Solventless composition and cured film

Abstract

The present invention addresses the problem of providing a solventless composition that makes it possible to increase film thickness and form a cured film having a low refractive index. Said problem is solved by a solvent-free composition that contains a triazine ring-containing polymer, a crosslinking agent, and hollow silica particles having a space inside the outer shell, and does not contain an organic solvent. The triazine ring-containing polymer contains a repeating unit structure represented by formula (1), has at least one triazine ring terminal, and at least a part of the triazine ring terminal is sealed with an amino group having a crosslinking group. The hollow silica particles are coated with at least one selected from the group consisting of silane compounds represented by formula (44), formula (45), and formula (46). Formula (44): R106 aSi(R107)4-a; Formula (45): [R108 bSi(R109)3-b]2Yc; Formula (46): R110 dSi(R111)4-d

Description

Solvent-free composition and cured film

[0001] The present invention relates to a solventless composition that does not contain an organic solvent, and more specifically to a solventless composition that contains a triazine ring-containing polymer and hollow silica particles and does not contain an organic solvent.

[0002] In recent years, in the development of electronic devices such as liquid crystal displays, organic electroluminescence (EL) displays, touch panels, optical semiconductor (e.g., light-emitting diodes (LEDs)), solid-state imaging devices, organic thin-film solar cells, dye-sensitized solar cells, and organic thin-film transistors (TFTs), there has been a demand for high-performance polymer materials capable of forming low-refractive-index films (e.g., cured films having a refractive index of 1.45 or less at a film thickness of 100 nm) or high-refractive-index films (e.g., cured films having a refractive index of 1.65 or more at a film thickness of 100 nm). Specific properties that are required include 1) heat resistance, 2) transparency, 3) high refractive index, 4) high solubility, 5) low volume shrinkage, 6) high-temperature and high-humidity resistance, and 7) high film hardness.

[0003] As a material having such properties, for example, 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, a high refractive index, high solubility, and low volume shrinkage, and a film-forming composition for producing electronic devices has been proposed (Patent Document 1).

[0004] In particular, for planarizing layers and light-scattering layers in organic EL lighting, a certain film thickness is required, and high refractive index materials have been used to achieve the desired film thickness. Thin films are generally produced by coating compositions in which such high refractive index materials are dissolved in organic solvents. However, there are cases in which highly polar solvents cannot be used to form transparent conductive films. Therefore, solventless compositions that do not contain organic solvents have been proposed (Patent Document 2).

[0005] International Publication No. 2022 / 225020 International Publication No. 2022 / 225017

[0006] Although all of these compositions form cured films having a high refractive index, a solventless composition capable of forming a film having a low refractive index while increasing the film thickness has not been known. Furthermore, solventless compositions are required to be able to maintain high solvent resistance, high transmittance, and low haze even when the film thickness of the cured film formed is large.

[0007] The present invention has been made in view of the above circumstances, and has as its first object to provide a solventless composition that can form a cured film having a low refractive index while enabling a thick film thickness to be achieved. Also, as a second object of the present invention, it has been made to provide a solventless composition that can maintain high solvent resistance, high transmittance, and low haze even when the film thickness of the formed low refractive index film is thick.

[0008] The present inventors have conducted extensive research to solve the above-mentioned problems and have found that by combining a triazine ring-containing polymer, which has been conventionally used as a material for imparting a high refractive index, and a specific structure with specific inorganic fine particles, it may be possible to produce a cured film that has a low refractive index and can be made thick. As a result of further research, the present inventors have completed the present invention.

[0009] That is, although not limited to the following, the present invention and various aspects thereof are as follows [1] to

[11] . [1] A solvent-free composition comprising: a triazine ring-containing polymer; a crosslinking agent; and hollow silica particles having a space inside an outer shell; and containing no organic solvent, wherein the triazine ring-containing polymer comprises a repeating unit structure represented by the following formula (1), has at least one triazine ring terminal, and at least a portion of the triazine ring terminal is blocked with an amino group having a crosslinking group: [Chemical Formula 1] (In formula (1), R and R′ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group; Q represents a divalent group having a ring structure and having 3 to 30 carbon atoms; and * represents a bond.) The hollow silica particles are represented by the following formulas (44), (45), and (46): R １０６ ａ Si(R １０７ ) ４－ａ Formula (44) [R １０８ ｂ Si(R １０９ ) ３－ｂ ] ２ Y ｃ Formula (45) R １１０ ｄ Si(R １１１ ) ４－ｄ Formula (46) (In formula (44), R １０６ are each an alkyl group, a halogenated alkyl group, an alkenyl group, an aryl group, or an organic group having an epoxy group, a (meth)acryloyl group, a mercapto group, an amino group, a ureido group, or a cyano group, and are bonded to a silicon atom by a Si—C bond, and R １０７ each represents an alkoxy group, an acyloxy group, or a halogen atom, a represents an integer of 1 to 3, and in formulas (45) and (46), R １０８ and R １１０ are each an alkyl group having 1 to 3 carbon atoms or an aryl group having 6 to 30 carbon atoms and bonded to a silicon atom by a Si—C bond, and R １０９ and R １１１ each represents an alkoxy group, an acyloxy group, or a halogen atom, Y represents an alkylene group, an NH group, or an oxygen atom, b is an integer of 1 to 3, c is an integer of 0 or 1, and d is an integer of 1 to 3. [2] The solventless composition according to [1], wherein Q in the formula (1) is a group having a structure in which at least two diphenyl ether skeletons represented by the following formula (16) are bonded to each other via a substituted or unsubstituted alkyl group. [Chemical Formula 2] (In formula (16), each A independently represents a halogen atom or a halogenated alkyl group having 1 to 10 carbon atoms, each p independently represents an integer of 0 to 4, and * represents a bond.) [3] The solventless composition according to [2], wherein Q in formula (1) is represented by the following formula (1-2): [Chemical Formula 3] (In formula (1-2), R″ represents hydrogen or halogen, and * represents a bond.) [4] The solventless composition according to [3], wherein Q in formula (1) is represented by the following formula (1-3): [Chemical Formula 4] (In formula (1-3), * represents a bond.) [5] The amino group having a crosslinking group is —NH—R １０２ or the solventless composition according to [1], represented by the following formula (1-4): [Chemical Formula 5] (In formula (1-4), R １０２ represents a bridging group, and * represents a bond.) [6] The R １０２ is a hydroxyalkyl group, a (meth)acryloyloxyalkyl group, or a group represented by the following formula (1-5): (In the formula, A １ represents an alkylene group having 1 to 10 carbon atoms; ２ represents a single bond or the following formula (1-6): A represents a group represented by ３ represents an (a+1)-valent aliphatic hydrocarbon group which may be substituted with a hydroxy group, A ４ represents a hydrogen atom or a methyl group, a represents 1 or 2, and * represents a bond. １０２ is a group selected from a hydroxymethyl group, a 2-hydroxyethyl group, a (meth)acryloyloxymethyl group, a (meth)acryloyloxyethyl group, and groups represented by the following formulas (1-5-1) to (1-5-4): (wherein * represents a bond) [8] The hollow silica particles contain aluminum atoms forming aluminosilicate sites, and when measured by a leaching method, Al is present on the surface of the hollow silica particles. ２ O ３ Converted to SiO ２The aluminum atoms are 100 to 20,000 ppm / SiO per 1 g ２ [9] A cured film comprising a triazine ring-containing polymer and hollow silica particles, wherein the triazine ring-containing polymer contains a repeating unit structure represented by the following formula (1), has at least one triazine ring terminal, and at least a portion of the triazine ring terminal is blocked with an amino group having a crosslinking group: [Chemical Formula 9] (In formula (1), R and R′ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group; Q represents a divalent group having a ring structure and having 3 to 30 carbon atoms; and * represents a bond.) The hollow silica particles are represented by the following formulas (44), (45), and (46): R １０６ ａ Si(R １０７ ) ４－ａ Formula (44) [R １０８ ｂ Si(R １０９ ) ３－ｂ ] ２ Y ｃ Formula (45) R １１０ ｄ Si(R １１１ ) ４－ｄ Formula (46) (In formula (44), R １０６ are each an alkyl group, a halogenated alkyl group, an alkenyl group, an aryl group, or an organic group having an epoxy group, a (meth)acryloyl group, a mercapto group, an amino group, a ureido group, or a cyano group, and are bonded to a silicon atom by a Si—C bond, and R １０７ each represents an alkoxy group, an acyloxy group, or a halogen atom, a represents an integer of 1 to 3, and in formulas (45) and (46), R １０８ and R １１０ are each an alkyl group having 1 to 3 carbon atoms or an aryl group having 6 to 30 carbon atoms and bonded to a silicon atom by a Si—C bond, and R １０９ and R １１１each represents an alkoxy group, an acyloxy group, or a halogen atom, Y represents an alkylene group, an NH group, or an oxygen atom, b is an integer of 1 to 3, c is an integer of 0 or 1, and d is an integer of 1 to 3.)

[10] The cured film according to [9], having a film thickness of 1,000 nm or more and 20,000 nm or less.

[11] The cured film according to [9], having a refractive index lower than that of the triazine ring-containing polymer.

[12] A solvent-free composition comprising: a monomer having an acrylamide skeleton; a crosslinking agent; and hollow silica particles having a space inside an outer shell; and containing no organic solvent, wherein the hollow silica particles are represented by the following formulas (44), (45), and (46): R １０６ ａ Si(R １０７ ) ４－ａ Formula (44) [R １０８ ｂ Si(R １０９ ) ３－ｂ ] ２ Y ｃ Formula (45) R １１０ ｄ Si(R １１１ ) ４－ｄ Formula (46) (In formula (44), R １０６ are each an alkyl group, a halogenated alkyl group, an alkenyl group, an aryl group, or an organic group having an epoxy group, a (meth)acryloyl group, a mercapto group, an amino group, a ureido group, or a cyano group, and are bonded to a silicon atom by a Si—C bond, and R １０７ each represents an alkoxy group, an acyloxy group, or a halogen atom, a represents an integer of 1 to 3, and in formulas (45) and (46), R １０８ and R １１０ are each an alkyl group having 1 to 3 carbon atoms or an aryl group having 6 to 30 carbon atoms and bonded to a silicon atom by a Si—C bond, and R １０９ and R １１１each represents an alkoxy group, an acyloxy group, or a halogen atom; Y represents an alkylene group, an NH group, or an oxygen atom; b is an integer of 1 to 3; c is an integer of 0 or 1; and d is an integer of 1 to 3.

