ ～R ⁹² And R is ⁹⁸ ～R ¹⁰¹ The hydrogen atom, halogen atom, sulfo group, alkyl group having 1 to 5 carbon atoms, haloalkyl group having 1 to 5 carbon atoms or alkoxy group having 1 to 5 carbon atoms are preferable, and hydrogen atom is more preferable.

In the triazine ring-containing polymer of the present invention, when Q includes an aromatic ring, at least one halogen atom or a haloalkyl group having 1 to 10 carbon atoms is preferably contained in at least one of the aromatic rings included in Q. In general, it is known that the refractive index tends to be lowered by introducing fluorine atoms into the compound, but the triazine ring-containing polymer of the present invention maintains a refractive index exceeding 1.7, although fluorine atoms are also introduced. The number of halogen atoms or haloalkyl groups in the aromatic ring may be any number that can be substituted on the aromatic ring, but is preferably 1 to 4, more preferably 1 to 2, still more preferably 1, from the viewpoint of maintaining the balance of refractive index and solubility in a solvent. In the case where the aromatic ring is a member in which a plurality of aromatic rings such as naphthalene rings are condensed, at least one of the above groups may be present as a whole.

In the case where Q contains a plurality of aromatic rings, at least one halogen atom or a haloalkyl group may be contained in at least one aromatic ring, but it is preferable that all aromatic rings contain at least one halogen atom or a haloalkyl group, and it is more preferable that all aromatic rings contain one halogen atom or a haloalkyl group.

In particular, Q is preferably at least one of the formulae (2), (5) to (13), and more preferably at least one of the formulae (2), (5), (7), (8), (11) to (13). Specific examples of the divalent groups represented by the above formulas (2) to (13) include, but are not limited to, groups represented by the following formulas.

Chemical formula 16

"Ph" means phenyl. * Representing a chemical bond.

Chemical formula 17

( Wherein A is a halogen atom or a haloalkyl group having 1 to 10 carbon atoms, p is an integer of 0 to 4, q is an integer of 0 to 3, r is an integer of 0 to 2, s is an integer of 0 to 5, t is an integer of 1 to 6, and u is an integer of 1 to 4. Wherein the sum of p, q, r, s in each group is 1 or more. "Ph" means phenyl. * Representing a chemical bond. )

Among them, Q is more preferably a divalent group represented by the following formula because a polymer having a higher refractive index can be obtained.

Chemical formula 18

"Ph" means phenyl. * Representing a chemical bond.

Chemical formula 19

( Wherein A, p, q, r and u are as defined above. "Ph" means phenyl. * Representing a chemical bond. )

In particular, in view of further improving the solubility of the triazine ring-containing polymer in an organic solvent such as a low-polarity solvent, the m-phenylene group represented by formula (17) is preferable as Q.

Chemical formula 20

(wherein, represents a bond.)

In particular, from the viewpoint of further increasing the refractive index of the triazine ring-containing polymer, Q is preferably a group having a diphenyl ether skeleton represented by formulae (18) to (20).

Chemical formula 21

( Wherein A and p are as defined above. * Representing a chemical bond. )

Chemical formula 22

( Wherein A and p are as defined above. * Representing a chemical bond. )

Chemical formula 23

(wherein, represents a bond.)

In addition, Q in the formula (1) represents at least one selected from the group represented by the formulas (102) to (115), for example.

Chemical formula 24

* Representing a chemical bond.

In the formulae (102) to (115), R is ¹ And R is ² Independently of each other, represents an alkylene group having 1 to 5 carbon atoms which may have a branched structure.

Examples of such alkylene groups include methylene, ethylene, propylene, trimethylene, tetramethylene, and pentamethylene, and in view of further improving the refractive index of the resulting polymer, alkylene groups having 1 to 3 carbon atoms and alkylene groups having 1 to 2 carbon atoms are preferable, and specifically, methylene and ethylene are more preferable, and methylene is most preferable.

< amino group having crosslinking group >)

In addition, the triazine ring-containing polymer of the invention has at least one triazine ring end, at least a portion of which is capped with an amino group having a crosslinking group.

The triazine ring-containing polymer of the present invention has at least one triazine ring end, and the triazine ring of the end generally has two halogen atoms that can be substituted with the above amino group having a crosslinking group. Therefore, the amino group having a crosslinking group may be bonded to the same triazine ring end, or may be bonded to different triazine ring ends when a plurality of triazine ring ends are provided.

The number of crosslinking groups in the amino group having a crosslinking group is not particularly limited, and may be any number, and is preferably 1 to 4, more preferably 1 to 2, and even more preferably 1, in view of the balance between solvent resistance and solubility in the reactive diluent.

When the amino group having a crosslinking group has a plurality of crosslinking groups, the plurality of crosslinking groups may have the same structure or may have different structures.

The amino group having a crosslinking group is represented by, for example, the following formula (X).

Chemical formula 25

( Wherein Z represents a group having a crosslinking group. * Representing a chemical bond. )

In the formula (X), Z may be a crosslinking group itself.

Preferably, the crosslinking group is bonded to the amino group via an arylene group.

The amino group having a crosslinking group is more preferably represented by the following formula (15), and particularly preferably by the following formula (16).

Chemical formula 26

(wherein R is ¹⁰² Represents a crosslinking group. * Representing a chemical bond. )

Chemical formula 27

(wherein R is ¹⁰² The same meaning as described above is indicated. * Representing a chemical bond. )

Examples of the crosslinking group include a hydroxyl group-containing group, a vinyl group-containing group, an epoxy group-containing group, an oxetane group-containing group, a carboxyl group-containing group, a sulfo group-containing group, a thiol group-containing group, a (meth) acryl group and the like, and a hydroxyl group-containing group and a (meth) acryl group are preferable in view of improving the heat resistance of the triazine ring-containing polymer and the solvent resistance (crack resistance) of the obtained film.

Examples of the hydroxyl-containing group include a hydroxyl group and a hydroxyalkyl group, and a hydroxyalkyl group having 1 to 10 carbon atoms is preferable, a hydroxyalkyl group having 1 to 5 carbon atoms is more preferable, and a hydroxyalkyl group having 1 to 3 carbon atoms is still more preferable.

Examples of the hydroxyalkyl group having 1 to 10 carbon atoms include a group having a primary carbon atom bonded to a hydroxyl group such as a hydroxymethyl group, a 2-hydroxyethyl group, a 3-hydroxypropyl group, a 4-hydroxybutyl group, a 5-hydroxypentyl group, a 6-hydroxyhexyl group, a 7-hydroxyheptyl group, an 8-hydroxyoctyl group, a 9-hydroxynonyl group, a 10-hydroxydecyl group, a 2-hydroxy-1-methylethyl group, a 2-hydroxy-1, 1-dimethylethyl group, a 3-hydroxy-1-methylpropyl group, a 3-hydroxy-2-methylpropyl group, a 3-hydroxy-1, 1-dimethylpropyl group, a 3-hydroxy-1, 2-dimethylpropyl group, a 3-hydroxy-2, 2-dimethylpropyl group, a 4-hydroxy-1-methylbutyl group, a 4-hydroxy-2-methylbutyl group, a 4-hydroxy-3-methylbutyl group; a group having a secondary or tertiary carbon atom as a carbon atom to which a hydroxyl group such as 1-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 1-hydroxyhexyl group, 2-hydroxyhexyl group, 1-hydroxyoctyl group, 2-hydroxyoctyl group, 1-hydroxydecyl group, 2-hydroxydecyl group, 1-hydroxy-1-methylethyl group, 2-hydroxy-2-methylpropyl group is bonded.

In particular, from the viewpoint of improving heat resistance and high temperature and high humidity resistance, a group having a carbon atom to which a hydroxyl group is bonded is preferable, among which a hydroxyalkyl group having 1 to 5 carbon atoms is more preferable, a hydroxyalkyl group having 1 to 3 carbon atoms is still more preferable, hydroxymethyl and 2-hydroxyethyl are still more preferable, and 2-hydroxyethyl is most preferable.

Examples of the (meth) acryl-containing group include a (meth) acryl group, a (meth) acryloyloxyalkyl group, a group represented by the following formula (i), and the like, and a (meth) acryloyloxyalkyl group having an alkylene group having 1 to 10 carbon atoms and a group represented by the following formula (i) are preferable, and a group represented by the following formula (i) is more preferable.

Chemical formula 28

(wherein A ¹ Represents an alkylene group having 1 to 10 carbon atoms, A ² Represents a single bond or a group represented by the following formula (j),

chemical formula 29

Examples of the alkylene group contained in the (meth) acryloyloxyalkyl group having an alkylene group (alkanediyl) having 1 to 10 carbon atoms include methylene, ethylene, trimethylene, propane-1, 2-diyl, tetramethylene, butane-1, 3-diyl, butane-1, 2-diyl, 2-methylpropane-1, 3-diyl, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene and the like. Among them, an alkylene group having 1 to 5 carbon atoms is preferable, an alkylene group having 1 to 3 carbon atoms is preferable, and an alkylene group having 1 or 2 carbon atoms is more preferable in view of improving heat resistance and high temperature and high humidity resistance.

Specific examples of the (meth) acryloyloxyalkyl group include a (meth) acryloyloxymethyl group, a 2- (meth) acryloyloxyethyl group, a 3- (meth) acryloyloxypropyl group, and a 4- (meth) acryloyloxybutyl group.

In formula (i), A ¹ The alkylene group having 1 to 10 carbon atoms is preferably an alkylene group having 1 to 5 carbon atoms, and more preferably a methylene group and an ethylene group. Examples of the alkylene group having 1 to 10 carbon atoms include the same groups as those contained in the above-mentioned (meth) acryloyloxyalkyl group.

A ² Represents a single bond or a group represented by formula (j), preferably a group represented by formula (j).

A ³ Is a hydroxyl groupSpecific examples of the substituted (a+1) valent aliphatic hydrocarbon group include an alkylene group having 1 to 5 carbon atoms and groups represented by the following formulas (k-1) to (k-3),

chemical formula 30

(wherein, the same as above.)

The alkylene group having 1 to 5 carbon atoms is preferable, the alkylene group having 1 to 3 carbon atoms is more preferable, and the methylene group and the ethylene group are still more preferable. As A ³ The alkylene group of (A) includes ¹ The alkylene group having 1 to 5 carbon atoms among the alkylene groups exemplified in the specification.

a represents 1 or 2, preferably 1.

As a preferred embodiment of the group represented by the formula (i), an embodiment represented by the following formula (i-1) is given.

Chemical formula 31

(wherein A ¹ 、A ³ 、A ⁴ And are the same as described above. )

More preferable examples of the group represented by the formula (i) include those represented by the following formulas (i-2) to (i-5).

Chemical formula 32

(wherein, the same as above.)

Examples of the vinyl-containing group include alkenyl groups having 2 to 10 carbon atoms and having a vinyl group at the terminal. Specific examples thereof include vinyl, 1-propenyl, allyl, isopropenyl, 1-butenyl, 2-butenyl, and 2-pentenyl.

Examples of the epoxy group-containing group include an epoxy group, a glycidyl group, and a glycidoxy group. Specific examples thereof include glycidyl methyl, 2-glycidyl ethyl, 3-glycidyl propyl, 4-glycidyl butyl and the like.

Examples of the oxetan-containing group include oxetan-3-yl, (oxetan-3-yl) methyl, 2- (oxetan-3-yl) ethyl, 3- (oxetan-3-yl) propyl, and 4- (oxetan-3-yl) butyl.

Examples of the carboxyl group-containing group include a carboxyl group and a carboxyalkyl group having 2 to 10 carbon atoms. The carboxyalkyl group having 2 to 10 carbon atoms is preferably a secondary carbon atom to which a carboxyl group is bonded, and specific examples thereof include carboxymethyl, 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl and the like.

Examples of the sulfo group-containing group include a sulfo group and a sulfoalkyl group having 1 to 10 carbon atoms. The sulfoalkyl group having 1 to 10 carbon atoms is preferably a primary carbon atom to which a sulfo group is bonded, and specific examples thereof include a sulfomethyl group, a 2-sulfoethyl group, a 3-sulfopropyl group, a 4-sulfobutyl group, and the like.

Examples of the thiol-containing group include a thiol group and a thiol alkyl group having 1 to 10 carbon atoms. The thiol alkyl group having 1 to 10 carbon atoms is preferably a primary carbon atom to which a thiol group is bonded, and specific examples thereof include a thiol methyl group, a 2-thiol ethyl group, a 3-thiol propyl group, a 4-thiol butyl group, and the like.

Specific examples of the amino group having a crosslinking group include, but are not limited to, groups represented by the following formula.

Chemical formula 33

/>

Wherein, represents a chemical bond.

In the production method described later, an arylamino group having a hydroxyalkyl group can be introduced using a corresponding hydroxyalkyl-substituted arylamino compound.

Specific examples of the hydroxyalkyl-substituted arylamino compound include (4-aminophenyl) methanol and 2- (4-aminophenyl) ethanol.

The arylamino group having a (meth) acryloyloxyalkyl group can be introduced by the following method: a method of using a corresponding (meth) acryloyloxyalkyl-substituted arylamino compound, or a method of introducing an arylamino group having a hydroxyalkyl group into a triazine ring-containing polymer and then allowing a (meth) acryloyl halide or a glycidyl (meth) acrylate to act on a hydroxyl group contained in the hydroxyalkyl group.

An arylamino group having a group represented by formula (i) can be introduced by the following method: a method of using an arylamino compound having a target crosslinking group, or a method of further allowing a (meth) acrylate compound having an isocyanate group represented by the following formula (i') to act on a hydroxyl group contained in the hydroxyalkyl group after introducing an arylamino group having a hydroxyalkyl group into a polymer containing a triazine ring.

Chemical formula 34

(wherein A ³ 、A ⁴ And a is the same as described above. )

Specific examples of the (meth) acryloyloxyalkyl-substituted arylamino compound include an ester compound obtained by allowing a (meth) acryloyl halide or a glycidyl (meth) acrylate to act on a hydroxyl group of the above-mentioned hydroxyalkyl-substituted arylamino compound.

Examples of the (meth) acryloyl halide include (meth) acryloyl chloride, (meth) acryloyl bromide, and (meth) acryloyl iodide.

Specific examples of the (meth) acrylate compound having an isocyanate group represented by the above formula (i') include 2-isocyanatoethyl acrylate (2-Isocyanato ethyl acrylate), 2-isocyanatoethyl methacrylate and 1,1- (bisacryloxymethyl) ethyl isocyanate. In the present invention, 2-isocyanatoethyl acrylate is preferable from the viewpoint of a simple synthesis method.

In the present invention, as particularly suitable triazine ring-containing polymers, there are exemplified polymers containing repeating units represented by formulae (21) to (28).

Chemical formula 35

(wherein, R, R', R) ¹ ～R ⁴ R is as follows ¹⁰² The same meaning as described above is indicated. )

Chemical formula 36

(wherein R is ¹ ～R ⁴ R is as follows ¹⁰² The same meaning as described above is indicated. ) Chemical formula 37

(wherein R is ¹⁰² The same meaning as described above is indicated. )

Chemical formula 38

(wherein R is ¹⁰² The same meaning as described above is indicated. )

Chemical formula 39

(wherein, R, R', R) ¹⁶ ～R ²³ R is as follows ¹⁰² The same meaning as described above is indicated. ) Chemical formula 40

(wherein R is ¹⁶ ～R ²³ R is as follows ¹⁰² The same meaning as described above is indicated. )

Chemical formula 41

(wherein R is ¹⁰² The same meaning as described above is indicated. )

Chemical formula 42

(wherein R is ¹⁰² The same meaning as described above is indicated. )

The weight average molecular weight of the polymer in the present invention is not particularly limited, but is preferably 500 to 500000, more preferably 500 to 100000, and is preferably 2000 or more from the viewpoint of further improving heat resistance and reducing shrinkage, and is preferably 50000 or less, more preferably 30000 or less, still more preferably 25000 or less, and most preferably 10000 or less from the viewpoint of further improving solubility and reducing viscosity of the obtained composition.

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

The triazine ring-containing polymer (hyperbranched polymer) of the present invention can be produced according to the method disclosed in the above-mentioned international publication No. 2010/128661.

That is, after reacting the trihalotriazine compound with the aryldiamino compound in an organic solvent, for example, with at least one amino compound selected from the amino compounds having a hydroxyalkyl group (hydroxyl-containing group), the amino compound having an acryloxyalkyl group (acryl-containing group), and the amino compound having a group represented by formula (i) (acryl-containing group) as a capping agent, the triazine ring-containing polymer of the present invention can be obtained.

For example, as shown in scheme 1 below, the triazine ring-containing polymer (23) can be obtained by reacting a triazine compound (29) and an aryldiamino compound (30) in an appropriate organic solvent, followed by reacting with at least one arylamino compound (31) selected from an arylamino compound having a hydroxyalkyl group and an arylamino compound having a group represented by formula (i) as a capping agent.

Chemical formula 43

Scheme 1

(wherein X independently represents a halogen atom, R ^a Represents a hydroxyalkyl group or a group represented by formula (i). )

Further, for example, as shown in the following scheme 2, the triazine ring-containing polymer (27) can be obtained by reacting the triazine compound (29) and the aryldiamino compound (32) in an appropriate organic solvent, and then reacting with at least one arylamino compound (31) selected from the group consisting of an arylamino compound having a hydroxyalkyl group and an arylamino compound having a group represented by the formula (i) as a capping agent.

Chemical formula 44

Scheme 2

In the above-mentioned scheme 1 or scheme 2, the feed ratio of the aryldiamino compound (30) or (32) may be arbitrary as long as the target polymer is obtainable, but the aryldiamino compound (30) or (32) is preferably 0.01 to 10 equivalents, more preferably 0.7 to 5 equivalents, relative to 1 equivalent of the triazine compound (29).

The aryl diamino compound (30) or (32) may be added as a pure substance or as a solution dissolved in an organic solvent, but the latter method is preferable in view of easiness of handling, easiness of reaction control, and the like.

The reaction temperature may be appropriately set within a range from the melting point of the solvent to the boiling point of the solvent, and is preferably about-30 to 150 ℃, more preferably about-10 to 100 ℃.

As another embodiment, a method shown in the following embodiment 3 is given. In this method, the triazine ring-containing polymer (23) can be obtained by reacting the triazine compound (29) and the aryldiamino compound (30) in an appropriate organic solvent, followed by reacting with the aryl amino compound (31 ') having a hydroxyalkyl group as a capping agent to obtain the triazine ring-containing polymer (23') (first stage), and then further allowing the (meth) acrylate compound having an isocyanate group represented by the formula (i ') to act on the hydroxyl group of the hydroxyalkyl group contained in the triazine ring-containing polymer (23') (second stage).

In the case where the triazine ring-containing polymer (23') is used as the target product, the reaction of the second stage may be terminated in the first stage without being performed.

Chemical formula 45

Scheme 3

(wherein R is ^a1 Represents hydroxyalkyl, X, A ³ 、A ⁴ 、R ^a And a represents the same meaning as described above. )

In addition, as another embodiment, a method shown in the following embodiment 4 is given. In this method, the triazine ring-containing polymer (27) can be obtained by reacting the triazine compound (29) and the aryldiamino compound (32) in an appropriate organic solvent, followed by reacting with the aryl amino compound (31 ') having a hydroxyalkyl group as a capping agent to obtain the triazine ring-containing polymer (27') (first stage), and then further reacting the (meth) acrylate compound having an isocyanate group represented by the formula (i ') with the alkyl group of the hydroxyalkyl group contained in the triazine ring-containing polymer (27') (second stage).

In the case where the triazine ring-containing polymer (27') is used as the target product, the reaction of the second stage may be terminated in the first stage without being performed.

Chemical formula 46

Scheme 4

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In the above scheme 3, the ratio of the aryl diamino compound (30) in the first stage and the method of addition, and the reaction temperature in the reaction until the triazine ring-containing polymer (23') is obtained can be the same as described in scheme 1.

In the second stage, the ratio of the (meth) acrylate compound having an isocyanate group represented by the formula (i ') to the triazine ring-containing polymer (23') can be arbitrarily set according to the ratio of the hydroxyalkyl group to the group represented by the formula (i), and is preferably 0.1 to 10 equivalents, more preferably 0.5 to 5 equivalents, still more preferably 0.7 to 3 equivalents, and still more preferably 0.9 to 1.5 equivalents, to 1 equivalent of the arylamino compound having a hydroxyalkyl group to be used. For example, in the case where all of the hydroxyalkyl groups contained in the triazine ring-containing polymer (23') are groups represented by the formula (i), the addition ratio of the (meth) acrylate compound is preferably 1.0 to 10 equivalents, more preferably 1.0 to 5 equivalents, still more preferably 1.0 to 3 equivalents, and still more preferably 1.0 to 1.5 equivalents, relative to 1 equivalent of the arylamino compound having a hydroxyalkyl group to be used.

The reaction temperature in this reaction is the same as that in the reaction for obtaining the triazine ring-containing polymer (23'), but is preferably 30 to 80 ℃, more preferably 40 to 70 ℃, still more preferably 50 to 60 ℃ in view of not polymerizing the (meth) acryloyl group in the reaction.

In the above-described scheme 4, the feed ratio and the addition method of the aryl diamino compound (32) and the reaction temperature can be the same as those described in scheme 2.

In the second stage, the ratio of the (meth) acrylate compound having an isocyanate group represented by the formula (i ') to the triazine ring-containing polymer (27') can be arbitrarily set according to the ratio of the hydroxyalkyl group to the group represented by the formula (i), and is preferably 0.1 to 10 equivalents, more preferably 0.5 to 5 equivalents, still more preferably 0.7 to 3 equivalents, and still more preferably 0.9 to 1.5 equivalents, to 1 equivalent of the arylamino compound having a hydroxyalkyl group to be used. For example, in the case where all of the hydroxyalkyl groups contained in the triazine ring-containing polymer (27') are groups represented by the formula (i), the ratio of the (meth) acrylic acid ester compound to be added is preferably 1.0 to 10 equivalents, more preferably 1.0 to 5 equivalents, still more preferably 1.0 to 3 equivalents, and still more preferably 1.0 to 1.05 equivalents, based on 1 equivalent of the arylamino compound having a hydroxyalkyl group to be used.

The reaction temperature in this reaction is the same, but in view of not polymerizing the (meth) acryloyl group during the reaction, it is preferably 30 to 80 ℃, more preferably 40 to 70 ℃, still more preferably 50 to 60 ℃.

In the second stage of schemes 3 and 4.

Examples of the polymerization inhibitor include N-methyl-N-nitrosoaniline, N-nitrosophenyl hydroxylamine or salts thereof, benzoquinone, phenolic polymerization inhibitor, phenothiazine, and the like. Among them, from the viewpoint of excellent polymerization inhibition effect, examples of N-nitrosophenyl hydroxylamine salts include N-nitrosophenyl hydroxylamine ammonium salts and N-nitrosophenyl hydroxylamine aluminum salts.

Examples of benzoquinone include p-benzoquinone and 2-methyl-1, 4-benzoquinone.

Examples of the phenolic polymerization inhibitor include hydroquinone, p-methoxyphenol, 4-t-butylcatechol, 2-t-butylhydroquinone, and 2, 6-di-t-butyl-4-methylphenol.

The amount of the polymerization inhibitor to be used is not particularly limited, and may be, for example, 1 to 200ppm or 10 to 100ppm in terms of mass ratio relative to the (meth) acrylate compound having an isocyanate group represented by the formula (i').

By using a polymerization inhibitor, polymerization of the (meth) acryloyl group can be suppressed to carry out the reaction of the second stage even when the reaction temperature is raised to about 60 to 80 ℃.

As the organic solvent, various solvents commonly used in such a reaction can be used, and examples thereof include Tetrahydrofuran (THF), dioxane and dimethyl sulfoxide; amide solvents such as N, N-dimethylformamide, N-methyl-2-pyrrolidone, tetramethylurea, hexamethylphosphoramide, N, N-dimethylacetamide, 3-methoxy-N, N-dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide, N-methyl-2-piperidone, N, N '-dimethylethyleneurea, N, N, N', N '-tetramethylmalonamide, N-methylcaprolactam, N-acetylpyrrolidine, N, N-diethylacetamide, N-ethyl-2-pyrrolidone, N, N-dimethylpropionamide, N, N-dimethylisobutyl amide, N-methylformamide, N, N' -dimethylpropyleneurea, and mixed solvents thereof.

Among them, N-dimethylformamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, N-dimethylacetamide, 3-methoxy-N, N-dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide and a mixture thereof are preferable, and N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 3-methoxy-N, N-dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide are particularly preferable.

In the reaction in the first stage of the above-mentioned scheme 1 or scheme 2, various bases generally used at the time of polymerization or after polymerization may be added.

Specific examples of the base include potassium carbonate, potassium hydroxide, sodium carbonate, sodium hydroxide, sodium hydrogencarbonate, sodium ethoxide, sodium acetate, lithium carbonate, lithium hydroxide, lithium oxide, potassium acetate, magnesium oxide, calcium oxide, barium hydroxide, trilithium phosphate, trisodium phosphate, tripotassium phosphate, cesium fluoride, aluminum oxide, ammonia, N-propylamine, trimethylamine, triethylamine, diisopropylamine, diisopropylethylamine, N-methylpiperidine, 2, 6-tetramethyl-N-methylpiperidine, pyridine, 4-dimethylaminopyridine, N-methylmorpholine, 2-aminoethanol, ethyldiethanolamine, diethylaminoethanol, and the like.

The amount of the base to be added is preferably 1 to 100 equivalents, more preferably 1 to 10 equivalents, based on 1 equivalent of the triazine compound (29). The alkali may be used in the form of an aqueous solution.

It is preferable that the raw material component does not remain in the obtained polymer, but a part of the raw material may remain as long as the effect of the present invention is not impaired.

After the completion of the reaction, the product can be easily purified by a reprecipitation method or the like.

As a capping method using an amino compound having a crosslinking group, a known method may be used.

In this case, the amount of the capping agent to be used is preferably about 0.05 to 10 equivalents, more preferably 0.1 to 5 equivalents, and even more preferably 0.5 to 2 equivalents, based on 1 equivalent of halogen atoms from the residual triazine compound not used in the polymerization reaction.

The reaction solvent or the reaction temperature may be the same as that described in the first-stage reaction of the above-mentioned scheme 1 or scheme 2, and the blocking agent may be added simultaneously with the aryldiamino compound (30) or (32).

It is to be noted that an unsubstituted arylamino compound having no crosslinking group may be used and two or more groups may be used for capping. Examples of the aryl group of the unsubstituted arylamino compound include the same groups as those described above.

Specific examples of the unsubstituted arylamino group include, but are not limited to, a group represented by the following formula (33).

Chemical formula 47

* Representing a chemical bond.

The unsubstituted arylamino group can be introduced using a corresponding unsubstituted arylamino compound.

Specific examples of the unsubstituted arylamino compound include aniline and the like.

In addition, when an unsubstituted arylamino group is introduced, the ratio of the amino compound having a crosslinking group to the unsubstituted arylamino compound is preferably 0.1 to 1.0 mol, more preferably 0.1 to 0.5 mol, still more preferably 0.1 to 0.3 mol, based on 1 mol of the amino compound having a crosslinking group, from the viewpoint of exhibiting good balance between solubility in an organic solvent and yellowing resistance.

In addition, in addition to the end-capping using an amino compound having a crosslinking group, an arylamino compound having a specific heteroatom-containing substituent may be used for end-capping. The refractive index of the resulting film can be further increased by capping with an arylamino group having a specific heteroatom-containing substituent.

Specific heteroatom-containing substituents include cyano, alkylamino, arylamino, nitro, alkylthiol, arylthiol, alkoxycarbonyl, and alkoxycarbonyloxy.

Examples of the arylamino group having a specific heteroatom-containing substituent include a group represented by the following formula (34).

Chemical formula 48

Wherein Y is a "specific heteroatom-containing substituent" and represents cyano, alkylamino, arylamino, nitro, alkylthiol, arylthiol, alkoxycarbonyl or alkoxycarbonyloxy. m represents an integer of 1 to 5. When m is 2 or more, Y may be the same or different. * Representing a chemical bond.

Wherein Y is preferably cyano or nitro. m is preferably 1. When m is 1, Y is preferably substituted in the para or meta position.

In addition, when an arylamino group having a specific heteroatom-containing substituent is introduced, the ratio of the amino compound having a crosslinking group and the arylamino compound having a specific heteroatom-containing substituent is preferably 0.1 to 1.0 mol, more preferably 0.1 to 0.5 mol, and even more preferably 0.1 to 0.3 mol, relative to 1 mol of the amino compound having a crosslinking group, from the viewpoint of exhibiting solvent resistance and high refraction in balance.

The content of the triazine ring-containing polymer in the solvent-free composition is not particularly limited, but is preferably 0.1 to 50% by mass, more preferably 1 to 10% by mass.

(2) Crosslinking agent

The crosslinking agent is not particularly limited as long as it is a compound having 2 or more substituents capable of reacting with the crosslinking group of the triazine ring-containing polymer.

Examples of such a compound include melamine compounds (e.g., a phenolic compound, an aminoplast compound, etc.) having a substituent that forms a crosslink such as a hydroxymethyl group or a methoxymethyl group, substituted urea compounds, compounds having a substituent that forms a crosslink such as an epoxy group or an oxetane group (e.g., a polyfunctional epoxy compound, a polyfunctional oxetane compound, etc.), compounds having a blocked isocyanate group, compounds having an acid anhydride group, compounds having a (meth) acryloyl group, etc., and from the viewpoints of heat resistance and storage stability, compounds having an epoxy group, a blocked isocyanate group, and a (meth) acryloyl group are preferable, and compounds having a blocked isocyanate group are particularly preferable, or polyfunctional epoxy compounds and/or polyfunctional (meth) acryloyl compounds that can provide a composition that can be photo-cured without using an initiator.

The polyfunctional epoxy compound is not particularly limited as long as it has two or more epoxy groups in one molecule.

Specific examples thereof include tris (2, 3-epoxypropyl) isocyanurate, 1, 4-butanediol diglycidyl ether, 1, 2-epoxy-4- (epoxyethyl) cyclohexane, glycerol triglycidyl ether, diethylene glycol diglycidyl ether, 2, 6-diglycidyl phenyl glycidyl ether, 1, 3-tris [ p- (2, 3-epoxypropoxy) phenyl ] propane, diglycidyl ester of 1, 2-cyclohexanedicarboxylate, 4' -methylenebis (N, N-diglycidyl aniline), 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexane carboxylate, trimethylolethane triglycidyl ether, bisphenol-A-diglycidyl ether, pentaerythritol polyglycidyl ether and the like.