[0010] According to the present invention, it is possible to provide a solventless composition that can form a low refractive index film having a thickness of, for example, 1000 nm or more. In addition, in one aspect of the present invention, it is possible to provide a solventless composition that can maintain high solvent resistance, high transmittance, and low haze even when the thickness of the formed cured film is large.

[0011] Compound P-1 in the Examples １ 1H-NMR spectrum measurement results of Compound P-2 in the example. １ 1A-1C are the results of H-NMR spectrum measurement. 1B-1C are micrographs of the cured film of Example 2-1-1 after solvent exposure. 1C-1C are micrographs of the cured film of Example 2-1-2 after solvent exposure. 1D-1C are micrographs of the cured film of Example 2-2-1 after solvent exposure. 1E-1C are micrographs of the cured film of Example 2-2-2 after solvent exposure.

[0012] The present invention provides a solventless composition comprising a triazine ring-containing polymer, a crosslinking agent, and hollow silica particles having a space inside the outer shell, and characterized by not containing an organic solvent. The solventless composition of the present invention will be described in more detail below. In the present invention, "not containing an organic solvent" means that the composition is substantially free of an organic solvent, and indicates, for example, that the organic solvent content is 10% by mass or less relative to the total mass of the composition. Among the solventless compositions of the present invention, those having an organic solvent content of 8% by mass or less are preferred, those having an organic solvent content of 5% by mass or less are more preferred, and those having an organic solvent content of 3% by mass or less are even more preferred.

[0013] (Triazine Ring-Containing Polymer) The triazine ring-containing polymer contained in the solventless composition of the present invention contains a repeating unit structure represented by the following formula (1). * represents a bond.

[0014] The triazine ring-containing polymer is, for example, a so-called hyperbranched polymer. A hyperbranched polymer is a highly branched polymer having an irregular branching structure. Here, "irregular" means that the branching structure is more irregular than that of a dendrimer, which is a highly branched polymer having a regular branching structure.

[0015] For example, a triazine ring-containing polymer that is a hyperbranched polymer includes, as a structure larger than the repeating unit structure represented by formula (1), a structure (structure A) in which the repeating unit structure represented by formula (1) is bonded to each of three bonds of the repeating unit structure represented by formula (1). In the triazine ring-containing polymer that is a hyperbranched polymer, structure A is distributed throughout the triazine ring-containing polymer except for the terminals.

[0016] In the triazine ring-containing polymer, which is a hyperbranched polymer, the repeating unit structure may essentially consist of only the repeating unit structure represented by formula (1).

[0017] <<R and R'>> In the above formula (1), R and R' each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group. Preferably, R and R' are both hydrogen atoms. In the present invention, the number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 20. In consideration of further improving the heat resistance of the polymer, the number of carbon atoms in the alkyl group is more preferably 1 to 10, and even more preferably 1 to 3. In addition, the structure of the alkyl group is not particularly limited, and may be, for example, linear, branched, cyclic, or a combination of two or more thereof.

[0018] Specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, s-butyl, t-butyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclobutyl, 1,2-dimethyl-cyclopropyl, 2,3-dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, n-hexyl, 1-methyl-n-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, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl- n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl-cyclobutyl, 2,4-dimethyl Examples thereof include 1-n-ethyl-cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-isopropyl-cyclopropyl, 2-isopropyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl, and 2-ethyl-3-methyl-cyclopropyl groups.

[0019] The number of carbon atoms in the alkoxy group is not particularly limited, but is preferably 1 to 20. In consideration of further improving the heat resistance of the polymer, the number of carbon atoms in the alkoxy group is more preferably 1 to 10, and even more preferably 1 to 3. The structure of the alkyl moiety is also not particularly limited, and may be, for example, linear, branched, cyclic, or a combination of two or more thereof.

[0020] Specific examples of the alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, s-butoxy, t-butoxy, n-pentoxy, 1-methyl-n-butoxy, 2-methyl-n-butoxy, 3-methyl-n-butoxy, 1,1-dimethyl-n-propoxy, 1,2-dimethyl-n-propoxy, 2,2-dimethyl-n-propoxy, 1-ethyl-n-propoxy, n-hexyloxy, 1-methyl-n-pentyloxy, 2-methyl-n-pentyloxy, and 3-methyl-n-pentyloxy. pentyloxy, 4-methyl-n-pentyloxy, 1,1-dimethyl-n-butoxy, 1,2-dimethyl-n-butoxy, 1,3-dimethyl-n-butoxy, 2,2-dimethyl-n-butoxy, 2,3-dimethyl-n-butoxy, 3,3-dimethyl-n-butoxy, 1-ethyl-n-butoxy, 2-ethyl-n-butoxy, 1,1,2-trimethyl-n-propoxy, 1,2,2-trimethyl-n-propoxy, 1-ethyl-1-methyl-n-propoxy, and 1-ethyl-2-methyl-n-propoxy groups.

[0021] The number of carbon atoms in the aryl group is not particularly limited, but is preferably 6 to 40. In consideration of further improving the heat resistance of the polymer, the number of carbon atoms in the aryl group is more preferably 6 to 16, and even more preferably 6 to 13. In the present invention, the 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, o-chlorophenyl, m-chlorophenyl, p-chlorophenyl, o-fluorophenyl, p-fluorophenyl, o-methoxyphenyl, p-methoxyphenyl, p-nitrophenyl, p-cyanophenyl, α-naphthyl, β-naphthyl, o-biphenylyl, m-biphenylyl, p-biphenylyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, and 9-phenanthryl groups.

[0022] The number of carbon atoms in the aralkyl group is not particularly limited, but preferably 7 to 20 carbon atoms. The structure of the alkyl portion is not particularly limited and may be, for example, linear, branched, cyclic, or a combination of two or more thereof. In the present invention, the aralkyl group includes aralkyl groups 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 aralkyl group include benzyl, p-methylphenylmethyl, m-methylphenylmethyl, o-ethylphenylmethyl, m-ethylphenylmethyl, p-ethylphenylmethyl, 2-propylphenylmethyl, 4-isopropylphenylmethyl, 4-isobutylphenylmethyl, and α-naphthylmethyl.

[0023] <<Q>> Q in formula (1) is not particularly limited as long as it is a divalent group having a ring structure and having 3 to 30 carbon atoms. The ring structure may be an aromatic ring structure or an alicyclic structure.

[0024] The above Q preferably represents at least one selected from the group represented by formulas (2) to (13).

[0025] The above R １ ~R ９２ each independently represents a hydrogen atom, a halogen atom, a hydroxy group, a carboxy group, a sulfo group, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms; R ９３ and R ９４ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; W １ and W ２ are each independently a single bond, CR ９５ R ９６ (R ９５ and R ９６ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms (which may be joined together to form a ring), or a halogenated alkyl group having 1 to 10 carbon atoms), C=O, O, S, SO, SO ２ , or NR ９７ (R ９７ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a phenyl group. ) Examples of halogen atoms include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of alkyl groups and alkoxy groups include those similar to those described above.

[0026] The halogenated alkyl group having 1 to 10 carbon atoms is one in which at least one hydrogen atom in the alkyl group having 1 to 10 carbon atoms is substituted with a halogen atom, and specific examples thereof include trifluoromethyl, 2,2,2-trifluoroethyl, perfluoroethyl, 3,3,3-trifluoropropyl, 2,2,3,3,3-pentafluoropropyl, 2,2,3,3-tetrafluoropropyl, 2,2,2-trifluoro-1-(trifluoromethyl)ethyl, perfluoropropyl, 4,4,4-trifluorobutyl, 3,3 , 4,4,4-pentafluorobutyl, 2,2,3,3,4,4,4-heptafluorobutyl, perfluorobutyl, 2,2,3,3,4,4,5,5,5-nonafluoropentyl, 2,2,3,3,4,4,5,5-octafluoropentyl, perfluoropentyl, 2,2,3,3,4,4,5,5,6,6,6-undecafluorohexyl, 2,2,3,3,4,4,5,5,6,6-decafluorohexyl, 3,3,4,4,5,5,6,6,6-nonafluorohexyl, and perfluorohexyl groups. In the present invention, in consideration of increasing the solubility of the triazine ring-containing polymer in low-polarity solvents and the like, perfluoroalkyl groups having 1 to 10 carbon atoms are preferred, and particularly perfluoroalkyl groups having 1 to 5 carbon atoms are more preferred, with trifluoromethyl groups being even more preferred.

[0027] Also, X １ and X ２ are each independently a single bond, an alkylene group having 1 to 10 carbon atoms, or a group represented by formula (14). The structure of these alkyl groups, halogenated alkyl groups, alkoxy groups, and alkylene groups is not particularly limited, and may be, for example, linear, branched, cyclic, or a combination of two or more thereof.

[0028]

[0029] The above R ９８ ~R １０１ each independently represents a hydrogen atom, a halogen atom, a carboxy group, a sulfo group, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms; Y １ and Y２ are each independently a single bond or an alkylene group having 1 to 10 carbon atoms. As the halogen atom, alkyl group, halogenated alkyl group, and alkoxy group, R １ ~R ９２ The halogen atom, alkyl group, halogenated alkyl group, and alkoxy group in R ９８ ~R １０１ The structure of the alkyl group and alkoxy group in Y is not particularly limited, and may be, for example, linear, branched, cyclic, or a combination of two or more thereof. １ and Y ２ The structure of the alkylene group in is not particularly limited, and may be, for example, linear, branched, cyclic, or a combination of two or more thereof.

[0030] Examples of the alkylene group having 1 to 10 carbon atoms include methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, etc. The structure of the alkylene group is not particularly limited and may be, for example, linear, branched, cyclic, or a combination of two or more thereof.

[0031] Among these, R １ ~R ９２ and R ９８ ~R １０１ is preferably a hydrogen atom, a halogen atom, a sulfo group, an alkyl group having 1 to 5 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms. １ ~R ９２ and R ９８ ~R １０１ is more preferably a hydrogen atom.

[0032] In particular, Q is preferably at least one of the groups represented by formulas (2) and (5) to (13), and more preferably at least one of the groups represented by formulas (2), (5), (7), (8), and (11) to (13). Specific examples of the divalent groups represented by formulas (2) to (13) include, but are not limited to, those represented by the following formulas:

[0033]

[0034] (In the formula, each A independently represents a halogen atom or a halogenated alkyl group having 1 to 10 carbon atoms. Each p independently represents an integer of 0 to 4. Each q independently represents an integer of 0 to 3. Each r independently represents an integer of 0 to 2. Each s independently represents an integer of 0 to 5. t is an integer of 1 to 6. u is an integer of 1 to 4. However, in each group, the total of p, q, r, and s is 1 or more. "Ph" represents a phenyl group. * represents a bond.)