As commercial products, YH-434 and YH434L (manufactured by Nitro chemical materials Co., ltd.) as epoxy resins having at least two epoxy groups can be used; epolate GT-401, epolate GT-403, epolate GT-301, epolate GT-302, CELLOXIDE 2021, CELLOXIDE 3000 (manufactured by celluloid corporation) as epoxy resins having cyclohexene oxide structure; jER1001, jER1002, jER1003, jER1004, jER1007, jER1009, jER1010, jER828 (manufactured by Mitsubishi chemical corporation) as bisphenol A type epoxy resins; jER807 (mitsubishi chemical company, inc.) as bisphenol F type epoxy resin; jER152, jER154 (above, mitsubishi chemical company), EPPN 201, EPPN 202 (above, manufactured by japan chemical company, inc.) as phenol novolac type epoxy resins; EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, EOCN-1027 (above, manufactured by Mitsubishi chemical Co., ltd.), jER180S75 (manufactured by Mitsubishi chemical Co., ltd.) as cresol novolac type epoxy resins; DENACOL EX-252 (manufactured by Daikin chemical Co., ltd. (Nagase ChemteX Corporation)), CY175, CY177, CY179 (manufactured by Siba geji Corporation (manufactured by CIBA-GEIGY A.G) above), araldite CY-182, araldite CY-192, araldite CY-184 (manufactured by Siba geji Corporation (manufactured by CIBA-GEIGY A.G) above), EPICLON 200, EPICLON 400 (manufactured by Di Sheng Co., ltd. (manufactured by DIC Corporation) above), jER871, jER872 (manufactured by Mitsubishi chemical Co., ltd., above), ED-5661, ED-5662 (manufactured by Sernis paint Co., ltd. (Celanese Corporation) above); DENACOL EX-611, DENACOL EX-612, DENACOL EX-614, DENACOL EX-622, DENACOL EX-411, DENACOL EX-512, DENACOL EX-522, DENACOL EX-421, DENACOL EX-313, DENACOL EX-314, DENACOL EX-321 (manufactured by Chang Chemie Co., ltd. (Nagase ChemteX Corporation)) and the like as aliphatic polyglycidyl ethers.

The polyfunctional (meth) acryl compound is not particularly limited as long as it has two or more (meth) acryl groups in one molecule.

Specific examples thereof include ethylene glycol diacrylate, ethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, ethoxylated bisphenol a diacrylate, ethoxylated bisphenol a dimethacrylate, ethoxylated trimethylolpropane triacrylate, ethoxylated trimethylolpropane trimethacrylate, ethoxylated glycerol triacrylate, ethoxylated glycerol trimethacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetramethacrylate, ethoxylated dipentaerythritol hexaacrylate, polyglycerol monoethylene oxide polyacrylate, polyglycerol polyethylene glycol polyacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tricyclodecane dimethanol diacrylate, tricyclodecane dimethanol dimethacrylate, 1, 6-hexanediol diacrylate, 1, 6-hexanediol dimethacrylate, and polybasic acid modified acrylic acid oligomer.

Further, the polyfunctional (meth) acryl compound is commercially available, and as a specific example thereof, examples thereof include NK ester A-200, NK ester A-400, NK ester A-600, NK ester A-1000, NK ester A-9300 (tris (2-acryloyloxyethyl) isocyanurate), NK ester A-9300-1CL, NK ester A-TMPT, NK ester UA-53 3996, NK ester UA-53:1: G, NK, ester 2G, NK, ester 3G, NK, ester 4G, NK, ester 9G, NK, ester 14G, NK, ester 23, G, NK, ABE-300, NK ester A-BPE-4, NK ester A-BPE-6, NK ester A-BPE-10, and NK ester A-BPE-20, NK ester A-BPE-30, NK ester BPE-80N, NK, NK ester BPE-100N, NK, NK ester BPE-200, NK ester BPE-500, NK ester BPE-900, NK ester BPE-1300N, NK ester A-GLY-3E, NK ester A-GLY-9E, NK ester A-GLY-20E, NK ester A-TMPT-3EO, NK ester A-TMPT-9EO, NK ester AT-20E, NK ester ATM-4E, NK, ATM-35E, APG-100, APG-200 (above, KAYARAD (registered trademark) DPEA-12, KAYARAD PEG DA, KAYARAD THE-330, KAYARAD RP-1040 (above, manufactured by japan chemical Co., ltd.), aronix M-210, M-350 (above, manufactured by eastern synthetic Co., ltd.), KAYARAD (registered trademark) DPHA, KAYARAD NPGDA, KAYARAD PET30 (above, manufactured by japan chemical Co., ltd.), NK esters A-DPH, NK esters A-TMPT, NK esters A-DCP, NK esters A-HD-N, NK ester TMPT, NK esters DCP, NK esters NPG, NK esters HD-N (above, manufactured by Nippon chemical Co., ltd.), NK OLIGO U-15HA (manufactured by Nippon chemical Co., ltd.), NK polymers Vanarsin GH-1203 (manufactured by Nippon chemical Co., ltd.), DN-0075 (manufactured by Nippon chemical Co., ltd.), and the like.

The polyacid-modified acrylic oligomer is also commercially available, and specific examples thereof include Aronix M-510, 520 (above, manufactured by Toyama Synthesis Co., ltd.).

The compound having an acid anhydride group is not particularly limited as long as it is a carboxylic anhydride obtained by dehydrating and condensing two molecules of carboxylic acid, and specific examples thereof include compounds having one acid anhydride group in a molecule such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, maleic anhydride, succinic anhydride, octylsuccinic anhydride, dodecenylsuccinic anhydride, and the like; and compounds having two anhydride groups in the molecule, such as 1,2,3, 4-cyclobutane tetracarboxylic dianhydride, pyromellitic anhydride, 3, 4-dicarboxyl-1, 2,3, 4-tetrahydro-1-naphthalene succinic anhydride, bicyclo [3.3.0] octane-2, 4,6, 8-tetracarboxylic dianhydride, 5- (2, 5-dioxotetrahydro-3-furyl) -3-methyl-3-cyclohexene-1, 2-dicarboxylic anhydride, 1,2,3, 4-butane tetracarboxylic dianhydride, 3', 4' -benzophenone tetracarboxylic dianhydride, 3', 4' -biphenyl tetracarboxylic dianhydride, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride, and 1, 3-dimethyl-1, 2,3, 4-cyclobutane tetracarboxylic dianhydride.

The blocked isocyanate group-containing compound is not particularly limited as long as it is a blocked isocyanate group having two or more isocyanate groups (-NCO) in one molecule and is blocked with an appropriate protecting group, and when exposed to a high temperature at the time of heat curing, the protecting group (blocked portion) is thermally dissociated and removed, and the generated isocyanate group and the crosslinking group (e.g., hydroxyl group-containing group) of the triazine ring-containing polymer of the present invention undergo a crosslinking reaction, and examples thereof include compounds having two or more groups represented by the following formula (it is necessary that these groups may be the same or different).

Chemical formula 49

(wherein R is _b An organic group representing a capping moiety. )

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

Examples of the compound having two or more isocyanate groups in one molecule include isophorone diisocyanate, 1, 6-hexamethylene diisocyanate, methylenebis (4-cyclohexyl isocyanate), polyisocyanates of trimethylhexamethylene diisocyanate, dimers and trimers of these, and reactants of these with diols, triols, diamines or triamines, and the like.

Examples of the blocking agent include alcohols such as methanol, ethanol, isopropanol, N-butanol, 2-ethoxyhexanol, 2-N, N-dimethylaminoethanol, 2-ethoxyethanol, and cyclohexanol; phenols such as phenol, o-nitrophenol, p-chlorophenol, o-cresol, m-cresol, and p-cresol; lactams such as epsilon-caprolactam, oximes such as acetone oxime, methyl ethyl ketoxime, methyl isobutyl ketoxime, cyclohexanone oxime, acetophenone oxime and benzophenone oxime; pyrazoles such as pyrazole, 3, 5-dimethylpyrazole and 3-methylpyrazole; thiols such as dodecyl mercaptan and phenyl mercaptan.

As specific examples of the blocked isocyanate group-containing compounds, there may be mentioned TAKENATE (registered trademark) B-830, B-815N, B-842N, B-870N, B-874N, B-882N, B-7005, B-7030, B-7075, B-5010 (above, manufactured by Mitsui chemical Co., ltd.), duranate (registered trademark) 17B-60PX, duranate TPA-B80E, duranate MF-B60X, duranate MF-K60X, duranate E402-B80T (above, manufactured by Asahi Kagaku chemical Co., ltd.), karenz MOI-BM (above, manufactured by Showa electric Co., ltd.), TRIXENE (registered trademark) BI-7950, BI-7951, BI-7960, BI-7963, BI-7982, BI-7991, BI-7992 (manufactured by Baston chemical Co., ltd.), and the like.

The aminoplast compound is not particularly limited as long as it has two or more methoxymethylene groups in one molecule, and examples thereof include CYMEL series such as hexamethoxymethyl melamine CYMEL (registered trademark) 303, tetrabutoxymethyl glycoluril CYMEL1170, tetramethoxymethyl benzoguanamine CYMEL1123 (above, manufactured by japan cyanogen technical company (Cytec industries Japan Ltd)), and the like; NIKALAC (registered trademark) MW-30HM, NIKALAC MW-390, NIKALAC MW-100LM, NIKALAC MX-750LM as methylated melamine resin; and NIKALAC-series melamine compounds such as NIKALAC MX-270, NIKALAC MX-280, and NIKALAC MX-290 (manufactured by Sanand chemical Co., ltd.).

The oxetane compound is not particularly limited as long as it has two or more oxetanes in one molecule, and examples thereof include oxetane-containing OXT-221, OX-SQ-H, OX-SC (manufactured by Toyama Co., ltd.).

The phenolic plastic compound has two or more hydroxymethylene groups in one molecule, and undergoes a crosslinking reaction with the crosslinking group of the triazine ring-containing polymer of the present invention by a dehydration condensation reaction when exposed to a high temperature at the time of thermal curing.

Examples of the phenolic plastic 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-bis (4-hydroxy-3, 5-dihydroxymethylphenyl) propane, bis (3-formyl-4-hydroxyphenyl) methane, bis (4-hydroxy-2, 5-dimethylphenyl) formylmethane, α -bis (4-hydroxy-2, 5-dimethylphenyl) -4-formyltoluene, and the like.

The phenolic compounds are also commercially available, and specific examples thereof include 26DMPC, 46DMOC, DM-BIPC-F, DM-BIOC-F, TM-BIP-A, BISA-F, BI X-DF, BI25X-TPA (manufactured by Asahi organic materials Co., ltd.), and the like.

Among them, from the viewpoint of being able to suppress the decrease in refractive index due to the incorporation of the crosslinking agent and to rapidly carry out the curing reaction, a polyfunctional (meth) acryl compound is preferable, and among them, a polyfunctional (meth) acryl compound having an isocyanuric acid skeleton described below is more preferable because of excellent compatibility with the triazine ring-containing polymer.

Examples of the polyfunctional (meth) acryl compound having such a skeleton include NK ester A-9300 and NK ester A-9300-1CL (all manufactured by Xinzhou chemical Co., ltd.).

Chemical formula 50

(wherein R is ¹¹¹ ～R ¹¹³ Independently of one another, are monovalent organic radicals having at least one (meth) acryloyl group at the end. )

In addition, from the viewpoint of further improving the curing speed and improving the solvent resistance, acid resistance and alkali resistance of the obtained cured film, it is preferable to use a polyfunctional (meth) acryl compound (hereinafter, referred to as a low-viscosity crosslinking agent) which is liquid at 25 ℃ and has a viscosity of 5000mpa·s or less, preferably 1 to 3000mpa·s, more preferably 1 to 1000mpa·s, still more preferably 1 to 500mpa·s, alone or in combination with the polyfunctional (meth) acryl compound having an isocyanuric acid skeleton.

Such a low-viscosity crosslinking agent is also commercially available, and examples thereof include crosslinking agents having relatively long chain lengths between (meth) acryloyl groups such as NK ester A-GLY-3E (85 mPas, 25 ℃) NK ester A-GLY-9E (95 mPas, 25 ℃), NK ester A-GLY-20E (200 mPas, 25 ℃), NK ester A-TMPT-3EO (60 mPas, 25 ℃), NK ester A-TMPT-9EO, NK ester ATM-4E (150 mPas, 25 ℃), NK ester ATM-35E (350 mPas, 25 ℃) (more than, manufactured by New Zhou chemical Co., ltd.).

In view of improving the alkali resistance of the obtained cured film, it is preferable to use at least one of NK ester A-GLY-20E (manufactured by Xinzhou chemical Co., ltd.) and NK ester ATM-35E (manufactured by Xinzhou chemical Co., ltd.) in combination with the above-mentioned polyfunctional (meth) acryl compound having an isocyanuric acid skeleton.

In addition, when a film comprising the triazine ring-containing polymer of the present invention is laminated on a protective film such as a PET or polyolefin film and light irradiation is performed through the protective film, good curability can be obtained without being hindered by oxygen even in the film laminated film. In this case, since the protective film needs to be peeled off after curing, it is preferable to use a polybasic acid-modified acrylic oligomer that provides a film having good peelability.

The above-mentioned crosslinking agents may be used alone or in combination of two or more.

The content of the crosslinking agent in the solvent-free composition is preferably 1 to 500 parts by mass, and is preferably 50 to 300 parts by mass, more preferably 100 to 150 parts by mass, in view of controlling the refractive index and solvent resistance, relative to 100 parts by mass of the triazine ring-containing polymer.

(3) Inorganic fine particles

By incorporating inorganic fine particles in the solvent-free composition containing the triazine ring-containing polymer, the viscosity can be reduced while maintaining a high refractive index. Since the solvent-free composition does not contain an organic solvent, the viscosity is generally easily increased, and the solvent-free composition of the present invention can reduce the viscosity. Therefore, the solvent-free composition of the present invention can be applied by a coating method requiring a relatively low viscosity, such as a slit coating method or an inkjet method.

In addition, even if inorganic fine particles are contained in the solvent-free composition containing the triazine ring-containing polymer, the low haze can be maintained in the obtained cured film.

As the inorganic fine particles, for example, oxides, sulfides or nitrides of 1 or 2 or more metals selected from the group consisting of Be, al, si, ti, V, fe, cu, zn, Y, zr, nb, mo, in, sn, sb, ta, W, pb, bi and Ce are included, and metal oxides containing them are particularly preferable. The inorganic fine particles may be used alone or in combination of 2 or more kinds.

Specific examples of the metal oxide include, for example, 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 Etc.

In addition, it is also effective to use a plurality of metal oxides as the composite oxide. The composite oxide is a mixture of 2 or more inorganic oxides at the stage of producing fine particles. For example, tiO may be mentioned ₂ With ZrO ₂ Composite oxide of (2) TiO ₂ With ZrO ₂ With SnO ₂ Composite oxide of (2), zrO ₂ With SnO ₂ And the like.

Further, the metal may be a compound of the above-mentioned metal. For example, znSb ₂ O ₆ 、BaTiO ₃ 、SrTiO ₃ 、SrSnO ₃ Etc. These compounds may be used alone or in combination of two or more kinds, or may be further used in combination with the above-mentioned oxides.

The inorganic fine particles may be, for example, third metal oxide particles (C) obtained by coating the surfaces of the first metal oxide particles (a) with the second metal oxide particles (B).

The first metal oxide particles (a) can be produced by a known method, for example, an ion exchange method, a peptization method, a hydrolysis method, or a reaction method. As an example of the ion exchange method, a method of treating an acid salt of at least one metal selected from the group consisting of Ti, fe, cu, zn, Y, zr, nb, mo, in, sn, sb, ta, W, pb, bi and Ce with a hydrogen type ion exchange resin or a method of treating a basic salt of the above metal with a hydroxyl type anion exchange resin. Examples of the peptization method include a method in which a gel obtained by neutralizing an acid salt of the metal with a base or neutralizing a basic salt of the metal with an acid is washed and peptized with an acid or a base. As an example of the hydrolysis method, a method of hydrolyzing the alkoxide of the metal or a method of hydrolyzing the basic salt of the metal under heating and then removing the unnecessary acid is mentioned. Examples of the reaction method include a method of reacting the powder of the metal with an acid.

The first metal oxide particles (a) are preferably oxides of metals having a valence of 2 to 6, more preferably oxides of at least one metal selected from the group consisting of Ti, fe, cu, zn, Y, zr, nb, mo, in, sn, sb, ta, W, pb, bi, ba, al, sr, hf and Ce. Examples of the form of the metal oxide include TiO ₂ 、Fe ₂ O ₃ 、CuO、ZnO、Y ₂ O ₃ 、ZrO ₂ 、Nb ₂ O ₅ 、MoO ₃ 、In ₂ O ₃ 、SnO ₂ 、Sb ₂ O ₅ 、Ta ₂ O ₅ 、WO ₃ 、PbO、Bi ₂ O ₃ 、BaO、Al ₂ O ₃ 、SrO、HfO ₂ 、CeO ₂ Etc. These metal oxides may be used singly or in combination of two or more. Examples of the method for combining the metal oxides include a method of mixing several of the metal oxides, a method of compounding the metal oxides, and a method of solid-dissolving the metal oxides at an atomic level.

Examples of the combination of the metal oxides include SnO ₂ Particles and TiO ₂ SnO in which particles are chemically bonded to each other at their interfaces to be composited ₂ -TiO ₂ Composite particles, snO ₂ Particles and WO ₃ Particles at their interfaceSnO compounded by chemical bonding ₂ -WO ₃ Composite particles, snO ₂ Particles and ZrO ₂ SnO in which particles are chemically bonded to each other at their interfaces to be composited ₂ -ZrO ₂ Composite particles, tiO ₂ With ZrO ₂ With SnO ₂ TiO obtained by forming solid solution at atomic level ₂ -ZrO ₂ -SnO ₂ Composite particles, and the like.

The first metal oxide particles (a) can be used as a compound by a combination of metal components, and examples thereof include ZnSb ₂ O ₆ 、InSbO ₄ 、ZnSnO ₃ Tin doped indium oxide (ITO), in ₂ O ₃ -ZnO、BaTiO ₃ 、SrTiO ₃ Aluminum-doped zinc oxide, and the like.

When the first metal oxide particles (A) contain TiO ₂ In the case of using TiO as the material contained in the particles ₂ Any of anatase type, rutile type, anatase-rutile mixed type, and brookite type crystal structures may be used, but the rutile type is preferably contained in view of refractive index and transparency of the obtained film.

Further, from the viewpoint of suppressing the activity (e.g., photocatalytic performance) thereof, the first metal oxide particles (a) may have a thin film layer formed of a metal oxide such as zirconia, silica, or alumina formed on the surface thereof. The thin film layer can be formed, for example, by adding a zirconium compound to an aqueous dispersion of the first metal oxide particles (a) and heating the mixture at 40 to 200 ℃. Examples of the zirconium compound include zirconium oxychloride, zirconium chloride, zirconium hydroxide, zirconium sulfate, zirconium nitrate, zirconyl nitrate, zirconium acetate, zirconium carbonate, zirconium ammonium carbonate, zirconium potassium carbonate, zirconium ethylhexanoate, zirconium stearate, zirconium octoate, zirconium ethoxide, zirconium n-propoxide, zirconium isopropoxide, zirconium n-butoxide, zirconium isopropoxide, zirconium tert-butoxide, zirconium tetra-acetylacetonate, and the like, with zirconium oxychloride being preferred. The amount of the zirconia compound used is preferably 3 to 50 mass% based on the amount of the first metal oxide particles (a) used.

The primary particle diameter (as observed by a transmission electron microscope) of the first metal oxide particles (a) is preferably 2 to 60nm, more preferably 2 to 30nm, and particularly preferably 2 to 20nm, from the viewpoints of dispersion stability, refractive index of the obtained film, and transparency.

The dynamic light scattering method particle diameter (based on the dynamic light scattering method) as the secondary particle diameter of the first metal oxide particles (a) is preferably 5 to 100nm, more preferably 5 to 50nm, particularly preferably 5 to 30nm, from the viewpoints of dispersion stability, refractive index of the obtained film, and transparency.

The first metal oxide particles (a) can be synthesized, for example, according to the method described in international publication No. 2013/081136.

The second metal oxide particles (B) are preferably oxide particles of at least one metal selected from the group consisting of Si, al, sn, zr, mo, sb and W. The second metal oxide particles (B) may be, for example, siO as a form of metal oxide ₂ 、Al ₂ O ₃ 、SnO ₂ 、ZrO ₂ 、MoO ₃ 、Sb ₂ O ₅ 、WO ₃ Etc. Further, one kind of these metal oxides may be used alone, or two or more kinds may be used in combination. Examples of the method for combining the metal oxides include a method of mixing several of the metal oxides, a method of compounding the metal oxides, and a method of solid-dissolving the metal oxides at an atomic level.

Specific examples of the second metal oxide particles (B) include SnO ₂ Particles and WO ₃ SnO in which particles are chemically bonded to each other at their interfaces to be composited ₂ -WO ₃ Composite particles, snO ₂ Particles and SiO ₂ SnO in which particles are chemically bonded to each other at their interfaces to be composited ₂ -SiO ₂ Composite particles, snO ₂ Particles and WO ₃ Particles and SiO ₂ SnO in which particles are chemically bonded to each other at their interfaces to be composited ₂ -WO ₃ -SiO ₂ Composite particles, snO ₂ Particles and MoO ₃ Particles and SiO ₂ SnO in which particles are chemically bonded to each other at their interfaces to be composited ₂ -MoO ₃ -SiO ₂ Composite particles, sb ₂ O ₅ Particles and SiO ₂ Sb in which particles are chemically bonded to and composited with each other at the interface ₂ O ₅ -SiO ₂ Composite particles, and the like.

When a plurality of metal oxides are used as the second metal oxide particles (B), the proportion (mass ratio) of the metal oxides contained is not particularly limited, for example, in SnO ₂ -SiO ₂ In the composite particles, siO ₂ /SnO ₂ The mass ratio of (B) is preferably 0.1 to 5, and Sb ₂ O ₅ -SiO ₂ In the composite particles, sb ₂ O ₅ /SiO ₂ The mass ratio of (2) is preferably 0.1 to 5.

The second metal oxide particles (B) can be produced by a known method, for example, an ion exchange method or an oxidation method. Examples of the ion exchange method include a method of treating an acid salt of the metal with a hydrogen ion exchange resin. Examples of the oxidation method include a method of reacting a powder of the metal or the oxide of the metal with hydrogen peroxide.

The primary particle diameter (as observed by a transmission electron microscope) of the second metal oxide particles (B) is preferably 5nm or less, more preferably 1 to 5nm, from the viewpoints of dispersion stability, refractive index of the obtained film, and transparency.

The third metal oxide particles (C) are metal oxide particles obtained by coating the surfaces of the first metal oxide particles (a) with the second metal oxide particles (B). Examples of the production method include the following first method and second method.

The first method is a method in which an aqueous dispersion containing first metal oxide particles (a) and an aqueous dispersion containing second metal oxide particles (B) are mixed so that the mass ratio (metal oxide equivalent) represented by (B)/(a) becomes 0.05 to 0.5, and then the aqueous dispersion is heated. For example, an aqueous dispersion containing the first metal oxide particles (A) and Sb-containing particles as the second metal oxide particles (B) ₂ O ₅ -SiO ₂ Composite particles (Sb) ₂ O ₅ /SiO ₂ The aqueous dispersion of =0.1 to 5) is mixed so that the mass ratio reaches 0.05 to 0.5, and the aqueous dispersion obtained by the mixing is heated at 70 to 350 ℃ to obtain the Sb-based aqueous dispersion ₂ O ₅ -SiO ₂ An aqueous dispersion of third metal oxide particles (C) in which the composite particles coat the surfaces of the first metal oxide particles (A).

The second method comprises mixing an aqueous dispersion containing first metal oxide particles (A) with water-soluble basic tin oxide salt and basic silicon oxide salt as second metal oxide particles (B) to obtain a mixture of SnO ₂ /SiO ₂ The mixture is mixed so that the mass ratio (metal oxide conversion value) is 0.1 to 5, and then cation-exchanged with SnO obtained by removing alkali metal ions ₂ -SiO ₂ And a method in which the aqueous dispersion of the composite particles is mixed so that the mass ratio (metal oxide equivalent) represented by (B)/(A) becomes 0.05 to 0.5, and then the aqueous dispersion obtained by the mixing is heated. The aqueous solution of the water-soluble alkali salt used in the second method can preferably be an aqueous solution of a sodium salt. For example, snO obtained by mixing an aqueous dispersion containing first metal oxide particles (A) with an aqueous solution of sodium stannate and sodium silicate as second metal oxide particles (B) and then cation-exchanging the mixture ₂ -SiO ₂ The aqueous dispersion of the composite particles is mixed so that the mass ratio thereof reaches 0.05 to 0.5, and the aqueous dispersion is heated at 70 to 350 ℃ to obtain a mixture containing the first metal oxide particles (A) as nuclei and SnO ₂ -SiO ₂ An aqueous dispersion of third metal oxide particles (C) in which the surfaces of the second metal oxide particles (B) are coated with the composite particles.

The temperature at which the first metal oxide particles (a) and the second metal oxide particles (B) are mixed is usually 1 to 100 ℃, preferably 20 to 60 ℃. The heating temperature after mixing is preferably 70 to 350 ℃, more preferably 70 to 150 ℃. The heating time after mixing is usually 10 minutes to 5 hours, preferably 30 minutes to 4 hours.

The aqueous dispersion of the third metal oxide particles (C) may contain any component. In particular, by containing the oxo carboxylic acid, the dispersibility and other properties of the third metal oxide particles (C) can be further improved. Examples of the oxo carboxylic acid include lactic acid, tartaric acid, citric acid, gluconic acid, malic acid, and glycolic acid. The content of the oxo carboxylic acid is preferably about 30 mass% or less with respect to the total metal oxides of the third metal oxide particles (C).

The dispersion of the third metal oxide particles (C) may contain an alkali component. Examples of the alkali component include alkali metal hydroxides such as Li, na, K, rb, cs; ammonia; primary, secondary and tertiary alkylamines such as ethylamine, isopropylamine, n-propylamine, n-butylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, triethylamine, tripropylamine, tributylamine, triisobutylamine, tripentylamine (tri-n-pentylamine), tri-n-hexylamine, tri-n-octylamine, dimethylpropylamine, dimethylbutylamine, dimethylhexylamine and the like; aralkylamines such as benzylamine and dimethylbenzylamine; alicyclic amines such as piperidine; alkanolamines such as monoethanolamine and triethanolamine; quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and the like. These may be used alone or in combination of 1 or more than 2. The content of the alkali component is preferably about 30 mass% or less with respect to the total metal oxides of the third metal oxide particles (C). These base components can be used in combination with the above-mentioned oxo carboxylic acid.

When it is desired to further increase the concentration of the aqueous dispersion of the third metal oxide particles (C), the aqueous dispersion can be concentrated to about 65 mass% at the maximum by a conventional method. Examples of the method include an evaporation method and an ultrafiltration method. In addition, when the pH of the aqueous dispersion is to be adjusted, the above-mentioned alkali metal hydroxide, amine, quaternary ammonium salt, oxo carboxylic acid, etc. may be added.

The concentration of the total metal oxide in the solvent dispersion of the third metal oxide particles (C) is preferably 10 to 60 mass%, more preferably 20 to 50 mass%.

The aqueous medium is replaced with a hydrophilic organic solvent with respect to the aqueous dispersion of the third metal oxide particles (C), thereby obtaining an organic solvent dispersion of the third metal oxide particles (C). The substitution can be carried out by a general method such as distillation or ultrafiltration. Examples of the hydrophilic organic solvent include lower alcohols such as methanol, ethanol, isopropanol and 1-propanol, ethers such as propylene glycol monomethyl ether, linear amides such as dimethylformamide and N, N-dimethylacetamide, cyclic amides such as N-methyl-2-pyrrolidone, ethylcellosolve and glycols such as ethylene glycol.

The primary particle diameter (as observed by a transmission electron microscope) of the third metal oxide particles (C) is preferably 20nm or less from the viewpoints of dispersion stability, refractive index of the obtained film, and transparency.

From the viewpoints of dispersion stability, refractive index of the obtained film, and transparency, the dynamic light scattering method particle diameter (based on dynamic light scattering method) as the secondary particle diameter of the third metal oxide particles (C) is preferably 2 to 100nm.

The inorganic fine particles used in the present invention may be surface-modified inorganic fine particles. The inorganic fine particles may have at least one of hydrophilic groups and crosslinkable groups on the surface.

The inorganic fine particles having at least one of a hydrophilic group and a crosslinkable group on the surface (hereinafter, sometimes referred to as "surface-modified inorganic fine particles") are obtained, for example, by using the inorganic fine particles as core particles and modifying the surfaces of the core particles with at least one of an organosilicon compound having a hydrophilic group and an organosilicon compound having a crosslinkable group.

By using the surface-modified inorganic fine particles as the inorganic fine particles, dispersion stability in the resin can be improved, and haze of the cured film can be further suppressed.

The organosilicon compound has a hydrolyzable group which generates a Si-OH group by hydrolysis. Examples of the hydrolyzable group include an alkoxy group bonded to a silicon atom, an acetoxy group bonded to a silicon atom, and the like. The number of the hydrolyzable groups in the organosilicon compound is not particularly limited, and examples thereof include 1 to 3.

Examples of the hydrophilic group include polyether groups such as polyoxyethylene group, polyoxypropylene group and polyoxybutylene group.

Examples of the organosilicon compound having a hydrophilic group include [ methoxy (polyethylene oxy) n-propyl ] trimethoxysilane, [ methoxy (polyethylene oxy) n-propyl ] triethoxysilane, [ methoxy (polyethylene oxy) n-propyl ] tripropoxysilane, [ methoxy (polyethylene oxy) n-propyl ] triacetoxysilane, [ methoxy (polypropylene oxy) n-propyl ] trimethoxysilane, [ methoxy (polypropylene oxy) n-propyl ] triethoxysilane, [ methoxy (polypropylene oxy) n-propyl ] tripropoxysilane, [ methoxy (polypropylene oxy) n-propyl ] triacetoxysilane, [ methoxy (polybutylene oxy) n-propyl ] trimethoxysilane, [ methoxy (polybutylene oxy) n-propyl ] tripropoxysilane, [ methoxy (polybutylene oxy) n-propyl ] triacetoxysilane, [ methoxy (polyethylene oxy) n-propyl ] dimethoxymethylsilane, [ methoxy (polyethylene oxy) n-propyl ] diethoxymethylsilane, [ methoxy (polyethylene oxy) n-propyl ] dimethylmethoxy (polypropylene) n-propyl ] dimethoxysilane, [ methoxy (polypropylene) n-propyl ] dimethoxymethylmethoxy (polyethylene oxy) n-propyl) propylmethoxy (methyl) silane [ methoxy (polypropyleneoxy) n-propyl ] diacetoxymethylsilane, [ methoxy (polybutyleneoxy) n-propyl ] dimethoxymethylsilane, [ methoxy (polybutyleneoxy) n-propyl ] diethoxymethylsilane, [ methoxy (polybutyleneoxy) n-propyl ] dipropoxymethylsilane, [ methoxy (polybutyleneoxy) n-propyl ] diacetoxymethylsilane, and the like.

The crosslinkable group is not particularly limited as long as it can react with a crosslinking agent to form a crosslinked structure, and examples thereof include a radical polymerizable group, an epoxy group, an amino group, and the like.

Examples of the radical polymerizable group include an allyl group, a (meth) acryloyloxy group, and the like.

Examples of the organosilicon compound having a radical polymerizable group include 3-acryloxypropyl methyl dimethoxy silane, 3-acryloxypropyl trimethoxy silane, 3-acryloxypropyl methyl diethoxy silane, 3-acryloxypropyl triethoxy silane, 3-methacryloxypropyl methyl dimethoxy silane, 3-methacryloxypropyl trimethoxy silane, 3-methacryloxypropyl methyl diethoxy silane, 3-methacryloxypropyl triethoxy silane, 8-methacryloxyoctyl trimethoxy silane, and 10-methacryloxydecyl trimethoxy silane.

Examples of the organosilicon compound having an epoxy group include 3-epoxypropoxypropyl trimethoxysilane and 8-epoxypropoxyoctyl trimethoxysilane.

Examples of the organosilicon compound having an amino group include N-2- (aminoethyl) -3-aminopropyl methyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, and 3-triethoxysilyl-N- (1, 3-dimethyl-butylene) propylamine.