[0035] Among these, Q is more preferably a divalent group represented by the following formula, since a polymer having a higher refractive index can be obtained.

[0036]

[0037] (In the formula, each A independently represents a halogen atom or a halogenated alkyl group having 1 to 10 carbon atoms. Each p independently represents an integer of 0 to 4. Each q independently represents an integer of 0 to 3. Each r independently represents an integer of 0 to 2, provided that in each group, the total of p, q, and r is 1 or more. "Ph" represents a phenyl group. * represents a bond.)

[0038] Q may contain a m-phenylene group represented by formula (15).

[0039] (In the formula, * represents a bond.)

[0040] Furthermore, Q may contain a group having a diphenyl ether skeleton represented by formula (16), (17), or (18).

[0041] (In the formula, each A independently represents a hydrogen atom, a halogen atom, or a halogenated alkyl group having 1 to 10 carbon atoms. Each p independently represents an integer of 0 to 4. * represents a bond.)

[0042] (In the formula, each A independently represents a hydrogen atom, a halogen atom, or a halogenated alkyl group having 1 to 10 carbon atoms. Each p independently represents an integer of 0 to 4. * represents a bond.) (In the formula, * represents a bond.)

[0043] Furthermore, Q in formula (1) may be, for example, at least one selected from the group represented by formulas (19) to (32). (In the formula, * represents a bond.)

[0044] In the formulas (19) to (32), the R １ and R ２ are each independently 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, with alkylene groups having 1 to 3 carbon atoms being preferred. The alkylene group is more preferably an alkylene group having 1 to 2 carbon atoms, such as a methylene group or an ethylene group, and particularly preferably a methylene group.

[0045] In one embodiment of the present invention, Q in formula (1) may be a group represented by the following formula (16) having a structure in which at least two diphenyl ether skeletons are bonded to each other via a substituted or unsubstituted alkyl group: (In formula (16), each A independently represents a hydrogen atom, a halogen atom, or a halogenated alkyl group having 1 to 10 carbon atoms, and each p independently represents an integer of 0 to 4. * represents a bond.)

[0046] When Q has a structure in which at least two diphenyl ether skeletons represented by formula (16) are bonded to each other via a substituted or unsubstituted alkyl group, the compatibility of the triazine ring-containing polymer with silica particles described below can be improved, and as a result, a cured film having a small refractive index and capable of being thickened can be produced using the solventless composition.

[0047] In one embodiment of the present invention, Q in formula (1) can be represented by the following formula (1-2). (In formula (1-2), R″ represents hydrogen or halogen, and * represents a bond.)

[0048] When Q has the structure of formula (1-2), the compatibility between the triazine ring-containing polymer and silica particles described below can be improved, and as a result, a cured film having a small refractive index and capable of being thickened can be produced using the solventless composition.

[0049] Furthermore, in one embodiment of the present invention, Q in formula (1) can be represented by the following formula (1-3). (In formula (1-3), * represents a bond.)

[0050] When Q has the structure of formula (1-3), even if the triazine ring-containing polymer does not contain a halogenated alkyl group, it is possible to improve compatibility with silica particles, which will be described later.

[0051] <Amino group having a crosslinking group> The triazine ring-containing polymer contained in the solventless composition of the present invention has at least one triazine ring terminal, and at least a portion of this triazine ring terminal is blocked with an amino group having a crosslinking group. The triazine ring-containing polymer has at least one triazine ring terminal, and this terminal triazine ring may be bonded to the same triazine ring terminal via an amino group having a crosslinking group. When there are multiple triazine ring terminals, each may be bonded to a different triazine ring terminal.

[0052] The number of crosslinking groups in the crosslinking group-containing amino group is not particularly limited and can be any number, but in consideration of solvent resistance, the number is preferably 1 to 4, more preferably 1 to 2, and even more preferably 1. When the crosslinking group-containing amino group has multiple crosslinking groups, the multiple crosslinking groups may have the same structure or different structures.

[0053] The amino group having a crosslinking group is represented, for example, by the following formula (X). (In the formula, Z represents a group having a crosslinking group, and * represents a bond.)

[0054] In formula (X), Z may be the bridging group itself. The bridging group is preferably linked to the amino group by an arylene group.

[0055] In one embodiment of the present invention, the amino group having a bridging group is —NH—R １０２ , or expressed by the following formula (1-4). (In formula (1-4), R １０２ represents a bridging group. * represents a bond.

[0056] The amino group having a crosslinking group is preferably represented by the following formula (33). (In the formula, R １０２ represents a bridging group. * represents a bond.

[0057] Examples of the crosslinking group include a hydroxy-containing group, a vinyl-containing group, an epoxy-containing group, an oxetane-containing group, a carboxy-containing group, a sulfo-containing group, a thiol-containing group, and a (meth)acryloyl-containing group.

[0058] Examples of the hydroxy-containing group include a hydroxy group and a hydroxyalkyl group, with a hydroxyalkyl group having 1 to 10 carbon atoms being preferred, a hydroxyalkyl group having 1 to 5 carbon atoms being more preferred, and a hydroxyalkyl group having 1 to 3 carbon atoms being even more preferred. Examples of the hydroxyalkyl group having 1 to 10 carbon atoms include hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 5-hydroxypentyl, 6-hydroxyhexyl, 7-hydroxyheptyl, 8-hydroxyoctyl, 9-hydroxynonyl, 10-hydroxydecyl, 2-hydroxy-1-methylethyl, 2-hydroxy-1,1-dimethylethyl, 3-hydroxy-1-methylpropyl, 3-hydroxy-2-methylpropyl, 3-hydroxy-1,1-dimethylpropyl, 3-hydroxy-1,2-dimethylpropyl, 3-hydroxy-2,2-dimethylpropyl, 4-hydroxypropyl, Examples thereof include those in which the carbon atom to which the hydroxy group is bonded is a primary carbon atom, such as 4-1-methylbutyl, 4-hydroxy-2-methylbutyl, and 4-hydroxy-3-methylbutyl groups; and those in which the carbon atom to which the hydroxy group is bonded is a secondary or tertiary carbon atom, such as 1-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 1-hydroxybutyl, 2-hydroxybutyl, 1-hydroxyhexyl, 2-hydroxyhexyl, 1-hydroxyoctyl, 2-hydroxyoctyl, 1-hydroxydecyl, 2-hydroxydecyl, 1-hydroxy-1-methylethyl, and 2-hydroxy-2-methylpropyl groups.

[0059] In particular, in consideration of improving heat resistance and resistance to high temperatures and high humidity, it is preferable that the carbon atom to which the hydroxy group is bonded is a primary carbon atom, and among these, a hydroxyalkyl group having 1 to 5 carbon atoms is more preferable, a hydroxyalkyl group having 1 to 3 carbon atoms is even more preferable, a hydroxymethyl group and a 2-hydroxyethyl group are even more preferable, and a 2-hydroxyethyl group is most preferable.

[0060] Examples of the vinyl-containing group include alkenyl groups having 2 to 10 carbon atoms and a vinyl group at the terminal, such as ethenyl, 1-propenyl, allyl, isopropenyl, 1-butenyl, 2-butenyl, and 2-pentenyl.

[0061] Examples of epoxy-containing groups include epoxy, glycidyl, and glycidyloxy groups, and specific examples include glycidylmethyl, 2-glycidylethyl, 3-glycidylpropyl, and 4-glycidylbutyl groups.

[0062] Examples of oxetane-containing groups include oxetan-3-yl, (oxetan-3-yl)methyl, 2-(oxetan-3-yl)ethyl, 3-(oxetan-3-yl)propyl, and 4-(oxetan-3-yl)butyl groups.

[0063] Examples of the carboxy-containing group include a carboxy group and a carboxyalkyl group having 2 to 10 carbon atoms. As the carboxyalkyl group having 2 to 10 carbon atoms, the carbon atom to which the carboxy group is bonded is preferably a primary carbon atom, and specific examples include a carboxymethyl group, a 2-carboxyethyl group, a 3-carboxypropyl group, and a 4-carboxybutyl group.

[0064] Examples of the sulfo-containing group include a sulfo group and a sulfoalkyl group having 1 to 10 carbon atoms. As the sulfoalkyl group having 1 to 10 carbon atoms, the carbon atom to which the sulfo group is bonded is preferably a primary carbon atom, and specific examples include sulfomethyl, 2-sulfoethyl, 3-sulfopropyl, and 4-sulfobutyl groups.

[0065] Examples of the thiol-containing group include a thiol group and a mercaptoalkyl group having 1 to 10 carbon atoms. As the mercaptoalkyl group having 1 to 10 carbon atoms, the carbon atom to which the thiol group is bonded is preferably a secondary carbon atom, and specific examples include mercaptomethyl, 2-mercaptoethyl, 3-mercaptopropyl, and 4-mercaptobutyl groups.

[0066] Examples of the (meth)acryloyl-containing group include a (meth)acryloyl group, a (meth)acryloyloxyalkyl group, and a group represented by the following formula (i). Of these, a (meth)acryloyloxyalkyl group having an alkylene group having 1 to 10 carbon atoms and a group represented by the following formula (i) are preferred, and a group represented by the following formula (i) is more preferred. (In the formula, A １ represents an alkylene group having 1 to 10 carbon atoms; ２ represents a single bond or the following formula (j): A represents a group represented by ３ represents an (a+1)-valent aliphatic hydrocarbon group which may be substituted with a hydroxy group, A ４ represents a hydrogen atom or a methyl group, a represents 1 or 2, and * represents a bond.

[0067] Examples of the alkylene group contained in the (meth)acryloyloxyalkyl group having an alkylene group (alkanediyl group) 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, and decamethylene. In consideration of improving heat resistance and high-temperature, high-humidity resistance, among these, those having an alkylene group having 1 to 5 carbon atoms are preferred, those having an alkylene group having 1 to 3 carbon atoms are more preferred, and those having an alkylene group having 1 or 2 carbon atoms are more preferred.

[0068] 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.

[0069] In formula (i), A １is an alkylene group having 1 to 10 carbon atoms, preferably an alkylene group having 1 to 5 carbon atoms, and more preferably a methylene group, an ethylene group, or a propylene group. Examples of the alkylene group having 1 to 10 carbon atoms include the same alkylene groups as those contained in the above-mentioned (meth)acryloyloxyalkyl group.