These may be used alone or in combination of 1 or more than 2.

The amount of the organic silicon compound bonded to the surface of the core particle is not particularly limited, but is preferably 0.1 to 30% by mass, more preferably 1 to 15% by mass, based on the core particle.

From the viewpoints of dispersion stability, refractive index of the obtained film, and transparency, the primary particle diameter (as observed by a transmission electron microscope) of the inorganic fine particles or the surface-modified inorganic fine particles is preferably 20nm or less.

The secondary particle diameter (based on dynamic light scattering method) of the inorganic fine particles or the surface-modified inorganic fine particles is preferably 2 to 100nm, more preferably 5 to 50nm, and even more preferably 5 to 20nm, from the viewpoints of dispersion stability, refractive index of the obtained film, and transparency.

For example, the surface-modified inorganic fine particles can be obtained by adding a predetermined amount of an organosilicon compound to an aqueous dispersion of core particles or a hydrophilic organic solvent dispersion, hydrolyzing the organosilicon compound with a catalyst such as dilute hydrochloric acid, and binding the organosilicon compound to the surfaces of the core particles.

The aqueous dispersion of the core particles or the hydrophilic organic solvent dispersion may be further replaced with a hydrophobic organic solvent. The substitution method can be carried out by a general method such as distillation or ultrafiltration. Examples of the hydrophobic solvent include ketones such as methyl ethyl ketone and methyl isobutyl ketone, cyclic ketones such as cyclopentanone and cyclohexanone, and esters such as ethyl acetate and butyl acetate.

The organic solvent dispersion of the core particles may contain any component. In particular, by containing phosphoric acid, a phosphoric acid derivative, a phosphoric acid-based surfactant, an oxo carboxylic acid, or the like, dispersibility of the core particles can be further improved. Examples of the phosphoric acid derivative include phenylphosphonic acid and metal salts thereof. Examples of the phosphoric acid-based surfactant include Disperbyk (manufactured by pick chemical Co., ltd.), phospinol (manufactured by eastern chemical industries, japan), and Nikkol (manufactured by sun light chemical Co., ltd.). Examples of the oxo carboxylic acid include lactic acid, tartaric acid, citric acid, gluconic acid, malic acid, and glycolic acid. The content of these optional components is preferably about 30 mass% or less with respect to the entire metal oxide of the core particle.

In view of the dispersion stability, the concentration of the organic solvent dispersion of the core particles is preferably 10 to 60 mass%, more preferably 30 to 50 mass%.

The refractive index of the inorganic fine particles is not particularly limited, but is preferably 1.6 to 2.6, more preferably 1.8 to 2.6, from the viewpoint of not decreasing the refractive index of the obtained film. The refractive index of the inorganic fine particles can be measured, for example, by a method of measuring the refractive index of a solvent having a known refractive index or a liquid of the inorganic fine particles dispersed in a resin by an Abbe refractometer and extrapolating the refractive index from the value, or a method of measuring the refractive index of a film containing the inorganic fine particles or a cured product by an Abbe refractometer or a spectroscopic ellipsometer and extrapolating the refractive index from the value.

The content of the inorganic fine particles in the solvent-free composition may be controlled in accordance with the target refractive index, transmittance, heat resistance, and the like of the film to be produced, as long as the dispersibility thereof is not impaired in the final composition to be obtained. For example, the amount of the triazine ring-containing polymer may be in the range of 0.1 to 1000 parts by mass, preferably 1 to 500 parts by mass, and more preferably 10 to 300 parts by mass, from the viewpoint of maintaining the film quality and obtaining a stable refractive index and solvent resistance.

(4) Reactive diluents

Preferably, the solventless composition of the present invention contains a reactive diluent.

The reactive diluent is a low molecular compound having a reactive group reactive with at least one of a crosslinking group of the triazine ring-containing polymer and a crosslinking agent, and particularly a substance having a low viscosity in a liquid state at ordinary temperature also has a viscosity adjusting function, and thus can be used instead of an organic solvent.

As such a reactive diluent, a compound having one radical polymerizable group or a compound having one cation polymerizable group such as an epoxy group, an oxetane group, a vinyl ether group is generally used.

The molecular weight of the reactive diluent is not particularly limited, and examples thereof include 200 or less.

The reactive diluent is preferably a compound having one radical polymerizable group, and more preferably at least one compound of the following formulae (a) and (B) from the viewpoint of excellent solubility of the triazine ring-containing polymer.

Chemical formula 51

In the formula (A), R ²⁰¹ And R is ²⁰³ Independently of one another, represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a group containing a polymerizable carbon-carbon double bond, R ²⁰² Represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Wherein R is ²⁰¹ R is as follows ²⁰³ Any one of them is a group containing a polymerizable carbon-carbon double bond, and R ²⁰¹ And R is ²⁰³ Both of them do not simultaneously contain a polymerizable carbon-carbonA group of double bonds. In addition, when R ²⁰¹ When the compound is a group containing a polymerizable carbon-carbon double bond, R ²⁰² And R is ²⁰³ A ring structure may also be formed with N.

The structure of the alkyl group is not particularly limited, and may be, for example, linear, branched, cyclic, or a combination of 2 or more thereof.

In the formula (B), R ²⁰⁴ Represents a hydrogen atom or a methyl group. n represents an integer of 1 to 2.

As a specific example of the alkyl group having 1 to 10 carbon atoms, examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1-dimethyl-n-propyl, 1, 2-dimethyl-n-propyl, 2-dimethyl-n-propyl, 1-ethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl 1, 1-dimethyl-n-butyl, 1, 2-dimethyl-n-butyl, 1, 3-dimethyl-n-butyl, 2-dimethyl-n-butyl, 2, 3-dimethyl-n-butyl, 3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1, 2-trimethyl-n-propyl, 1, 2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, and the like.

Preferably an alkyl group having 1 to 5 carbon atoms.

The group containing a polymerizable carbon-carbon double bond is not particularly limited, and a hydrocarbon group (alkenyl group) containing a carbon-carbon double bond having 2 to 10 carbon atoms, preferably 2 to 5 carbon atoms, for example, examples of the vinyl group include vinyl group (vinyl group), n-1-propenyl group, n-2-propenyl group (allyl group), 1-methylethenyl group, n-1-butenyl group, n-2-butenyl group, n-3-butenyl group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, 1-ethylvinyl group, 1-methyl-1-propenyl group, 1-methyl-2-propenyl group, n-1-pentenyl group, n-2-pentenyl group, n-4-pentenyl group, 1-n-propylvinyl group, 1-methyl-1-butenyl group, 1-methyl-2-butenyl group, 1-methyl-3-butenyl group, 2-ethyl-2-propenyl group, 2-methyl-1-butenyl group, 2-methyl-2-butenyl group, 2-methyl-3-butenyl group, 3-methyl-1-butenyl group, 3-methyl-2-butenyl group, 1-dimethyl-2-propenyl group, 1-isopropylvinyl group, 1, 2-dimethyl-1-propenyl group, 1, 2-dimethyl-2-propenyl group, 2-dimethyl-propenyl group, N-1-hexenyl, n-2-hexenyl, n-3-hexenyl, n-4-hexenyl, n-5-hexenyl, n-heptenyl, n-octenyl, n-nonenyl, n-decenyl, and the like.

Specific examples of the compound represented by the formula (A) include N-vinylformamide, N-vinylacetamide, N-allylformamide, N-allylacetamide, 4-acryloylmorpholine, (meth) acrylamide, N-methyl (meth) acrylamide, N-dimethyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-diisopropyl (meth) acrylamide, and the like, with N-vinylformamide, 4-acryloylmorpholine, N-dimethylacrylamide, N-diethyl (meth) acrylamide being preferred.

Specific examples of the compound represented by the formula (B) include tetrahydrofuran-2-ylmethyl acrylate, tetrahydrofuran-2-ylmethyl methacrylate, tetrahydrofuran-2-ylethyl acrylate and tetrahydrofuran-2-ylethyl methacrylate.

The reactive diluents may be used alone or in combination of two or more.

The content of the reactive diluent in the solvent-free composition is not particularly limited, but is preferably 1 to 2000 parts by mass, more preferably 500 to 1800 parts by mass, and even more preferably 1000 to 1500 parts by mass, in view of the degree of improvement in refractive index, solvent resistance, and viscosity of the resulting film, relative to 100 parts by mass of the triazine ring-containing polymer.

In the solvent-free composition of the present invention, an initiator may be blended depending on each crosslinking agent and reactive diluent. In the case of using a polyfunctional epoxy compound and/or a polyfunctional (meth) acryl compound as a crosslinking agent, as described above, the photocuring is performed without using an initiator to obtain a cured film, but in this case, an initiator may be used.

In the case of using a polyfunctional epoxy compound as a crosslinking agent, a photoacid generator or a photobase generator can be used.

The photoacid generator may be appropriately selected from known ones, and may be used, for example, as an onium salt derivative such as diazonium salt, sulfonium salt, or iodonium salt.

Specific examples thereof include aryl diazonium salts such as phenyl diazonium hexafluorophosphate, 4-methoxyphenyl diazonium hexafluoroantimonate, and 4-methylphenyl diazonium hexafluorophosphate; diaryliodonium salts such as diphenyliodonium hexafluoroantimonate, bis (4-methylphenyl) iodonium hexafluorophosphate, and bis (4-tert-butylphenyl) iodonium hexafluorophosphate; triarylsulfonium salts such as triphenylsulfonium hexafluoroantimonate, tris (4-methoxyphenyl) sulfonium hexafluorophosphate, diphenyl-4-thiophenoxyphenylsulfonium hexafluoroantimonate, 4' -bis (diphenylsulfonium) phenylsulfide-bis hexafluorophosphate, 4' -bis [ bis (. Beta. -hydroxyethoxy) phenylsulfonium ] phenylsulfide-bis hexafluoroantimonate, 4' -bis [ bis (. Beta. -hydroxyethoxy) phenylsulfonium ] phenylsulfide-bis-hexafluorophosphate, 4- [4' - (benzoyl) phenylthio ] phenyl-bis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- [4' - (benzoyl) phenylthio ] phenyl-bis (4-fluorophenyl) sulfonium hexafluorophosphate, and the like.

As specific examples of such onium salts, SAN-AID SI-60, SI-80, SI-100, SI-60-L, SI-80-L, SI-100L, SI-L145, SI-L150, SI-L160, SI-L110, SI-L147 (manufactured by Sanxinshi chemical Co., ltd.), UVI-6950, UVI-6970, UVI-6974, UVI-6990, UVI-6992 (manufactured by Union carbide Co., ltd.), CPI-100P, CPI-100A, CPI-200K, CPI-200S (manufactured by Sanyo chemical Co., ltd.), adeka Optomer SP-150, SP-151, SP-170, SP-171 (manufactured by Sanyo chemical Co., ltd.), manufactured by Asahi Denka Co., ltd.), irgacure 261 (manufactured by Basv Co., ltd.), CI-2481, CI-2624, CI-2639, CI-2064 (manufactured by Nippon Caddy Co., ltd.), CD-1010, CD-1011, CD-1012 (manufactured by Sadolma Co., ltd.), DS-100, DS-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, BENZONIN TOSYLATE, MBZ-101, MBZ-301, NAI-102, NAI-106, NAI-100, SI-101, SI-105, BENZONIN TOSYLATE, PYR-100, PYR-200, DNB-101, NB-201, BBI-101, BBI-102, BBI-103, BBI-109 (above, manufactured by Midori Kagaku Co., ltd.), PCI-061T, PCI-062T, PCI-020T, PCI-022T (above, manufactured by Japanese chemical Co., ltd.), IBPF, IBCF (manufactured by Sanand chemical Co., ltd.), and the like.

On the other hand, the photobase generator may be appropriately selected from known ones and used, and for example, cobalamine complex-based, oxime carboxylate-based, carbamate-based, quaternary ammonium salt-based photobase generators and the like can be used.

Specific examples thereof include 2-nitrobenzyl cyclohexyl carbamate, triphenylmethanol, O-carbamoyl hydroxyamide, O-carbamoyl oxime, [ [ (2, 6-dinitrobenzyl) oxy ] carbonyl ] cyclohexylamine, [ [ (2-nitrobenzyl) oxy ] carbonyl ] hexane 1, 6-diamine, 4- (methylthiobenzoyl) -1-methyl-1-morpholinoethane, (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane, N- (2-nitrobenzyloxycarbonyl) pyrrolidine, hexaammobalt (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.

As the photo-base generator, commercially available ones can be used, and specific examples thereof include TPS-OH, NBC-101, ANC-101 (all of which are product names, manufactured by Afforestation Co., ltd.), and the like.

When the photoacid or photobase generator is used, it is preferably used in the range of 0.1 to 15 parts by mass, more preferably 1 to 10 parts by mass, relative to 100 parts by mass of the polyfunctional epoxy compound.

The epoxy resin curing agent may be blended in an amount of 1 to 100 parts by mass based on 100 parts by mass of the polyfunctional epoxy compound, if necessary.

On the other hand, in the case of using a polyfunctional (meth) acryl compound, a photo radical polymerization initiator can be used.

The photo radical polymerization initiator may be appropriately selected from known ones and used, and examples thereof include acetophenones, benzophenones, miller benzoyl benzoate (Michler's benzoyl benzoate), amyl oxime esters, tetramethylthiuram monosulfide, thioxanthones, and the like.

Particularly preferred are photocleavable photo-radical polymerization initiators. Photo-cleavage type photo-radical polymerization initiators are described in the latest UV curing technology (page 159, publisher: gao Bao Yihong, publisher: society of technical information, co., ltd., release 1991).

Examples of the commercially available photo radical polymerization initiator include trade names manufactured by basf corporation: irgacure 127, 184, 369, 379EG, 651, 500, 754, 819, 903, 907, 784, 2959, CGI1700, CGI1750, CGI1850, CG24-61, OXE01, OXE02, darocur 1116, 1173, MBF, trade names manufactured by Basv Co., ltd.): lucirin TPO, trade name manufactured by the company (UCB): trade names manufactured by EBECRYL P36, fratai Li Langbo, inc (Fratelli Lamberti): esacure KIP150, KIP65LT, KIP100F, KT37, KT55, KTO46, KIP75/B, and the like.

When the photo radical polymerization initiator is used, it is preferably used in the range of 0.1 to 200 parts by mass, more preferably 1 to 150 parts by mass, per 100 parts by mass of the polyfunctional (meth) acrylate compound.

In the solvent-free composition of the present invention, a polyfunctional thiol compound having two or more thiol groups in the molecule may be added for the purpose of promoting the reaction between the triazine ring-containing polymer and the crosslinking agent, for example.

Specifically, a polyfunctional thiol compound represented by the following formula is preferable.

Chemical formula 52

The above-mentioned L represents a 2-4 valent organic group, preferably a 2-4 valent aliphatic group having 2-12 carbon atoms or a 2-4 valent heterocyclic ring-containing group, more preferably a 2-4 valent aliphatic group having 2-8 carbon atoms or a 3-valent group having an isocyanuric acid skeleton (1, 3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione ring) represented by the following formula.

N represents an integer of 2 to 4 corresponding to the valence of L.

Chemical formula 53

(wherein "·" represents a bond to an oxygen atom.)

Specific examples of the compound include 1, 4-bis (3-mercaptobutyryloxy) butane, 1,3, 5-tris (3-mercaptobutyryloxy ethyl) -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione, pentaerythritol tetrakis (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), and trimethylolethane tris (3-mercaptobutyrate).

These polyfunctional thiol compounds are also commercially available, and examples thereof include Karenz MT-BD1, karenz MT NR1, karenz MT PE1, TPMB, and TEMB (manufactured by Showa electric Co., ltd.).

These polyfunctional thiol compounds may be used singly or in combination of two or more.

In the case of using the polyfunctional thiol compound, the amount to be added is not particularly limited as long as it does not adversely affect the film obtained, and in the present invention, the solid content is preferably 0.01 to 10% by mass, more preferably 0.03 to 6% by mass, based on 100% by mass of the solid content.

The solvent-free composition of the present invention may contain other components than the triazine ring-containing polymer and the crosslinking agent, for example, additives such as a leveling agent, a surfactant, and a silane coupling agent, as long as the effects of the present invention are not impaired.

Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkylaryl ethers such as polyoxyethylene octyl phenol ether and polyoxyethylene nonyl phenol ether; polyoxyethylene-polyoxypropylene block copolymers; sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate; polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate such as polyoxyethylene sorbitan tristearate, fluorine-containing surfactants such as polyoxyethylene sorbitan fatty acid esters such as EFTOP EF301, EF303, EF352 (manufactured by Mitsubishi materials electric chemical Co., ltd.), fluorine-containing surfactants such as trade names MEGAFACE F, F173, R-08, R-30, R-40, F-553, F-554, RS-75, RS-72-K (manufactured by DIC Co., ltd.), FLUORAD FC430, FC431 (manufactured by Sumitomo 3M Co., ltd.), asahi guard AG710, surfon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Mitsubishi materials electric chemical Co., ltd.), organosiloxane polymer KP341 (manufactured by Sangyo chemical Co., ltd.), K302, K307, BYK-323, BYK 322, BYK-333, BYK-BYK 322, BYK-BYK, etc.).

These surfactants may be used either singly or in combination. 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 still more preferably 0.01 to 0.5 part by mass, based on 100 parts by mass of the triazine ring-containing polymer.

The solvent-free composition of the present invention can be applied to a substrate followed by heating or light irradiation to obtain a desired cured film.

The solvent-free composition may be applied by any method, for example, spin coating, dip coating, flow coating, ink jet, spray dispenser, spray, bar coating, gravure coating, slit coating, roll coating, transfer printing, brush coating, doctor blade coating, air knife coating, or the like.

Examples of the substrate include substrates made of silicon, glass having an Indium Tin Oxide (ITO) film formed thereon, glass having an Indium Zinc Oxide (IZO) film formed thereon, metal nanowires, polyethylene terephthalate (PET), plastics, glass, quartz, ceramics, and the like, and flexible substrates having flexibility can be used.

The firing temperature is not particularly limited for evaporating the solvent, and may be, for example, 110 to 400 ℃.

The firing method is not particularly limited, and for example, a hot plate or an oven may be used, and evaporation may be performed under an appropriate atmosphere such as an inert gas such as atmosphere or nitrogen, vacuum, or the like.

The firing temperature and the firing time may be selected so as to be suitable for the process steps of the target electronic device, and the firing conditions may be selected so that the physical properties of the obtained film are suitable for the required characteristics of the electronic device.

The conditions under which the light is irradiated are not particularly limited, and the irradiation energy and the irradiation time may be appropriately used depending on the triazine ring-containing polymer and the crosslinking agent to be used.

The film or cured film of the present invention obtained as described above can achieve high heat resistance, high refractive index and low volume shrinkage, and therefore can be suitably used in the field of electronic devices or optical materials for manufacturing one member such as a liquid crystal display, an organic EL element (organic EL display or organic EL illumination), a touch panel, an optical semiconductor (LED) element, a solid-state imaging element, an organic thin-film solar cell, a dye-sensitized solar cell, an organic thin-film transistor (TFT), a lens, a prism camera, a binoculars, a microscope, a semiconductor exposure device, and the like.

In particular, since the film or cured film made of the solvent-free composition of the present invention is high in transparency and also high in refractive index, it is possible to improve the light extraction efficiency (light diffusion efficiency) thereof and to improve the durability thereof in the case of being used as a planarization film, a light scattering layer or a sealing material for organic EL illumination.

In the case where the solvent-free composition of the present invention is used for a light scattering layer for organic EL illumination, a known organic-inorganic composite light diffusing agent, organic light diffusing agent, or inorganic light diffusing agent can be used as the light diffusing agent, and is not particularly limited. These may be used alone, or two or more of the same kind may be used in combination, or two or more of different kinds may be used in combination.

Examples of the organic-inorganic composite light diffusing agent include melamine resin-silica composite particles.

Examples of the organic light diffusing agent include crosslinked polymethyl methacrylate (PMMA) particles, crosslinked polymethyl acrylate particles, crosslinked polystyrene particles, crosslinked styrene acrylic acid copolymer particles, melamine-formaldehyde particles, silicone resin particles, silica-acrylic composite particles, nylon particles, benzoguanamine-formaldehyde particles, benzoguanamine-melamine-formaldehyde particles, fluororesin particles, epoxy resin particles, polyphenylene sulfide resin particles, polyethersulfone resin particles, polyacrylonitrile particles, polyurethane particles, and the like.

Examples of the inorganic light diffusing agent include calcium carbonate (CaCO) ₃ ) Titanium oxide (TiO) ₂ ) Barium sulfate (BaSO) ₄ ) Aluminum hydroxide (Al (OH) ₃ ) Silicon dioxide (SiO) ₂ ) Talc and the like are preferably titanium oxide (TiO ₂ ) Agglomerated silica particles, more preferably non-agglomerated titanium oxide (TiO ₂ )。

As the light diffusing agent, a light diffusing agent surface-treated with an appropriate surface modifier can be used.

Examples

The present invention will be described more specifically with reference to synthesis examples and examples, but the present invention is not limited to the examples. The measurement devices used in the examples were as follows.

[ ¹ H-NMR]

The device comprises: brookfield NMR System (Bruker NMR System) AVANCE III HD (500 MHz).

Measuring solvent: deuterated dimethyl sulfoxide (DMSO-d) ₆ )。

Reference substance: tetramethylsilane (TMS) (δ0.0ppm).

[GPC]

The device comprises: HLC-8200GPC, manufactured by Tosoh Co., ltd.

Column: east Cao TSKgel alpha-3000+east Cao TSKgel alpha-4000.

Column temperature: 40 ℃.

Solvent: dimethylformamide (DMF).

A detector: UV (271 nm).

Calibration curve: standard polystyrene.

[ viscosity ]

The device comprises: EMS-1000 of Kyoto electronic Co.

[ ellipsometer ]

The device comprises: multi-angle-of-incidence ellipsometer vast manufactured by JA Wu Lamu Japan (j.a. woollam (Japan)).

[ spectrocolorimeter ]

The device comprises: CM-3700A manufactured by Konikoku Meida Co.

[ optical microscope ]

The device comprises: olympuSBX51 manufactured by Olympus optical industries Co.

Exposure

The device comprises: compact ultraviolet LED irradiator NS395-CLT-100W3020 manufactured by nitride semiconductor corporation (Nitride Semiconductors Co,. Ltd.).

[1] Synthesis of triazine ring-containing Polymer

Synthesis example 1 Synthesis of Polymer Compound [5]

Chemical formula 54

Into a 3000mL four-necked flask, 1, 3-phenylenediamine [2] (52.78 g, 0.48mol, manufactured by An Nuo chemical Co., ltd. (Amino-Chem.), 2 '-bis (trifluoromethyl) -4,4' -diaminodiphenyl ether [3] (82.05 g,0.244mol, manufactured by Wuhan sun light Co., ltd. (Wuhan sun) and N-methyl-2-pyrrolidone (NMP, 1822.89g, manufactured by Kato chemical Co., ltd.), nitrogen substitution were charged, and after stirring, 1, 3-phenylenediamine [2] and 2,2 '-bis (trifluoromethyl) -4,4' -diaminodiphenyl ether [3] were dissolved in NMP. Then, the mixture was cooled to-5℃by an ethanol-dry ice bath, 2,4, 6-trichloro-1, 3, 5-triazine [1] (150.00 g,0.813mol, manufactured by Tokyo chemical Co., ltd.) was charged while confirming that the internal temperature was not 5℃or higher, and finally, the mixture was rinsed with NMP (227.86 g). After stirring for 30 minutes, the reaction solution was warmed to an internal temperature of 85 ℃ + -5 ℃. After stirring for 1 hour, 2- (4-aminophenyl) ethanol [4] (156.22 g,1.139mol, manufactured by Oakwood Co., ltd.) dissolved in NMP (227.86) g was added dropwise thereto, and the mixture was stirred for 3 hours. Then, 2-aminoethanol (149.05 g, tokyo chemical Co., ltd.) was added dropwise thereto, followed by stirring for 30 minutes, and then stirring was stopped. Tetrahydrofuran (THF, 1147 g), ammonium acetate (1291 g) and ion-exchanged water (1291 g) were added to the reaction solution, and stirred for 30 minutes. After stopping stirring, the solution was transferred to a separating funnel, separated into an organic layer and an aqueous layer, and the organic layer was recovered. The recovered organic layer was dropped into methanol (2869 g) and ion-exchanged water (4303 g) to reprecipitate. The obtained precipitate was separated by filtration and dried at 150℃for 8 hours using a reduced pressure dryer to obtain 280.3g of the target polymer compound [5] (hereinafter referred to as P-1).

The weight average molecular weight Mw of the compound P-1 as measured by GPC in terms of polystyrene was 6495, and the polydispersity Mw/Mn was 3.5. By combining compound P-1 ¹ The measurement results of the H-NMR spectrum are shown in FIG. 1.

Synthesis example 2 Synthesis of Polymer Compound [6]

Chemical formula 55

Into a 300mL four-necked flask, P-1[5 (40.00 g) obtained in Synthesis example 1 and 135.08g of tetrahydrofuran (THF, manufactured by Nitro Chemicals Co., ltd.) were charged, replaced with nitrogen, and then stirred to dissolve the materials. Next, the solution was warmed to an internal temperature of 65℃and 0.0040g of N-nitrosophenyl hydroxylamine aluminum salt (Q-1301, manufactured by Fuji film and Wako pure chemical industries, ltd.) and 17.89g of 2-isocyanatoethyl acrylate (2-Isocyanato ethyl acrylate) (AOI-VM, manufactured by Showa electric Co., ltd.) were added dropwise thereto, and the internal temperature was kept at 65℃and stirred for 1 hour. After stirring for 1 hour, 135.08g of tetrahydrofurfuryl acrylate (THFA, manufactured by Tokyo chemical industry Co., ltd.) was added, and THF was completely distilled off by an evaporator to obtain a 30% by mass THFA solution (hereinafter referred to as P-1 solution)

Synthesis example 3 Synthesis of Polymer Compound [7]

Chemical formula 56

Into a 3000mL four-necked flask, 1, 3-phenylenediamine [2] (47.5 g,0.439mol, manufactured by An Nuo chemical Co., ltd., amino-Chem.) and 799.2g of 3-methoxy-N, N-dimethylpropionamide (KJCMP A-100, manufactured by KJ chemical Co., ltd.) were charged with nitrogen, and after replacing the nitrogen, the mixture was stirred to dissolve the 1, 3-phenylenediamine [2] in KJCMP A-100. Then, the mixture was cooled to-5℃by an ethanol-dry ice bath, 2,4, 6-trichloro-1, 3, 5-triazine [1] (900.00 g,0.488mol, manufactured by Tokyo chemical Co., ltd.) was charged while confirming that the internal temperature was not 5℃or higher, and finally, the mixture was rinsed with KJCMP A-100 (192.6 g). After stirring for 30 minutes, the reaction solution was warmed to an internal temperature of 85.+ -. 5 ℃ and N-ethyldiethanolamine (78.0 g, manufactured by Kanto chemical Co., ltd.) was added while confirming that the internal temperature was not higher than 90 ℃. After stirring for 4 hours, 2- (4-aminophenyl) ethanol [4] (93.7 g,0.683mol, manufactured by Oakwood Co., ltd.) dissolved in KJCMPA-100 (180.0 g) was added dropwise, and the mixture was washed with KJCMPA-100 (20.7 g) and N-ethyldiethanolamine (52.0 g) was added dropwise thereto and stirred for 3 hours. Then, 2-aminoethanol (29.8 g, manufactured by tokyo chemical industry Co., ltd.) was added dropwise thereto, and after stirring for 30 minutes, the stirring was stopped. Tetrahydrofuran (THF, 360g, manufactured by Nikkiso Co., ltd.), ammonium acetate (900.0 g) and ion-exchanged water (900.0 g) were added to the reaction solution, and the mixture was stirred for 30 minutes. After stopping stirring, the solution was transferred to a separating funnel, separated into an organic layer and an aqueous layer, and the organic layer was recovered. The recovered organic layer was dropped into a mixed solution of methanol (1260 g) and ion-exchanged water (2160 g) to reprecipitate. The obtained precipitate was separated by filtration and dried at 150℃for 8 hours using a reduced pressure dryer to obtain 122.2g of the target polymer compound [7] (hereinafter referred to as P-2).

The weight average molecular weight Mw of the compound P-2 as measured by GPC in terms of polystyrene was 3816, and the polydispersity Mw/Mn was 2.9. By combining compound P-2 ¹ The measurement results of the H-NMR spectrum are shown in FIG. 2.

Synthesis example 4 Synthesis of Polymer Compound [8]

Chemical formula 57

Into a 1000mL four-necked flask, P-2[7 (80.0 g) and THF (289.09 g) obtained in Synthesis example 3 were charged, and after nitrogen substitution, the mixture was stirred to dissolve the mixture. Next, the solution was warmed to an internal temperature of 65℃and 0.0080g of N-nitrosophenyl hydroxylamine aluminum salt (Q-1301, fuji film and Wako pure chemical industries, ltd.) was added dropwise thereto, 43.90g of 2-isocyanatoethyl acrylate (2-Isocyananethyl acrylate) (AOI-VM, manufactured by Showa Denko K.K.) was kept at 65℃and stirred for 3 hours. After stirring for 3 hours, 289.09g of tetrahydrofurfuryl acrylate (THFA, manufactured by Tokyo chemical industry Co., ltd.) was added, and THF was completely distilled off by an evaporator to obtain a 30% by mass THFA solution (hereinafter referred to as P-2 solution).

[2] Preparation of surface-treated inorganic particles

The method and the measuring apparatus for measuring physical properties performed in production examples 1 to 4 below are shown below.

(1) Moisture content: the results were obtained by karl-fischer titration.

(2) Primary particle diameter: the dispersion was dried on a copper wire mesh, and 100 particle diameters were measured by observation with a transmission electron microscope, and the average value was obtained as the primary particle diameter.

(3) Specific gravity: the temperature was determined by a float-scale method (20 ℃ C.).

(4) Viscosity: was determined by means of an Ohnder viscometer (20 ℃).

(5) Particle size based on dynamic light scattering method: the measurement was performed by a nanoparticle potential analyzer (Zetasizer Nano) manufactured by Malvern instruments (Malvern).

(6) Concentration of solid content: obtained from the solid residue obtained when the mixture was fired at 500 ℃.

(7) The bonding amount of the organosilane compound: the amount of the organosilane compound bonded to the modified metal oxide colloidal particles was determined by elemental analysis.

The device comprises: series IICHNS/O Analyzer2400 manufactured by Perkinelmer instruments Inc. (Perkinelmer).