[0070] A ２ represents a single bond or a group represented by formula (j), and a group represented by formula (j) is preferred.

[0071] A ３ is an (a+1)-valent aliphatic hydrocarbon group which may be substituted with a hydroxy group, and specific examples thereof include alkylene groups having 1 to 5 carbon atoms and the following formulae (k-1) to (k-3): (wherein * represents a bond), and alkylene groups having 1 to 5 carbon atoms are preferred, alkylene groups having 1 to 3 carbon atoms are more preferred, and methylene and ethylene groups are even more preferred. ３ The alkylene group of A １ Among the alkylene groups exemplified above, alkylene groups having 1 to 5 carbon atoms can be mentioned.

[0072] a represents 1 or 2, with 1 being preferred.

[0073] A preferred embodiment of the group represented by formula (i) is one represented by the following formula (i-1). (In the formula, A １ represents an alkylene group having 1 to 10 carbon atoms; ３ represents an (a+1)-valent aliphatic hydrocarbon group which may be substituted with a hydroxy group, A ４ represents a hydrogen atom or a methyl group, a represents 1 or 2, and * represents a bond.

[0074] More preferred embodiments of the group represented by formula (i) include those represented by the following formulae (i-2) to (i-5). (In the formula, * represents a bond.)

[0075] Specific examples of the amino group having a crosslinking group include, but are not limited to, those represented by the following formulae:

[0076] (In the formula, * represents a bond.)

[0077] An amino group having a (meth)acryloyloxyalkyl group can be introduced by a method using a corresponding (meth)acryloyloxyalkylamino compound, or by a method in which an amino group having a hydroxyalkyl group is introduced into a triazine ring-containing polymer, and then a (meth)acrylic acid halide or glycidyl (meth)acrylate is allowed to react with the hydroxy group contained in the hydroxyalkyl group.

[0078] The amino group having a group represented by formula (i) can be introduced by a method using an amino compound having the desired crosslinking group, or by a method in which an amino group having a hydroxyalkyl group is introduced into a triazine ring-containing polymer, and then a (meth)acrylic acid ester compound having an isocyanate group represented by the following formula (i') is allowed to react with the hydroxy group contained in the hydroxyalkyl group: (In the formula, A ３ represents an (a+1)-valent aliphatic hydrocarbon group which may be substituted with a hydroxy group, A ４ represents a hydrogen atom or a methyl group, a represents 1 or 2, and * represents a bond.

[0079] Specific examples of (meth)acryloyloxyalkylamino compounds include ester compounds obtained by reacting a (meth)acrylic acid halide or glycidyl (meth)acrylate with the hydroxy group of the above-mentioned hydroxyalkylamino compound. Examples of the above-mentioned (meth)acrylic acid halide include (meth)acrylic acid chloride, (meth)acrylic acid bromide, and (meth)acrylic acid iodide. Specific examples of (meth)acrylic acid ester compounds having an isocyanate group represented by formula (i') above include 2-isocyanatoethyl acrylate, 2-isocyanatoethyl methacrylate, and 1,1-(bisacryloyloxymethyl)ethyl isocyanate. In the present invention, 2-isocyanatoethyl acrylate is preferred from the viewpoint of a simple synthesis method.

[0080] In one embodiment of the present invention, the bridging group R １０２ is a hydroxyalkyl group, a (meth)acryloyloxyalkyl group, or a group represented by the following formula (1-5): (In the formula, A １ represents an alkylene group having 1 to 10 carbon atoms; ２ represents a single bond or the following formula (1-6): A represents a group represented by ３ represents an (a+1)-valent aliphatic hydrocarbon group which may be substituted with a hydroxy group, A ４ represents a hydrogen atom or a methyl group, a represents 1 or 2, and * represents a bond.

[0081] In one embodiment of the present invention, the R １０２ is a group selected from a hydroxymethyl group, a 2-hydroxyethyl group, a (meth)acryloyloxymethyl group, a (meth)acryloyloxyethyl group, and groups represented by the following formulas (1-5-1) to (1-5-4). (In the formula, * represents a bond.)

[0082] Crosslinking group R １０２ However, the above structure can improve the heat resistance of the triazine ring-containing polymer and the solvent resistance (crack resistance) of the resulting film.

[0083] The weight-average molecular weight of the triazine ring-containing polymer in the present invention is not particularly limited, but is preferably 500 to 500,000, more preferably 500 to 100,000. From the viewpoints of further improving heat resistance and reducing shrinkage, it is preferably 2,000 or more. From the viewpoint of reducing the viscosity of the resulting composition, it is preferably 50,000 or less, more preferably 30,000 or less, even more preferably 25,000 or less, and still more preferably 10,000 or less. The weight-average molecular weight in the present invention is the average molecular weight obtained by gel permeation chromatography (hereinafter referred to as GPC) analysis in terms of standard polystyrene.

[0084] <Method for producing triazine ring-containing polymer> The above-mentioned triazine ring-containing polymer (hyperbranched polymer) contained in the solventless composition of the present invention can be produced in accordance with the method disclosed in the above-mentioned WO 2010 / 128661.

[0085] For example, as shown in Scheme 1 below, the triazine ring-containing polymer (37) can be obtained by reacting a triazine compound (34) with a diamino compound (35) in an appropriate organic solvent, followed by reaction with an amino compound (36) having a group (Z) having a crosslinking group, which is an end-capping agent. (In the formula, X's each independently represent a halogen atom, Q represents a divalent group having a ring structure and 3 to 30 carbon atoms, and Z represents a group having a crosslinking group.)

[0086] In the above scheme 1, the charging ratio of the diamino compound (35) is arbitrary as long as the target polymer is obtained, but 0.01 to 10 equivalents of the diamino compound (35) per equivalent of the triazine compound (34) is preferred, and 0.7 to 5 equivalents is more preferred. The diamino compound (35) may be added neat or as a solution dissolved in an organic solvent, but the latter method is preferred in consideration of ease of operation and ease of reaction control. The reaction temperature may be set appropriately within the range from the melting point to the boiling point of the solvent used, but is preferably about -30°C to 150°C, and more preferably -10°C to 100°C.

[0087] Another embodiment is the method shown in Scheme 2 below. In this method, the triazine ring-containing polymer (43) is prepared by reacting a triazine compound (38) with a diamino compound (39) in an appropriate organic solvent, followed by the addition of a hydroxyalkyl group (A １ The triazine ring-containing polymer (41) can be obtained by reacting the triazine ring-containing polymer (41) with an arylamino compound (40) having a hydroxyl group (a group corresponding to a hydroxyalkyl group) (a group corresponding to a hydroxyalkyl group) of the triazine ring-containing polymer (41) (first step), and then reacting a (meth)acrylic acid ester compound (42) having an isocyanate group with the hydroxyl group of the hydroxyalkyl group contained in the triazine ring-containing polymer (41) (second step). (In the formula, X's each independently represent a halogen atom, Q's each represent a divalent group having a ring structure and having 3 to 30 carbon atoms, and A １ A' represents a hydroxyalkyl group having 1 to 10 carbon atoms; ３ represents an (a+1)-valent aliphatic hydrocarbon group which may be substituted with a hydroxy group, A ４ represents a hydrogen atom or a methyl group, A １ represents an alkylene group having 1 to 10 carbon atoms.

[0088] In the above scheme 2, the charge ratio and addition method of the diamino compound (39) in the first step, and the reaction temperature in the reaction until the triazine ring-containing polymer (41) is obtained can be the same as those explained in scheme 1. In addition, in the second step, the charge ratio of the (meth)acrylic acid ester compound (42) having an isocyanate group to the triazine ring-containing polymer (41) can be the same as that explained in scheme 1. １ The amount of the hydroxyalkyl group (A′) contained in the triazine ring-containing polymer (41) can be arbitrarily set depending on the ratio of the hydroxyalkyl group (A′) to the isocyanate group, and is preferably 0.1 to 10 equivalents, more preferably 0.5 to 5 equivalents, even more preferably 0.7 to 3 equivalents, and even more preferably 0.9 to 1.5 equivalents relative to 1 equivalent of the arylamino compound (40) having a hydroxyalkyl group used. １ When all of the (meth)acrylic acid ester compounds (42) are groups represented by formula (i), the charge ratio is preferably 1.0 to 10 equivalents, more preferably 1.0 to 5 equivalents, even more preferably 1.0 to 3 equivalents, and still more preferably 1.0 to 1.5 equivalents, of the (meth)acrylic acid ester compound (42) relative to 1 equivalent of the arylamino compound (40) having a hydroxyalkyl group used. The reaction temperature in this reaction is the same as the reaction temperature in the reaction to obtain the triazine ring-containing polymer (41); however, in consideration of preventing polymerization of the (meth)acryloyl groups during the reaction, the reaction temperature is preferably 30 to 80°C, more preferably 40 to 70°C, and even more preferably 50 to 60°C.

[0089] In the second step of Scheme 2, the reaction may be carried out in the presence of a polymerization inhibitor to prevent polymerization of the (meth)acryloyl group during the reaction. Examples of polymerization inhibitors include N-methyl-N-nitrosoaniline, N-nitrosophenylhydroxyamine or its salts, benzoquinones, phenolic polymerization inhibitors, and phenothiazine. Among these, N-nitrosophenylhydroxyamine or its salts are preferred due to their excellent polymerization inhibitory effect. Examples of N-nitrosophenylhydroxyamine salts include N-nitrosophenylhydroxyamine ammonium salt and N-nitrosophenylhydroxyamine aluminum salt. Examples of benzoquinones include p-benzoquinone and 2-methyl-1,4-benzoquinone. Examples of phenolic polymerization inhibitors include hydroquinone, p-methoxyphenol, 4-t-butylcatechol, 2-t-butylhydroquinone, and 2,6-di-t-butyl-4-methylphenol. The amount of the polymerization inhibitor used is not particularly limited, and may be, for example, 1 ppm to 200 ppm, or 10 ppm to 100 ppm, in mass ratio relative to the (meth)acrylic acid ester compound having an isocyanate group represented by formula (i'). By using the polymerization inhibitor, the second-stage reaction can be carried out while suppressing polymerization of the (meth)acryloyl group, even if the reaction temperature is raised to about 60° C. to 80° C.