Production example 1: production of core particle (A) and core particle (A1)

126.2g of pure water and 438g of a 35% by mass tetraethylammonium hydroxide aqueous solution (manufactured by Sankai chemical Japan Co., ltd.; sachem Japan) and 17.8g of metastannic acid (as SnO) were added to a1 liter vessel with stirring ₂ 15g, titanium tetraisopropoxide 284g (as TiO) ₂ 80g in terms of conversion, A-1 manufactured by Sedum Kabushiki Kaisha, japan) and oxalic acid dihydrate 98 (70 g in terms of oxalic acid, manufactured by Seisakusho Kaisha). For the obtained mixed solution, the molar ratio of oxalic acid/titanium atom was 0.78, and the molar ratio of tetraethylammonium hydroxide/titanium atom was 1.04. The mixed solution was kept at 80℃for 2 hours, and then depressurized to 580Torr for 2 hours to prepare a titanium mixed solution. The pH of the prepared titanium mixed solution was 4.7, the conductivity was 27.2mS/cm, and the metal oxide concentration was 10.0 mass%. 950g of the above titanium mixed solution and 950g of pure water were put into a 3 liter autoclave vessel having a glass liner, and the hydrothermal treatment was performed at 140℃for 5 hours. After cooling to room temperature, the taken out solution after the hydrothermal treatment was a pale milky aqueous dispersion of colloidal particles containing titanium oxide. The pH of the resulting dispersion was 3.9, the conductivity was 19.7mS/cm, and the TiO was ₂ The concentration was 4.2 mass%, the tetraethylammonium hydroxide concentration was 8.0 mass%, the oxalic acid concentration was 3.7 mass%, the particle size by dynamic light scattering was 16nm,elliptical particles having a primary particle diameter of 4 to 10nm were observed in the observation by a transmission electron microscope. The powder obtained by drying the obtained dispersion at 110℃was subjected to X-ray diffraction analysis, and it was confirmed that the powder was rutile crystal. The obtained colloidal particles containing titanium oxide were used as the core particles (a). Next, zirconium oxychloride (as ZrO ₂ Comprises 21.19% by mass of 70.8g of a zirconium oxychloride aqueous solution (as ZrO) prepared separately by diluting with 429.2g of pure water ₂ Containing 3.0 mass%), 1000g of a dispersion (water-dispersible sol) of the core particles (a) desalted with an ultrafiltration membrane was added thereto with stirring. Then, the solution was heated to 95℃to hydrolyze the solution, thereby obtaining a water-dispersible sol of titanium oxide-containing core particles (A1) (hereinafter, core particles (A1)) having a thin film layer of zirconium oxide formed on the surface thereof. The pH of the resulting aqueous dispersion was 1.2, the concentration of the entire metal oxide was 20 mass%, and colloidal particles having a primary particle diameter of 4 to 10nm were observed by observation under a transmission electron microscope.

Production example 2: production of coating particles (B)

JIS No. 3 sodium Silicate (SiO) ₂ 29.8 mass% of sodium stannate NaSnO, fuji chemical Co., ltd.) 77.2g was dissolved in 1282g of pure water ₃ ·H ₂ O (as SnO) ₂ 55.1 mass% of the solution was dissolved in a solvent of 20.9g of Showa chemical Co., ltd.). The aqueous solution thus obtained was passed through a column packed with a hydrogen cation exchange resin (Amberlite (registered trademark) IR-120B) to obtain an aqueous dispersion sol (ph 2.4 as SnO) of acidic silica-tin oxide composite colloidal particles (B1) ₂ Contains 0.44 mass% of SiO ₂ Contains 0.87 mass% of SiO ₂ /SnO ₂ Mass ratio of 2.0) 2634g. Next, 6.9g of diisopropylamine was added to the resulting water-dispersible sol. The obtained sol was a water-dispersible sol of basic silica-tin oxide composite colloidal particles (B1) (hereinafter, coating particles (B1)), and had a ph of 8.0. In this water-dispersible sol, colloidal particles having a primary particle diameter of 4nm or less were observed by a transmission electron microscope.

Production example 3: production of modified colloidal particles (C1)

1455g of the water-dispersible sol of the core particle (A1) obtained in production example 1 was added to 2634g of the water-dispersible sol of the coating particle (B1) prepared in production example 2 with stirring. Next, a column packed with 500 ml of anion exchange resin (Amberlite (registered trademark) IRA-410, manufactured by Oeno corporation, japan) was introduced. Next, the introduced aqueous dispersion was heated at 95 ℃ for 3 hours, and then introduced into a column filled with a hydrogen cation exchange resin (Amberlite (registered trademark) IR-120B), stabilized with tri-n-pentylamine, and concentrated by an ultrafiltration membrane method, whereby a silica-tin oxide composite oxide-coated titanium oxide-containing colloidal particle (C1) (hereinafter, modified colloidal particle (C1)) having an intermediate thin film layer composed of zirconia formed between the core particle (A1) and the coating particle (B1) was obtained. The total metal oxide concentration of the resulting water-dispersible sol was 20 mass%, and the primary particle diameter of the sol was 4 to 10nm as observed by a transmission electron microscope. Next, the dispersant of the obtained water-dispersible sol was replaced with methanol using a rotary evaporator to obtain a methanol-dispersible sol of modified colloidal particles (C1). The total metal oxide concentration of the methanol dispersion sol was 30 mass%, the viscosity was 1.5 mPas, the particle diameter by the dynamic light scattering method was 18nm, and the water content was 1.0 mass%.

Production example 4: production of surface-modified colloidal particles (D1)

To 533g of the methanol dispersion sol of the modified colloidal particles (C1) obtained in production example 3, 8.0g of polyether-modified silane (trade name: X-12-641, manufactured by Xinyue chemical Co., ltd.) was added, and the mixture was heated at 70℃for 5 hours under reflux. Next, 6.4g of 3-methacryloxypropyl trimethoxysilane (trade name: KBM-503, manufactured by Xinyue chemical Co., ltd.) was added, and reflux heating was performed at 70℃for 5 hours, to thereby obtain a methanol dispersion in which polyether-modified silane and methacryloxypropyl silane were bonded to the surface of the surface-modified colloidal particles (D1) (hereinafter, surface-modified colloidal particles (D1)). Next, methanol was distilled off while adding propylene glycol monomethyl ether at 80Torr using an evaporator to replace methanol with propylene glycol monomethyl ether, thereby obtaining 530g of propylene glycol monomethyl ether dispersion of surface-modified colloidal particles (D1). The specific gravity of the obtained dispersion was 1.209, the viscosity was 3.6 mPas, the concentration of the entire metal oxide was 30.0 mass%, the primary particle diameter was 4 to 10nm based on observation by a transmission electron microscope, and the dynamic light scattering particle diameter was 11nm. In the obtained surface-modified colloidal particles (D1), the polyether-modified silane bonded to the surface of the modified colloidal particles (C1) was 4.0 mass% with respect to the total metal oxides of the modified colloidal particles (C1), and the methacryloxypropyl silane bonded to the particle surface was 2.5 mass% with respect to the total metal oxides of the modified colloidal particles (C1).

PREPARATION EXAMPLE 5

Into a 1L eggplant-shaped flask were placed 310.83g of propylene glycol monomethyl ether dispersion (total metal oxide concentration: 30.0 mass%) of the surface-modified colloidal particles (D1) obtained in production example 4 and 217.73g of acryloylmorpholine (ACMO, manufactured by Tokyo chemical Co., ltd.) and the propylene glycol monomethyl ether was completely distilled off by an evaporator to obtain a 30 mass% ACMO solution (hereinafter referred to as T-1 solution).

Production example 6: production of core particle (A2)

255.2g of pure water was placed in a 1 liter vessel, and 438g of a 35 mass% tetraethylammonium hydroxide aqueous solution (manufactured by Sankai chemical Japan Co., ltd.; and 10.1g of metastannic acid (as SnO) was added with stirring ₂ The obtained product contained 8.6g of titanium tetraisopropoxide 325.2g (as TiO) ₂ 91.4g of oxalic acid dihydrate (53.6 g, manufactured by Kagaku Co., ltd., japan) was contained in the amount of 91.4g in terms of oxalic acid. The molar ratio of oxalic acid/titanium atom of the obtained mixed solution was 0.52, and the molar ratio of tetraethylammonium hydroxide/titanium atom was 0.70. 1000g of the mixed solution was kept at 80℃for 2 hours, and isopropanol was distilled off under reduced pressure to 580Torr to prepare a titanium mixed solution. The pH of the prepared titanium mixed solution was 5.2, the conductivity was 25.2mS/cm, and the metal oxide concentration was 10.0 mass%. 1000g of the above titanium mixed solution and 1000g of pure water were charged into a 3 liter autoclave equipped with a glass liner, and a hydrothermal treatment was performed at 140℃for 5 hours. After cooling to room temperature, the taken out solution after the hydrothermal treatment is light milky colloid particles containing titanium oxide An aqueous dispersion. The pH of the resulting dispersion was 3.9, the conductivity was 19.2mS/cm, and the TiO was ₂ The concentration was 5.0 mass%, the tetraethylammonium hydroxide concentration was 7.7 mass%, the oxalic acid concentration was 2.7 mass%, the particle diameter by dynamic light scattering was 15nm, and elliptical particles having a primary particle diameter of 4 to 10nm were observed by observation with a transmission electron microscope. The powder obtained by drying the dispersion at 110℃was subjected to X-ray diffraction analysis, and it was confirmed that the powder was rutile crystal. The obtained colloidal particles containing titanium oxide were used as core particles (A2).

Production example 7: production of modified colloidal particles (C2)

2000g of dispersion sol containing core particles (A2) desalted by ultrafiltration was slowly added to 1145g of dispersion sol of coated particles (B1) obtained in production example 2 under stirring, and the mixture was kept at 95℃for 2 hours. Next, the mixture was introduced into a column packed with a hydrogen cation exchange resin (Amberlite (registered trademark) IR-120B), stabilized with tri-n-pentylamine, and concentrated by an ultrafiltration membrane method to obtain a water-dispersible sol of silica-tin oxide composite oxide-coated titanium oxide-containing colloidal particles (C2) (hereinafter, modified colloidal particles (C2)). The total metal oxide concentration of the resulting water-dispersible sol was 18 mass%, and the primary particle diameter of the sol was 4 to 10nm as observed by a transmission electron microscope. Next, the dispersant of the obtained water-dispersible sol was replaced with methanol using a rotary evaporator to obtain a methanol-dispersible sol of modified colloidal particles (C2). The total metal oxide concentration of the methanol dispersion sol was 30 mass%, the viscosity was 1.3 mPas, the particle diameter by the dynamic light scattering method was 15nm, and the water content was 1.2 mass%.

Production example 8: production of surface-modified colloidal particles (D2)

5.8g of polyether-modified silane (trade name: X-12-641, manufactured by Xinyue chemical Co., ltd.) was added to 383g of the methanol-dispersed sol of the modified colloidal particles (C2) obtained in production example 7, and the mixture was heated at 70℃for 5 hours under reflux. Next, while adding propylene glycol monomethyl ether at 80Torr using an evaporator, methanol was distilled off to replace methanol with propylene glycol monomethyl ether, thereby obtaining 288g of propylene glycol monomethyl ether dispersion of surface-modified colloidal particles (D2). The resulting dispersion had a specific gravity of 1.365, a viscosity of 5.3 mPas, a total metal oxide concentration of 40.5 mass%, a primary particle diameter of 4 to 10nm as observed by a transmission electron microscope, and a dynamic light scattering particle diameter of 11nm. In the obtained surface-modified colloidal particles (D2), the polyether-modified silane bonded to the surface of the modified colloidal particles (C2) was 4.0 mass% relative to the total metal oxides of the modified colloidal particles (C2).

Production example 9

Into a 1L eggplant-shaped flask were placed 246.9g of propylene glycol monomethyl ether dispersion (total metal oxide concentration: 40.5 mass%) of the surface-modified colloidal particles (D2) obtained in production example 8 and 233.3g of acryloylmorpholine (ACMO, manufactured by Tokyo chemical Co., ltd.) and the propylene glycol monomethyl ether was completely distilled off by an evaporator to obtain a 30 mass% ACMO solution (hereinafter referred to as T-2 solution).

Production example 10: production of surface-modified colloidal particles (D3)

To 533g of the methanol dispersion sol of the modified colloidal particles (C1) obtained in production example 3, 8.0g of polyether-modified silane (trade name: X-12-641, manufactured by Xinyue chemical Co., ltd.) was added, and the mixture was heated at 70℃for 5 hours under reflux. A methanol dispersion of surface-modified colloidal particles (D3) (hereinafter, surface-modified colloidal particles (D3)) having polyether-modified silane bonded to the surface thereof was obtained. Next, methanol was distilled off while adding propylene glycol monomethyl ether at 80Torr using an evaporator to replace methanol with propylene glycol monomethyl ether, thereby obtaining 530g of propylene glycol monomethyl ether dispersion of surface-modified colloidal particles (D3). The resulting dispersion had a specific gravity of 1.212, a viscosity of 3.2 mPas, a concentration of 30.3 mass% of the entire metal oxide, a primary particle diameter of 4 to 10nm as observed by a transmission electron microscope, and a dynamic light scattering particle diameter of 10nm. In the obtained surface-modified colloidal particles (D3), the polyether-modified silane bonded to the surface of the modified colloidal particles (C1) was 3.9 mass% relative to the total metal oxides of the modified colloidal particles (C1).

PREPARATION EXAMPLE 11

Into a 1L eggplant-shaped flask were placed 300g of propylene glycol monomethyl ether dispersion (total metal oxide concentration: 30.3 mass%) of the surface-modified colloidal particles (D3) obtained in production example 10 and 212.1g of acryloylmorpholine (ACMO, manufactured by Tokyo chemical Co., ltd.) and the propylene glycol monomethyl ether was completely distilled off by an evaporator to obtain a 30 mass% ACMO solution (hereinafter referred to as T-3 solution).

Production example 12: production of surface-modified colloidal particles (D4)

To 298g of the methanol dispersion sol of the modified colloidal particles (C2) obtained in production example 7, 6.7g of 3-acryloxypropyl trimethoxysilane (trade name: KBM-5103, manufactured by Xinyue chemical Co., ltd.) was added, and the mixture was heated at 70℃under reflux for 5 hours, thereby obtaining a methanol dispersion of the surface-modified colloidal particles (D4). The resulting dispersion had a specific gravity of 1.063, a viscosity of 1.8 mPas, a concentration of 29.9 mass% of the entire metal oxide, a primary particle diameter of 4 to 10nm as observed by a transmission electron microscope, and a dynamic light scattering particle diameter of 18nm. In the obtained surface-modified colloidal particles (D4), the 3-acryloxypropyl trimethoxysilane bonded to the surface of the modified colloidal particles (C2) was 2.0 mass% relative to the total metal oxide of the modified colloidal particles (C2).

Production example 13

100g of the methanol dispersion (total metal oxide concentration: 29.9 mass%) of the surface-modified colloidal particles (D4) obtained in production example 12 and 70.0g of acryloylmorpholine (ACMO, manufactured by Tokyo chemical industry Co., ltd.) were put into a 1L eggplant-shaped flask, and methanol was completely distilled off by an evaporator to obtain a 30 mass% ACMO solution (hereinafter referred to as a T-4 solution).

[3] Preparation of film-forming composition containing crosslinking agent and preparation of cured film

Examples 1 to 1

To the P-1 solution (4.913 g) synthesized in Synthesis example 2, were added the T-1 solution (14.740 g) obtained in preparation example 5, DN-0075 (manufactured by Japanese chemical Co., ltd.) as a crosslinking agent 1.769g, pentaerythritol tetrakis (3-mercaptobutyrate) (Karenz MT PE1, manufactured by Showa electric Co., ltd.) as a UV radical curing auxiliary agent 0.884g, OXE-02 (manufactured by Basf) 3.519g as a UV radical initiator, MEGAFACE R-40 (manufactured by DIC Co., ltd.) as a 10% by mass THFA solution of a surfactant 0.442g and THFA3.626g as an additional diluent, and the dissolution was visually confirmed to prepare a solvent-free solution (hereinafter referred to as NP-1).

The NP-1 solution was spin-coated on a 50 mm. Times.50 mm. Times.0.7 mm alkali-free glass substrate with a spin coater at 200rpm for 5 seconds, then at 1480rpm for 30 seconds, pre-dried at 100℃for 3 minutes using a hot plate, and then irradiated with light of 395nm wavelength at 900mJ/cm with a UV-LED irradiation apparatus ² To obtain a cured film (hereinafter referred to as NP-1 film).

Examples 1 to 2

A solvent-free solution (hereinafter referred to as NP-2 solution) was prepared in the same manner as in example 1-1, except that the inorganic fine particle solution used was changed to the T-2 solution (14.740 g) obtained in production example 9.

A cured film (hereinafter referred to as NP-2 film) was obtained using the NP-2 solution under the same conditions as in example 1-1.