[0090] The organic solvent used in the above scheme can be any of various solvents commonly used in this type of reaction, and examples thereof include tetrahydrofuran, dioxane, dimethyl sulfoxide; amide solvents such as N,N-dimethylformamide, N-methyl-2-pyrrolidone, tetramethylurea, hexamethylphosphoramide, N,N-dimethylacetamide, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, N-methyl-2-piperidone, N,N'-dimethylethyleneurea, N,N,N',N'-tetramethylmalonic acid amide, N-methylcaprolactam, N-acetylpyrrolidine, N,N-diethylacetamide, N-ethyl-2-pyrrolidone, N,N-dimethylpropionic acid amide, N,N-dimethylisobutyramide, N-methylformamide, and N,N'-dimethylpropyleneurea; and mixed solvents thereof. Among these, N,N-dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, and mixtures thereof are preferred, and N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 3-methoxy-N,N-dimethylpropanamide, and 3-butoxy-N,N-dimethylpropanamide are particularly suitable.

[0091] In addition, in the reaction of Scheme 1 above, various bases that are commonly used may be added during or after polymerization. Specific examples of this base include potassium carbonate, potassium hydroxide, sodium carbonate, sodium hydroxide, sodium bicarbonate, 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, 2,2,6,6-tetramethyl-N-methylpiperidine, pyridine, 4-dimethylaminopyridine, N-methylmorpholine, 2-aminoethanol, ethyldiethanolamine, and diethylaminoethanol. The amount of base added is preferably 1 to 100 equivalents, and more preferably 1 to 10 equivalents, relative to 1 equivalent of triazine compound (34). These bases may be used in the form of an aqueous solution. It is preferable that no raw material components remain in the resulting polymer, but some raw materials may remain as long as the effects of the present invention are not impaired. After completion of the reaction, the product can be easily purified by a reprecipitation method or the like.

[0092] Known methods may be employed for the terminal-capping method using an amino compound having a crosslinking group. In this case, the amount of the terminal-capping agent 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, relative to 1 equivalent of halogen atoms derived from the excess triazine compound not used in the polymerization reaction. The reaction solvent and reaction temperature may be the same as those described for the reaction in Scheme 1 or the first-step reaction in Scheme 2 above. The terminal-capping agent may be charged simultaneously with the diamino compound (35) or (39). Terminal blocking may also be performed with two or more groups using an unsubstituted amino compound not having a crosslinking group.

[0093] The content of the triazine ring-containing polymer in the solventless composition is not particularly limited, but is preferably from 1 to 50% by mass, more preferably from 5 to 30% by mass.

[0094] <Crosslinking Agent> The solventless composition of the present invention contains a crosslinking agent. The crosslinking agent that can be used in the present invention is not particularly limited as long as it is a compound that can undergo a crosslinking reaction alone or together with the above-mentioned triazine ring-containing polymer to form a crosslinked structure. Examples of such compounds include melamine-based compounds having a crosslinking substituent such as a methylol group or a methoxymethyl group (e.g., phenoplast compounds, aminoplast compounds, etc.), substituted urea-based compounds, compounds containing a crosslinking substituent such as an epoxy group or an oxetane group (e.g., multifunctional epoxy compounds, multifunctional oxetane compounds, etc.), compounds containing a blocked isocyanate group, compounds containing an acid anhydride group, and compounds containing a (meth)acrylic group. From the viewpoint of heat resistance and storage stability, compounds containing an epoxy group, a blocked isocyanate group, or a (meth)acrylic group are preferred. In particular, compounds having a blocked isocyanate group and multifunctional epoxy compounds and / or multifunctional (meth)acrylic compounds that provide a photocurable composition without the use of an initiator are preferred.

[0095] 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-diglycidylphenyl glycidyl ether, 1,1,3-tris[p-(2,3-epoxypropoxy)phenyl]propane, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, 4,4'-methylenebis(N,N-diglycidylaniline), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, trimethylolethane triglycidyl ether, bisphenol-A diglycidyl ether, and pentaerythritol polyglycidyl ether.

[0096] Commercially available products include epoxy resins having at least two epoxy groups, such as YH-434 and YH434L (manufactured by Nippon Steel Chemical & Material Co., Ltd.); epoxy resins having a cyclohexene oxide structure, such as Epolead GT-401, GT-403, GT-301, GT-302, Celloxide 2021, and 3000 (manufactured by Daicel Corporation); bisphenol A epoxy resins, such as jER1001, jER1002, jER1003, jER1004, jER1007, jER1009, jER1010, and jER828 (all manufactured by Mitsubishi Chemical Corporation); and bisphenol F epoxy resins. jER807 (manufactured by Mitsubishi Chemical Corporation), phenol novolac epoxy resins jER152 and jER154 (both manufactured by Mitsubishi Chemical Corporation), EPPN201 and EPPN202 (both manufactured by Nippon Kayaku Co., Ltd.), cresol novolac epoxy resins EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, and EOCN-1027 (all manufactured by Nippon Kayaku Co., Ltd.), jER180S75 (manufactured by Mitsubishi Chemical Corporation), alicyclic epoxy resins Denacol EX-252 (manufactured by Nagase ChemteX Corporation), CY175, CY177, and CY179 (all manufactured by CIBA-GEIGY Co., Ltd.), AG), Araldite CY-182, CY-192, and CY-184 (all manufactured by CIBA-GEIGY AG), Epiclon 200 and 400 (all manufactured by DIC Corporation), jER871 and jER872 (all manufactured by Mitsubishi Chemical Corporation), ED-5661 and ED-5662 (all manufactured by Celanese Coatings Co., Ltd.), and aliphatic polyglycidyl ethers such as Denacol EX-611, EX-612, EX-614, EX-622, EX-411, EX-512, EX-522, EX-421, EX-313, EX-314, and EX-321 (manufactured by Nagase ChemteX Corporation) can also be used.

[0097] The polyfunctional (meth)acrylic compound is not particularly limited as long as it has two or more (meth)acrylic groups in one molecule. Specific examples thereof include ethylene glycol diacrylate, ethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, ethoxylated bisphenol A diacrylate, ethoxylated bisphenol A dimethacrylate, ethoxylated trimethylolpropane triacrylate, ethoxylated trimethylolpropane trimethacrylate, ethoxylated glycerin triacrylate, ethoxylated glycerin trimethacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetramethacrylate, ethoxylated dipentaerythritol hexaacrylate, polyglycerin monoethylene oxide, ethylene glycol diacrylate, polyethylene glycol dimethacrylate, ethoxylated bisphenol A diacrylate, ethoxylated trimethylolpropane trimethacrylate, ethoxylated glycerin triacrylate, ethoxylated pentaerythritol tetramethacrylate, ethoxylated dipentaerythritol hexaacrylate, polyglycerin monoethylene oxide, ethylene glycol diacrylate, polyethylene glycol dimethacrylate, ethoxylated bisphenol A diacrylate, ethoxylated trimethylolpropane trimethacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated dipentaerythritol hexaacrylate, polyglycerin monoethylene oxide, ethylene glycol diacrylate ... ethylene glycol diacrylate, ethylene glycol diacrylate, ethylene glycol diacrylate, ethylene glycol diacrylate, ethylene glycol diacrylate, ethylene glycol diacrylate, ethylene glycol diacrylate, ethylene glycol diacrylate, ethylene glycol diacrylate, ethylene glycol diacrylate, ethylene glycol diacrylate, ethylene glycol diacrylate, ethylene glycol diacrylate Examples of the polyacrylate include polyglycerin polyethylene glycol polyacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tricyclodecane dimethanol diacrylate, tricyclodecane dimethanol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, and polybasic acid-modified acrylic oligomers.

[0098] The polyfunctional (meth)acrylic compound is commercially available, and specific examples thereof include NK Ester A-200, A-400, A-600, A-1000, A-9300 (tris(2-acryloyloxyethyl) isocyanurate), A-9300-1CL, A-TMPT, UA-53H, 1G, 2G, 3G, 4G, 9G, 14G, 23G, ABE-300, A-BPE-4, A-BPE-6, A-BPE-10, A-BPE-20, and A-BPE-3. 0, BPE-80N, BPE-100N, BPE-200, BPE-500, BPE-900, BPE-1300N, A-GLY-3E, A-GLY-9E, A-GLY-20E, A-TMPT-3EO, A-TMPT-9EO, AT-20E, ATM-4E, ATM-35E, A-DPH, A-TMPT, A-DCP, A-HD-N, TMPT, DCP, NPG, HD-N, A-DPH-12E, A-DPH-48E, A-DPH-96E, NK Oligo U-15HA, NK Polymer Vanarasin GH-1203, APG-100, APG-200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD (registered trademark) DPHA, same N PGDA, PET30, DPEA-12, PEG400DA, THE-330, RP-1040, DN-0075 (all of which are manufactured by Nippon Kayaku Co., Ltd. ), Aronix M-210, Aronix M-303, Aronix M-305, Aronix M-306, Aronix M-309, Aronix M-306, Aronix M-310, Aronix M-313, Aronix M-315, M-321, M-350, M-360, M-400, M-402, M-403, M-404, M-405, M-4 06, M-408, M-450, M-452, M-460 (manufactured by Toagosei Co., Ltd.), DPGDA, HDDA, TPGDA, HPND A, PETIA, PETRA, TMPTA, TMPEOTA, EBECRYL11, 40, 135, 140, 145, 150, 180 , 1142, 204, 205, 210, 215, 220, 230, 244, 245, 265, 270, 280 / 15IB, 284, 294 / 25HD, 303, 436, 438, 446, 450, 524, 525, 600, 605, 645,648, 767, 770, 800, 810, 811, 812, 846, 851, 852, 853, 860, 884, 885, 1259, 1290, 1606, 1830, 1870, 3500, 3603, 3608, 3700, 3701, 3702, 3703, 3708, 4820, 4858, 5129, 6040, 8210, 8454, 8301R, 8307, 8311, 8402, 8405, 8411, 8465, 8701, 8800, 8804, 8807, 9270, 9227EA, 936, KRM8200, 8200AE, 7735, 8296, 08452, 8904, 8528, 8912, OTA480, IRR214-K, 616, 679, 742, 793, PEG400DA-D(ACA)Z200M, Z230AA, Z250, Z251, Z300, Z320, and Z254F (all manufactured by Daicel Allnex Co., Ltd.). The polybasic acid-modified acrylic oligomer is also commercially available, and specific examples thereof include Aronix M-510 and 520 (both manufactured by Toagosei Co., Ltd.).

[0099] The compound having an acid anhydride group is not particularly limited as long as it is a carboxylic acid anhydride obtained by dehydration condensation of two molecules of carboxylic acid, and specific examples thereof include compounds having one acid anhydride group in the molecule such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, maleic anhydride, succinic anhydride, octyl succinic anhydride, and dodecenyl succinic anhydride; 1,2,3,4-cyclobutanetetracarboxylic dianhydride, pyromellitic anhydride, and 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene. Examples of the dianhydride include succinic dianhydride, bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic dianhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 1,2,3,4-butanetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, and 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, which have two acid anhydride groups in the molecule.

[0100] The compound containing a blocked isocyanate group is not particularly limited as long as it has two or more blocked isocyanate groups in one molecule, in which the isocyanate group (—NCO) is blocked with a suitable protecting group, and when exposed to high temperatures during thermal curing, the protecting group (blocking moiety) is thermally dissociated and removed, and the resulting isocyanate group undergoes a crosslinking reaction with a crosslinking group (e.g., a hydroxy-containing group) of the triazine ring-containing polymer included in the present invention. For example, a compound having two or more groups represented by the following formula in one molecule (note that these groups may be the same or different from each other) may be mentioned. (In the formula, R ｂ represents an organic group in the block portion.)

[0101] Such compounds 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 compounds having two or more isocyanate groups in one molecule include polyisocyanates such as isophorone diisocyanate, 1,6-hexamethylene diisocyanate, methylenebis(4-cyclohexylisocyanate), and trimethylhexamethylene diisocyanate, as well as dimers and trimers thereof, and reaction products of these with diols, triols, diamines, or triamines. Examples of the blocking agent include alcohols such as methanol, ethanol, isopropanol, n-butanol, 2-ethoxyhexanol, 2-N,N-dimethylaminoethanol, 2-ethoxyethanol, and cyclohexanol; phenols such as phenol, o-nitrophenol, p-chlorophenol, and o-, m-, or p-cresol; lactams such as ε-caprolactam; oximes such as acetone oxime, methyl ethyl ketone oxime, methyl isobutyl ketone oxime, cyclohexanone oxime, acetophenone oxime, and benzophenone oxime; pyrazoles such as pyrazole, 3,5-dimethylpyrazole, and 3-methylpyrazole; and thiols such as dodecanethiol and benzenethiol.

[0102] Compounds containing a blocked isocyanate group are also commercially available, and specific examples thereof include Takenate (registered trademark) B-830, B-815N, B-842N, B-870N, B-874N, B-882N, B-7005, B-7030, B-7075, and B-5010 (all manufactured by Mitsui Chemicals, Inc.), Duranate (registered trademark) 17B-60PX, TPA-B80E, MF-B60X, MF-K60X, and E402-B80T (all manufactured by Asahi Kasei Corporation), Karenz MOI-BM (registered trademark) (all manufactured by Showa Denko K.K.), and TRIXENE (registered trademark). Examples include BI7950, BI7951, BI7960, BI7961, BI7963, BI7982, BI7990, BI7991, and BI7992 (all manufactured by Baxenden Chemical Co.).

[0103] The aminoplast compound is not particularly limited as long as it has two or more methoxymethylene groups in one molecule, and examples thereof include melamine compounds such as the Cymel series, including hexamethoxymethylmelamine CYMEL (registered trademark) 303, tetrabutoxymethylglycoluril 1170, and tetramethoxymethylbenzoguanamine 1123 (all manufactured by Nippon Cytec Industries Co., Ltd.); and the Nikalac series, including methylated melamine resins Nikalac (registered trademark) MW-30HM, MW-390, MW-100LM, and MX-750LM; and methylated urea resins MX-270, MX-280, and MX-290 (all manufactured by Sanwa Chemical Co., Ltd.). The oxetane compound is not particularly limited as long as it has two or more oxetanyl groups in one molecule, and examples thereof include OXT-221, OX-SQ-H, and OX-SC (all manufactured by Toagosei Co., Ltd.), which contain oxetanyl groups.

[0104] The phenoplast compound has two or more hydroxymethylene groups per molecule, and when exposed to high temperatures during heat curing, it undergoes a crosslinking reaction via a dehydration condensation reaction with the phenolic hydroxyl groups of the triazine ring-containing polymer of the present invention. Examples of the phenoplast compound include 2,6-dihydroxymethyl-4-methylphenol, 2,4-dihydroxymethyl-6-methylphenol, bis(2-hydroxy-3-hydroxymethyl-5-methylphenyl)methane, bis(4-hydroxy-3-hydroxymethyl-5-methylphenyl)methane, 2,2-bis(4-hydroxy-3,5-dihydroxymethylphenyl)propane, bis(3-formyl-4-hydroxyphenyl)methane, bis(4-hydroxy-2,5-dimethylphenyl)formylmethane, and α,α-bis(4-hydroxy-2,5-dimethylphenyl)-4-formyltoluene. Phenoplast compounds are also available as commercially available products, and specific examples thereof include 26DMPC, 46DMOC, DM-BIPC-F, DM-BIOC-F, TM-BIP-A, BISA-F, BI25X-DF, and BI25X-TPA (all manufactured by Asahi Organic Chemicals Co., Ltd.).

[0105] Among these, polyfunctional (meth)acrylic compounds are preferred because the curing reaction proceeds quickly, and the following polyfunctional (meth)acrylic compounds having an isocyanuric acid skeleton are more preferred because they have excellent compatibility with triazine ring-containing polymers. Examples of such polyfunctional (meth)acrylic compounds include NK Ester A-9300 and A-9300-1CL (both manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0106] (In the formula, R １０３ ~R １０５ are each independently a monovalent organic group having at least one (meth)acrylic group at its terminal.

[0107] Furthermore, from the viewpoint of further improving the curing rate and enhancing the solvent resistance, acid resistance, and alkali resistance of the resulting cured film, a polyfunctional (meth)acrylic compound that is liquid at 25°C and has a viscosity of 5,000 mPa·s or less (hereinafter also referred to as a low-viscosity crosslinking agent) can also be used. The viscosity of the low-viscosity crosslinking agent may be preferably 1 Pa·s to 3,000 mPa·s, more preferably 1 Pa·s to 1,000 mPa·s, and even more preferably 1 Pa·s to 500 mPa·s. The low-viscosity crosslinking agent is preferably used alone or in combination of two or more types, or in combination with the above-mentioned polyfunctional (meth)acrylic compound having an isocyanuric acid skeleton. Such low-viscosity crosslinking agents are also commercially available, and examples thereof include crosslinking agents having a relatively long chain length between (meth)acrylic groups, such as NK Ester A-GLY-3E (85 mPa·s, 25°C), A-GLY-9E (95 mPa·s, 25°C), A-GLY-20E (200 mPa·s, 25°C), A-TMPT-3EO (60 mPa·s, 25°C), A-TMPT-9EO, ATM-4E (150 mPa·s, 25°C), and ATM-35E (350 mPa·s, 25°C) (all manufactured by Shin-Nakamura Chemical Co., Ltd.), among the above-mentioned polyfunctional (meth)acrylic compounds.

[0108] Furthermore, in order to improve the alkali resistance of the resulting cured film, it is preferable to use at least one of NK Ester A-GLY-20E (manufactured by Shin-Nakamura Chemical Co., Ltd.) and NK Ester ATM-35E (manufactured by Shin-Nakamura Chemical Co., Ltd.) in combination with the polyfunctional (meth)acrylic compound having an isocyanuric acid skeleton.

[0109] Furthermore, when a film made of the triazine ring-containing polymer of the present invention is laminated on a protective film such as a PET or polyolefin film and irradiated with light through the protective film, the film-laminated film can also be cured well without being inhibited by oxygen. 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 gives a film with good peelability.

[0110] The above-mentioned crosslinking agents may be used alone or in combination of two or more. The content of the crosslinking agent in the pattern-forming composition of the present invention is preferably 1 to 200 parts by mass relative to 100 parts by mass of the triazine ring-containing polymer. In consideration of solvent resistance, the lower limit is preferably 2 parts by mass, more preferably 5 parts by mass. Furthermore, in consideration of controlling the refractive index and residue in unexposed areas, the upper limit is preferably 150 parts by mass, more preferably 100 parts by mass, and even more preferably 90 parts by mass.

[0111] <Hollow Silica Particles> The solventless composition of the present invention contains hollow silica particles having a space inside an outer shell.

[0112] Hollow silica particles have a silica shell with a space inside the shell. Hollow silica particles can be obtained by forming a shell mainly composed of silica on the surface of a part corresponding to the core, called a template, in a dispersion medium, and then removing the part corresponding to the core.

[0113] The hollow silica particles contained in the solventless composition of the present invention are coated with a silane compound described below. By coating the hollow silica particles with the silane compound, when the unexposed portions of a cured film obtained from the solventless composition are developed with an alkaline developer, the hollow silica particles in the unexposed portions are easily removed by the alkaline developer together with other components such as the triazine ring-containing polymer and the crosslinking agent. As a result, the pattern formability is good despite the inclusion of hollow silica particles.

[0114] The silane compound can be coated with at least one silane compound selected from the group consisting of the following formulas (44), (45), and (46) (hollow silica coated with a silane compound may also be referred to as "surface-modified hollow silica particles"). R １０６ ａ Si(R １０７ ) ４－ａ Formula (44) [R １０８ ｂ Si(R １０９ ) ３－ｂ ] ２ Y ｃ Formula (45) R １１０ ｄ Si(R １１１ ) ４－ｄ Formula (46)

[0115] In the above formula (44), R １０６ are each an alkyl group, a halogenated alkyl group, an alkenyl group, an aryl group, or an organic group having a polyether group, an epoxy group, a (meth)acryloyl group, a mercapto group, an amino group, a ureido group, or a cyano group, and are bonded to a silicon atom by a Si—C bond, and R １０７ represents an alkoxy group, an acyloxy group, or a halogen group, and a represents an integer of 1 to 3. In formulas (45) and (46), R １０８ and R １１０ are each an alkyl group having 1 to 3 carbon atoms or an aryl group having 6 to 30 carbon atoms and bonded to a silicon atom by a Si—C bond, and R １０９ and R １１１each represents an alkoxy group, an acyloxy group, or a halogen group; Y represents an alkylene group, an NH group, or an oxygen atom; b is an integer of 1 to 3; c is an integer of 0 or 1; and d is an integer of 1 to 3.