Examples 1 to 3

A solvent-free solution (hereinafter referred to as NP-3 solution) was prepared in the same manner as in example 1-1, except that the inorganic fine particle solution used was changed to the T-3 solution (14.740 g) obtained in production example 11.

A cured film (hereinafter referred to as NP-3 film) was obtained using the NP-3 solution under the same conditions as in example 1-1.

Examples 1 to 4

To the P-2 solution (3.682 g) synthesized in Synthesis example 4, the T-4 solution (19.330 g) obtained in preparation example 13, DN-0075 (manufactured by Japanese Kagaku Co., ltd., 0.663 g) as a crosslinking agent, pentaerythritol tetrakis (3-mercaptobutyrate) (Karenz MT PE1, manufactured by Showa electric Co., ltd.) 0.663g as a UV radical initiator, 0.331g of OXE-02 (manufactured by Basf) as a UV radical initiator, MEGAFACE R-40 (manufactured by DIC Co., ltd.) as a 10% by mass THFA solution of a surfactant, 0.066g as an additional diluent, and FA (5.265 g) as an additional diluent were added, and the dissolution was visually confirmed to prepare a solvent-free solution (hereinafter referred to as NP-4 solution).

The NP-4 solution was applied on a 50 mm. Times.50 mm. Times.0.7 mm alkali-free glass substrate at 200r using a spin coater pm 5 sec, 500rpm 30 sec spin coating, using a hot plate at 100deg.C pre-drying for 3 min, UV-LED irradiation device through 395nm wavelength light at 900mJ/cm ² The exposure amount of (a) was irradiated in the presence of nitrogen to obtain a cured film (hereinafter, referred to as an NP-4 film).

Examples 1 to 5

A solvent-free solution (hereinafter referred to as NP-5 solution) was prepared in the same manner as in examples 1-4, except that the UV radical curing auxiliary was removed.

A cured film (hereinafter referred to as NP-5 film) was obtained using the NP-5 solution under the same conditions as in examples 1 to 4.

Examples 1 to 6

A solvent-free solution (hereinafter referred to as NP-6 solution) was prepared in the same manner as in examples 1-4 except that a UV radical curing auxiliary was not used and that the UV radical initiator used was changed from 0.331g of OXE-02 (manufactured by Basf) to 0.331g of Omnirad 819 (manufactured by Basf).

A cured film (hereinafter referred to as NP-6 film) was obtained using the NP-6 solution under the same conditions as in examples 1 to 4.

The cured film obtained above was measured for refractive index, film thickness, b-x, transmittance at 400 to 800nm, and haze. The results are shown in tables 1-1 and 1-2. The average transmittance at 400 to 800nm was calculated for the transmittance, and is shown in tables 1 to 1 and 1 to 2.

TABLE 1-1

	Example 1-1	Examples 1 to 2	Examples 1 to 3
				Refractive index (@ 550 nm)	1.706	1.743	1.707
Film thickness (nm)	1031	1008	1002
				b*	0.7	0.8	0.8
Transmittance (%)	96.6	95.9	96.5
				Haze (%)	0.07	0.09	0.07

TABLE 1-2

	Examples 1 to 4	Examples 1 to 5	Examples 1 to 6
				Refractive index (@ 550 nm)	1.85	1.91	1.91
Film thickness (nm)	4163	2946	2959
				b*	1.7	2.1	1.3
Transmittance (%)	93.6	92.2	92.6
				Haze (%)	0.04	0.00	0.00

From these results, it was found that cured films produced using the solvent-free compositions obtained in examples 1-1 to 1-6 have excellent effects of maintaining a high refractive index, a high transmittance, and maintaining a low haze.

[ measurement of viscosity ]

Examples 2 to 1

The viscosity at 25℃to 45℃was measured using the NP-1 solution obtained in example 1-1 using an EMS viscometer.

Examples 2 to 2

The viscosity of the NP-2 solution obtained in example 1-2 was measured in the same manner as in example 2-1.

Examples 2 to 3

The viscosity of the NP-3 solution obtained in example 1-3 was measured in the same manner as in example 2-1.

Examples 2 to 4

The viscosity of the NP-4 solution obtained in example 1-4 was measured in the same manner as in example 2-1.

Examples 2 to 5

The viscosity of the NP-5 solution obtained in example 1-5 was measured in the same manner as in example 2-1.

Examples 2 to 6

The viscosity of the NP-6 solution obtained in example 1-6 was measured in the same manner as in example 2-1.

The measured viscosity under each temperature condition is shown in tables 2-1 and 2-2.

TABLE 2-1

TABLE 2-2

From these results, it is found that when the temperature is increased to 35℃or higher, the viscosity of the ink reaches a low viscosity of about 20 mPas or lower, and the ink can be sufficiently applied to ink jet coating and the like.

[ solvent resistance (crack resistance) of thick film (10 μm or more), transmittance, haze measurement ]

Examples 3-1-1

The NP-1 solution obtained in example 1-1 was spin-coated on a 50 mm. Times.50 mm. Times.0.7 mm alkali-free glass substrate with a spin coater at 200rpm for 5 seconds and 200rpm for 30 seconds, and after predrying at 100℃for 3 minutes using a hot plate, it was irradiated with light of 395nm wavelength at 900mJ/cm using a UV-LED irradiation apparatus ² To obtain a cured film (hereinafter referred to as NP-1)A film).

The substrate with the cured film prepared above was mounted on a spin coater, and 1mL of Propylene Glycol Monomethyl Ether (PGME) was applied. Next, the cured film was exposed to the solvent by rotating at 50rpm for 60 seconds in such a manner that the liquid did not fly off the substrate. Then, the solvent was removed from the substrate by rotating at 1000rpm for 30 seconds. Finally, after drying at 120℃for 10 seconds using a hot plate, the refractive index and film thickness were measured, the residual film ratio was calculated, and the film surface was observed with an optical microscope.

The residual film rate was calculated by the following formula.

Film residue (%) = (film thickness after solvent exposure)/(film thickness before solvent exposure) ×100

In addition, the transmittance and haze were also measured before solvent exposure.

Examples 3-1-2

A cured film was produced and solvent resistance was tested in the same manner as in example 2-1, except that the solvent used for coating was changed to Propylene Glycol Monomethyl Ether Acetate (PGMEA).

Examples 3-1 to 3

A cured film was produced and solvent resistance was tested in the same manner as in example 2-1, except that the solvent used for coating was changed to Cyclopentanone (CPN).

Examples 3-2-1

A cured film was produced and solvent resistance was tested in the same manner as in example 3-1-1, except that the solution used was changed to NP-2.

Examples 3-2-2

A cured film was produced and solvent resistance was tested in the same manner as in example 3-1-2, except that the solution used was changed to NP-2.

Examples 3-2-3

A cured film was produced and solvent resistance was tested in the same manner as in examples 3-1 to 3, except that the solution used was changed to NP-2.

Examples 3 to 1

A cured film was produced and solvent resistance was tested in the same manner as in example 3-1-1, except that the solution used was changed to NP-3.

Examples 3 to 2

A cured film was produced and solvent resistance was tested in the same manner as in example 3-1-2, except that the solution used was changed to NP-3.

Examples 3 to 3

A cured film was produced and solvent resistance was tested in the same manner as in examples 3-1 to 3, except that the solution used was changed to NP-3.

The results of film thickness measurement, residual film ratio, average transmittance of 400 to 800nm and haze of examples 3-1 to 3-1-3 are shown in Table 3, the results of examples 3-2-1 to 3-2-3 are shown in Table 4, the results of examples 3-3-1 to 3-3 are shown in Table 5, the microscopic photographs of the surfaces of the cured films of examples 3-1 to 3-1-3 after solvent exposure are shown in FIGS. 3 to 5, the microscopic photographs of the surfaces of the cured films of examples 3-2-1 to 3-2-3 after solvent exposure are shown in FIGS. 6 to 8, and the microscopic photographs of the surfaces of the cured films of examples 3-3-1 to 3-3 after solvent exposure are shown in FIGS. 9 to 11.

TABLE 3 Table 3

TABLE 4 Table 4

TABLE 5

[ solvent resistance (crack resistance) ]

Examples 3 to 4 to 1

The NP-4 films obtained in examples 1-4 were mounted on a spin coater and coated with 1mL of Propylene Glycol Monomethyl Ether (PGME). Next, the cured film was exposed to the solvent by rotating at 50rpm for 60 seconds in such a manner that the liquid did not fly off the substrate. Then, the solvent was removed from the substrate by rotating at 1000rpm for 30 seconds. Finally, after drying at 100℃for 10 seconds using a hot plate, the refractive index and film thickness were measured, and the film residue was calculated and the film surface was observed with an optical microscope.

The residual film rate was calculated by the following formula.

Residual film ratio (%) = [ film thickness before solvent exposure ]/(film thickness after solvent exposure) ]. Times.100

Examples 3 to 4 to 2

A cured film was produced and solvent resistance was tested in the same manner as in example 3-4-1, except that the solvent used for coating was changed to Propylene Glycol Monomethyl Ether Acetate (PGMEA).

Examples 3 to 4 to 3

A cured film was produced and solvent resistance was tested in the same manner as in example 3-4-1, except that the solvent used for coating was changed to Cyclopentanone (CPN).

Examples 3 to 5 to 1

Solvent resistance test was performed in the same manner as in example 3-4-1, except that the film used was changed to NP-5 film.

Examples 3 to 5 to 2

Solvent resistance test was performed in the same manner as in example 3-4-2, except that the film used was changed to NP-5 film.

Examples 3 to 5 to 3

Solvent resistance test was performed in the same manner as in example 3-4-3, except that the film used was changed to NP-5 film.

Examples 3 to 6 to 1

Solvent resistance test was performed in the same manner as in example 3-4-1, except that the film used was changed to NP-6 film.

Examples 3 to 6 to 2

Solvent resistance test was performed in the same manner as in example 3-4-2, except that the film used was changed to NP-6 film.

Examples 3 to 6 to 3

Solvent resistance test was performed in the same manner as in example 3-4-3, except that the film used was changed to NP-6 film.

Table 6 shows the results of film thickness measurement of examples 3-4-1 to 3-4-3, examples 3-5-1 to 3-5-3, and examples 3-6-1 to 3-6-3, and the microscopic photographs of the cured films after solvent exposure are shown in FIGS. 12 to 20.

TABLE 6

From these results, it was found that the cured films obtained from the NP-1 to NP-6 solutions had excellent effects of maintaining high solvent resistance and high transmittance and low haze even when the film thickness was thick. In addition, it is found that the inorganic fine particles have no crosslinked portion and maintain high solvent resistance.

Claims

1. A solvent-free composition characterized in that,

the solvent-free composition comprises a triazine ring-containing polymer, a cross-linking agent, and inorganic particles, and does not contain an organic solvent,

the triazine ring-containing polymer comprises a repeating unit structure represented by the following formula (1) having at least one triazine ring end, at least a part of the triazine ring end being blocked with an amino group having a crosslinking group,

chemical formula 1

In the formula (1), R and R' independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or an aralkyl group, Q represents a divalent group having 3 to 30 carbon atoms and having a ring structure, and x represents a chemical bond.

2. The solventless composition of claim 1 wherein,

q in the formula (1) represents at least one selected from the group represented by the formulas (2) to (13) and the formulas (102) to (115),

chemical formula 2

In the formulas (2) to (13), R ¹ ～R ⁹² Independently of each other, a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms,

R ⁹³ and R is ⁹⁴ Represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms,

W ¹ and W is ² Independently of each other, represent a single bond, CR ⁹⁵ R ⁹⁶ 、C＝O、O、S、SO、SO ₂ Or NR (NR) ⁹⁷ ，R ⁹⁵ And R is ⁹⁶ Independently of one another, represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a haloalkyl group having 1 to 10 carbon atoms, the alkyl groups having 1 to 10 carbon atoms together forming a ring or not forming a ring, R ⁹⁷ Represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a phenyl group,

X ¹ and X ² Independently of each other, represents a single bond, an alkylene group having 1 to 10 carbon atoms or a group represented by the formula (14),

chemical formula 3

In the formula (14), R ⁹⁸ ～R ¹⁰¹ Independently of each other, a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms,

Y ¹ and Y ² Independently of each other, represents a single bond or an alkylene group having 1 to 10 carbon atoms,

* Represents a chemical bond and is used to form a bond,

chemical formula 4

In the formulas (102) to (115), R ¹ And R is ² Independently of each other, an alkylene group having 1 to 5 carbon atoms and having a branched structure or not, and a chemical bond.

3. The solventless composition of claim 1 wherein,

the R in the formulas (2) to (13) ¹ ～R ⁹² And R is ⁹⁸ ～R ¹⁰¹ Independently of one another, a hydrogen atom, a halogen atom or a haloalkyl group having 1 to 10 carbon atoms.

4. The solventless composition of claim 1 wherein,

the arylamino group having a crosslinking group is represented by formula (15),

chemical formula 5

In the formula (15), R ¹⁰² Represents a crosslinking group, and represents a chemical bond.

5. The solventless composition of claim 4 wherein,

the amino group having a crosslinking group is represented by formula (16),

chemical formula 6

In the formula (16), R ¹⁰² Meaning the same as above, meaning chemical bond.

6. The solventless composition of claim 4 wherein,

the R is ¹⁰² Is a hydroxyl-containing group or a (meth) acryloyl-containing group.

7. The solventless composition of claim 6 wherein,

the R is ¹⁰² Is a hydroxyalkyl group, (meth) acryloyloxyalkyl group or a group represented by the following formula (i),

chemical formula 7

In the formula (i), A ¹ Represents an alkylene group having 1 to 10 carbon atoms, A ² Represents a single bond or a group represented by the following formula (j),

chemical formula 8

A ³ Represents an (a+1) -valent aliphatic hydrocarbon group substituted or unsubstituted with a hydroxyl group, A ⁴ Represents a hydrogen atom or a methyl group, a represents 1 or 2, and a represents a bond.

8. The solventless composition of claim 7 wherein,

the R is ¹⁰² Is a group selected from the group consisting of hydroxymethyl, 2-hydroxyethyl, (meth) acryloyloxymethyl, (meth) acryloyloxyethyl and groups represented by the following formulas (i-2) to (i-5),

chemical formula 9

In the formulas (i-2) to (i-5), the chemical bond is represented.

9. The solventless composition of claim 2 wherein,

at least one halogen atom or a halogenated alkyl group having 1 to 10 carbon atoms is contained in at least one aromatic ring in Q in the formula (1).

10. The solventless composition of claim 1 wherein,

a portion of the triazine ring ends are further capped with unsubstituted arylamino groups.

11. The solventless composition of claim 1 wherein,

the unsubstituted arylamino group is represented by formula (33),

chemical formula 10

In formula (33), the chemical bond is represented.

12. The solventless composition of claim 1 wherein,

Q in the formula (1) is represented by the formula (17),

chemical formula 11

In formula (17), the chemical bond is represented.

13. The solventless composition of claim 1 wherein,

q in the formula (1) is represented by the formula (20),

chemical formula 12

In formula (20), represents a chemical bond.

14. The solventless composition of claim 1 wherein,

the crosslinking agent is a polyfunctional (meth) acryloyl compound.

15. The solventless composition of claim 1 wherein,

the inorganic particles comprise a metal oxide, a metal sulfide, or a metal nitride.

16. The solventless composition of claim 1 wherein,

the solventless composition also contains a reactive diluent.

17. The solventless composition of claim 16 wherein,

the reactive diluent is a compound having one free radically polymerizable group.

18. The solventless composition of claim 1 wherein,

the solvent-free composition is a photocurable composition.

19. A film, wherein,

the film is obtained from the solvent-free composition of any one of claims 1 to 18.

20. An electronic device, wherein,

the electronic device having a substrate and the film of claim 19 formed on the substrate.

21. An optical component, wherein,

the optical component having a substrate and the film of claim 19 formed on the substrate.