[0116] The alkyl group is an alkyl group having 1 to 18 carbon atoms, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclopropyl group, an n-butyl group, an i-butyl group, an s-butyl group, a t-butyl group, a cyclobutyl group, a 1-methyl-cyclopropyl group, a 2-methyl-cyclopropyl group, an n-pentyl group, a 1-methyl-n-butyl group, a 2-methyl-n-butyl group, a 3-methyl-n-butyl group, a 1,1-dimethyl-n-propyl group, a 1,2-dimethyl-n-propyl group, a 2,2-dimethyl-n-propyl group, a 1-ethyl -n-propyl group, cyclopentyl group, 1-methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group, 2-ethyl-cyclopropyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group group, 2,2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, cyclohexyl group, 1-methyl-cyclopentyl group, 2-methyl-cyclopentyl group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group group, 3-ethyl-cyclobutyl group, 1,2-dimethyl-cyclobutyl group, 1,3-dimethyl-cyclobutyl group, 2,2-dimethyl-cyclobutyl group, 2,3-dimethyl-cyclobutyl group, 2,4-dimethyl-cyclobutyl group, 3,3-dimethyl-cyclobutyl group, 1-n-propyl-cyclopropyl group, 2-n-propyl-cyclopropyl group, 1-i-propyl-cyclopropyl group, 2-i-propyl-cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, 1,2,3-trimethyl-cyclopropyl group, 2,2,Examples of the cyclopropyl group include, but are not limited to, 3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl, and 2-ethyl-3-methyl-cyclopropyl groups, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl groups.

[0117] The alkylene group may be an alkylene group derived from the alkyl group described above.

[0118] The aryl group is an aryl group having 6 to 30 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, an anthracene group, and a pyrene group.

[0119] The alkenyl group is an alkenyl group having 2 to 10 carbon atoms, for example, an ethenyl group, a 1-propenyl group, a 2-propenyl group, a 1-methyl-1-ethenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a 2-methyl-1-propenyl group, a 2-methyl-2-propenyl group, a 1-ethylethenyl group, a 1-methyl-1-propenyl group, a 1-methyl-2-propenyl group, a 1-pentenyl group, a 2-pentenyl group, a 3-pentenyl group, a 4-pentenyl group, a 1-n-propylethenyl group, a 1-methyl-1-butenyl group, a 1-methyl-2-butenyl group, a 1-methyl-3-butenyl group, a 2-ethyl-2-propenyl group, a 2-methyl-1-butenyl group, a 2-methyl-2-butenyl group, a 2-methyl-3-butenyl group, Examples of alkyl groups include, but are not limited to, a 3-methyl-1-butenyl group, a 3-methyl-2-butenyl group, a 3-methyl-3-butenyl group, a 1,1-dimethyl-2-propenyl group, a 1-i-propylethenyl group, a 1,2-dimethyl-1-propenyl group, a 1,2-dimethyl-2-propenyl group, a 1-cyclopentenyl group, a 2-cyclopentenyl group, a 3-cyclopentenyl group, a 1-hexenyl group, a 2-hexenyl group, a 3-hexenyl group, a 4-hexenyl group, a 5-hexenyl group, a 1-methyl-1-pentenyl group, a 1-methyl-2-pentenyl group, a 1-methyl-3-pentenyl group, a 1-methyl-4-pentenyl group, a 1-n-butylethenyl group, a 2-methyl-1-pentenyl group, and a 2-methyl-2-pentenyl group.

[0120] The alkoxy group is an alkoxy group having 1 to 10 carbon atoms, and examples thereof include, but are not limited to, a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, an s-butoxy group, a t-butoxy group, an n-pentyloxy group, a 1-methyl-n-butoxy group, a 2-methyl-n-butoxy group, a 3-methyl-n-butoxy group, a 1,1-dimethyl-n-propoxy group, a 1,2-dimethyl-n-propoxy group, a 2,2-dimethyl-n-propoxy group, a 1-ethyl-n-propoxy group, and an n-hexyloxy group.

[0121] The acyloxy group is an acyloxy group having 2 to 10 carbon atoms, and examples thereof include, but are not limited to, a methylcarbonyloxy group, an ethylcarbonyloxy group, an n-propylcarbonyloxy group, an i-propylcarbonyloxy group, an n-butylcarbonyloxy group, an i-butylcarbonyloxy group, an s-butylcarbonyloxy group, a t-butylcarbonyloxy group, an n-pentylcarbonyloxy group, a 1-methyl-n-butylcarbonyloxy group, a 2-methyl-n-butylcarbonyloxy group, a 3-methyl-n-butylcarbonyloxy group, a 1,1-dimethyl-n-propylcarbonyloxy group, a 1,2-dimethyl-n-propylcarbonyloxy group, a 2,2-dimethyl-n-propylcarbonyloxy group, a 1-ethyl-n-propylcarbonyloxy group, an n-hexylcarbonyloxy group, a 1-methyl-n-pentylcarbonyloxy group, and a 2-methyl-n-pentylcarbonyloxy group.

[0122] The halogen atoms include fluorine, chlorine, bromine, iodine, and the like.

[0123] The organic group having a polyether group includes a polyetherpropyl group having an alkoxy group. For example, (CH ３ O) ３ SiC ３ H ６ (OC ２ H ４ ) ｎ OCH ３ n can be in the range of 1 to 100, or 1 to 10.

[0124] Examples of the organic group having an epoxy group include a 2-(3,4-epoxycyclohexyl)ethyl group and a 3-glycidoxypropyl group.

[0125] The (meth)acryloyl group refers to both an acryloyl group and a methacryloyl group. Examples of organic groups having a (meth)acryloyl group include a 3-methacryloxypropyl group and a 3-acryloxypropyl group.

[0126] An example of the organic group having a mercapto group is a 3-mercaptopropyl group.

[0127] Examples of the organic group having an amino group include a 2-aminoethyl group, a 3-aminopropyl group, an N-2-(aminoethyl)-3-aminopropyl group, an N-(1,3-dimethyl-butylidene)aminopropyl group, an N-phenyl-3-aminopropyl group, and an N-(vinylbenzyl)-2-aminoethyl-3-aminopropyl group.

[0128] An example of the organic group having a ureido group is a 3-ureidopropyl group.

[0129] An example of the organic group having a cyano group is a 3-cyanopropyl group. Compounds of formula (45) and formula (46) are preferably compounds capable of forming trimethylsilyl groups on the surface of hollow silica particles. Examples of such compounds include the following compounds: In the above formula, R １１２ is an alkoxy group, examples of which include a methoxy group and an ethoxy group. As the silane compound, a silane compound manufactured by Shin-Etsu Chemical Co., Ltd. can be used.

[0130] The silane compound reacts with hydroxyl groups on the surface of hollow silica particles (e.g., silanol groups in the case of silica particles) to form siloxane bonds, thereby coating the surface of the silica particles with the silane compound. The reaction temperature can be from 20°C to the boiling point of the dispersion medium, for example, in the range of 20°C to 100°C. The reaction time can be about 0.1 to 6 hours.

[0131] The silane compound is used in such a manner that the number of silicon atoms in the silane compound is 0.1 / nm as a coating amount on the surface of the hollow silica particles. ２ ~6.0 pieces / nm ２ The surface of the hollow silica particles can be coated by adding a silane compound corresponding to the coating amount to the silica sol.

[0132] The silanol groups on the surface of hollow silica particles can react with aluminic acid to form aluminosilicate sites. The aluminosilicate sites impart a negative charge to the hollow silica particles in the silica sol. The aluminosilicate sites increase the negative zeta potential, thereby improving the stability of the silica particles in the dispersion medium. This improves the compatibility of the hollow silica particles with organic solvents and charged resins.

[0133] In one embodiment of the present invention, the hollow silica particles contain aluminum atoms forming aluminosilicate sites, and when measured by a leaching method, Al is present on the surface of the hollow silica particles. ２ O ３ Converted to SiO ２ The aluminum atoms are 100 ppm / SiO per 1 g ２ ~20000ppm / SiO ２ can be bonded in a ratio of

[0134] The hollow silica particles are prepared by leaching silica particles with an aqueous solution of at least one mineral acid selected from the group consisting of sulfuric acid, nitric acid, and hydrochloric acid, and the aluminum atoms are converted to Al by measuring the aluminum present on the surface of the silica particles. ２ O ３ The aluminum atoms are measured by the leaching method, and the aluminum atoms are attached to the surface of the hollow silica particles. ２ O ３ Converted to SiO ２ The aluminum atoms are 100 ppm / SiO per 1 g ２ ~20000ppm / SiO ２ The ratio may be preferably 100 ppm / SiO ２ ~15000ppm / SiO ２ More preferably, 100 ppm / SiO ２ ~10000ppm / SiO ２ More preferably, 100 ppm / SiO ２ ~3000ppm / SiO ２ More preferably, 200 ppm / SiO ２~5000ppm / SiO ２ and even more preferably 500 ppm / SiO ２ ~5000ppm / SiO ２ and even more preferably 800 ppm / SiO ２ ~3000ppm / SiO ２ It is important for the hollow silica particles to be present on their surfaces to form aluminosilicate sites in order to disperse them in a solvent or resin. When producing an acidic hollow silica sol, it is desirable to increase the absolute value of the zeta potential of the hollow silica particles in the acidic region. ２ O ３ The aluminum atom content is converted to 100 ppm / SiO ２ By setting the ratio to the above, the stability of the hollow silica particles is improved. ２ O ３ The aluminum atom content is calculated as 20,000 ppm / SiO ２ or less, it is possible to prevent the particle size after doping from increasing compared to the particle size measured by dynamic light scattering (DLS particle size) before doping with aluminum atoms by an aluminum compound at the stage of the aluminum-containing hollow silica aqueous sol.

[0135] The aluminum atoms present on the surface of the hollow silica particles as aluminosilicate are leached (eluted) in a structure similar to aluminum salt, aluminum oxide, or aluminum hydroxide by an aqueous solution of at least one mineral acid selected from the group consisting of sulfuric acid, nitric acid, and hydrochloric acid. The aluminum atoms can be measured from the solution using an ICP emission spectrometer. ２ O ３The pH can be expressed in terms of the pH of the silica particles. In particular, a leaching (elution) method using an aqueous nitric acid solution is used. The nitric acid solution used for leaching can be used at a pH in the range of 0.5 to 4.0, 0.5 to 3.0, 0.5 to 2.0, or 1.0 to 1.5, and typically, an aqueous nitric acid solution with a pH of 1.0 can be used. For example, 100 mL of the above aqueous nitric acid solution is added to 1 g of silica, and the mixture is kept at a temperature of 20°C to 70°C or 40°C to 60°C for 10 to 24 hours to elute the aluminum compound from the surface of the silica particles, which can then be used as an analytical sample.

[0136] In this specification, the surface of the hollow silica particles refers to the area where the aluminum compound can be eluted by the above-mentioned leaching. The surface of the hollow silica particles is the area where the amount of aluminum bonded to the surface of the silica particles (Al ２ O ３ / SiO ２ The surface of the hollow silica particles can be expressed as the aluminum content in ppm. The solvent was evaporated from the silica sol, and the silica gel was dried at 250°C and crushed to obtain silica powder. 20 mL of a nitric acid solution at pH 1.0 was added to 0.2 g of the silica powder, and the mixture was thoroughly shaken. The mixture was then placed in a thermostatic chamber at 50°C for 17 hours, and the aluminum content in the filtrate obtained by centrifugal filtration was measured using an ICP atomic emission spectrometer. ２ O ３ The aluminum content can be determined by dividing the converted aluminum content by the mass of the silica powder.

[0137] The content of hollow silica particles in the solventless composition of the present invention may be within a range that does not impair the dispersibility of the final solventless composition obtained, and can be controlled in accordance with the target transmittance, heat resistance, etc. of the film to be produced. For example, the content of hollow silica particles can be added in a range of 0.1 parts by mass to 1,000 parts by mass per 100 parts by mass of the triazine ring-containing polymer. The content of hollow silica particles is preferably 1 part by mass to 500 parts by mass, more preferably 10 parts by mass to 300 parts by mass, per 100 parts by mass of the triazine ring-containing polymer. By having the content of hollow silica particles within the above range, solvent resistance can be obtained while maintaining film quality.

[0138] The solventless composition of the present invention is characterized by not containing any organic solvent. In the present invention, "not containing any organic solvent" means, as described above, that the organic solvent is substantially not contained, and indicates, for example, that the content of the organic solvent is 10% by mass or less relative to the mass of the entire composition. Among the solventless compositions of the present invention, those having an organic solvent content of 8% by mass or less are preferred, those having an organic solvent content of 5% by mass or less are more preferred, and those having an organic solvent content of 3% by mass or less are even more preferred.

[0139] Here, the organic solvent refers to an organic substance that is liquid at room temperature and normal pressure and is generally used to dissolve a solute. That is, examples of the organic solvent include toluene, p-xylene, o-xylene, m-xylene, ethylbenzene, styrene, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, diethylene glycol diethyl ether, dipropylene glycol monomethyl ether, diethylene glycol monomethyl ether, dipropylene glycol monoethyl ether, diethylene glycol monoethyl ether, triethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol Licorice, 1-octanol, ethylene glycol, hexylene glycol, trimethylene glycol, 1-methoxy-2-butanol, cyclohexanol, diacetone alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, propylene glycol, benzyl alcohol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, γ-butyrolactone, acetone, methyl ethyl ketone, methyl isopropyl ketone, diethyl ketone, methyl isobutyl ketone, methyl n-butyl ketone ton, cyclopentanone, cyclohexanone, ethyl acetate, isopropyl acetate, n-propyl acetate, isobutyl acetate, n-butyl acetate, ethyl lactate, methanol, ethanol, isopropanol, tert-butanol, allyl alcohol, n-propanol, 2-methyl-2-butanol, isobutanol, n-butanol, 2-methyl-1-butanol, 1-pentanol, 2-methyl-1-pentanol, 2-ethylhexanol, 1-methoxy-2-propanol, tetrahydrofuran, 1,4-dioxane, N,Examples include N-dimethylformamide, N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, and N-cyclohexyl-2-pyrrolidinone.

[0140] The solvent-free composition of the present invention does not contain the above organic solvents, and therefore can be suitably used, for example, in the formation of transparent conductive films in which highly polar solvents cannot be used.

[0141] <Reactive Diluent> The solventless composition of the present invention may contain a reactive diluent. The reactive diluent is a low-molecular-weight compound having one reactive group that reacts with at least one of the crosslinking group of the triazine ring-containing polymer and the crosslinking agent. In particular, a reactive diluent that is liquid and has a low viscosity at room temperature also has a viscosity adjusting function and can be used in place of an organic solvent.

[0142] As such a reactive diluent, a compound having one radically polymerizable group or a compound having one cationically polymerizable group such as an epoxy group, an oxetanyl group, or a vinyl ether group can be used.

[0143] The molecular weight of the reactive diluent is not particularly limited, and may be, for example, 200 or less.

[0144] As the reactive diluent, a compound having one radically polymerizable group is preferred, and a compound of the following formula (A) or (B) is more preferred in terms of excellent solubility of the triazine ring-containing polymer.

[0145] In formula (A), R １１３ and R １１５ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a group containing a polymerizable carbon-carbon double bond; R １１４ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. １１３ and R １１５ is a polymerizable carbon-carbon double bond-containing group, and R １１３ and R １１５ Both of R cannot be polymerizable carbon-carbon double bond-containing groups at the same time. １１３is a polymerizable carbon-carbon double bond-containing group, R １１４ and R １１５ may form a ring structure together with N. The structure of the alkyl group is not particularly limited, and may be, for example, linear, branched, cyclic, or a combination of two or more thereof. １１６ represents a hydrogen atom or a methyl group, and n represents an integer of 1 or 2.

[0146] Specific examples of alkyl groups having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, 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, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, etc. Preferred are alkyl groups having 1 to 5 carbon atoms.

[0147] The polymerizable carbon-carbon double bond-containing group is not particularly limited, but is preferably a carbon-carbon double bond-containing hydrocarbon group (alkenyl group) having 2 to 10 carbon atoms, preferably 2 to 5 carbon atoms, such as ethenyl (vinyl), n-1-propenyl, n-2-propenyl (allyl group), 1-methylethenyl, n-1-butenyl, n-2-butenyl, n-3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylethenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, n-1-pentenyl, n-2-pentenyl, n-3-pentenyl, n-4-pentenyl, 1-n-propylethenyl, 1-methyl-2-propenyl, n-propyl- ... 1-methyl-2-propenyl, n-propyl-ethenyl, 1-methyl-2-propenyl, 1-methyl-2-propenyl, 1-methyl-2-propenyl, 1-methyl-2-propenyl, -methyl-1-butenyl, 1-methyl-2-butenyl, 1-methyl-3-butenyl, 2-ethyl-2-propenyl, 2-methyl-1-butenyl, 2-methyl-2-butenyl, 2-methyl-3-butenyl, 3-methyl-1-butenyl, 3-methyl-2-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1-isopropylethenyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, n-1-hexenyl, n-2-hexenyl, n-3-hexenyl, n-4-hexenyl, n-5-hexenyl, n-heptenyl, n-octenyl, n-nonenyl, n-decenyl group, and the like.

[0148] Specific examples of the compound represented by formula (A) include N-vinylformamide, N-vinylacetamide, N-allylformamide, N-allylacetamide, 4-acryloylmorpholine, (meth)acrylamide, N-methyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-ethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, and N,N-diisopropyl(meth)acrylamide, with N-vinylformamide, 4-acryloylmorpholine, N,N-dimethylacrylamide, and N,N-diethyl(meth)acrylamide being preferred. Specific examples of the compound represented by formula (B) include tetrahydrofuran-2-ylmethyl acrylate, tetrahydrofuran-2-ylmethyl methacrylate, tetrahydrofuran-2-ylethyl acrylate, and tetrahydrofuran-2-ylethyl methacrylate. The reactive diluents described above may be used alone or in combination of two or more.

[0149] The content of the reactive diluent in the solventless composition is not particularly limited, but is preferably 1 part by mass to 2000 parts by mass relative to 100 parts by mass of the triazine ring-containing polymer. The content of the reactive diluent can be appropriately adjusted taking into consideration the degree of improvement in the refractive index of the resulting film, the solvent resistance, and the viscosity. The content of the reactive diluent may be preferably 500 parts by mass to 1800 parts by mass, more preferably 1000 parts by mass to 1500 parts by mass.

[0150] <Initiator> The solventless composition of the present invention can also contain an initiator appropriate for each crosslinking agent. As described above, when a polyfunctional epoxy compound and / or a polyfunctional (meth)acrylic compound is used as the crosslinking agent, photocuring proceeds to give a cured film even without the use of an initiator, but in this case, an initiator may be used.

[0151] When a polyfunctional epoxy compound is used as a crosslinking agent, a photoacid generator or a photobase generator can be used. The photoacid generator may be appropriately selected from known ones, and examples of the photoacid generator include onium salt derivatives such as diazonium salts, sulfonium salts, and iodonium salts. Specific examples thereof include aryl diazonium salts such as phenyl diazonium hexafluorophosphate, 4-methoxyphenyl diazonium hexafluoroantimonate, and 4-methylphenyl diazonium hexafluorophosphate; diaryl iodonium salts such as diphenyl iodonium hexafluoroantimonate, bis(4-methylphenyl)iodonium hexafluorophosphate, and bis(4-tert-butylphenyl)iodonium hexafluorophosphate; triphenylsulfonium hexafluoroantimonate, tris(4-methoxyphenyl)sulfonium hexafluorophosphate, diphenyl-4-thiophenoxyphenylsulfonium hexafluoroantimonate, and diphenyl-4-thiophenoxyphenylsulfonium hexafluorophosphate. triarylsulfonium salts such as 4,4'-bis(diphenylsulfonio)phenylsulfide-bishexafluoroantimonate, 4,4'-bis(diphenylsulfonio)phenylsulfide-bishexafluorophosphate, 4,4'-bis[di(β-hydroxyethoxy)phenylsulfonio]phenylsulfide-bishexafluoroantimonate, 4,4'-bis[di(β-hydroxyethoxy)phenylsulfonio]phenylsulfide-bis-hexafluorophosphate, 4-[4'-(benzoyl)phenylthio]phenyl-di(4-fluorophenyl)sulfonium hexafluoroantimonate, and 4-[4'-(benzoyl)phenylthio]phenyl-bis(4-fluorophenyl)sulfonium hexafluorophosphate.

[0152] These onium salts may be commercially available products, and specific examples thereof include San-Aid SI-60, SI-80, SI-100, SI-60L, SI-80L, SI-100L, SI-L145, SI-L150, SI-L160, SI-L110, and SI-L147 (all manufactured by Sanshin Chemical Industry Co., Ltd.), UVI-6950, and UVI-6970. , UVI-6974, UVI-6990, UVI-6992 (all manufactured by Union Carbide Corporation), CPI-100P, CPI-100A, CPI-200K, CPI-200S (all manufactured by San-Apro Co., Ltd.), Adeka Optomer SP-150, SP-151, SP-170, SP-171 (all manufactured by Asahi Denka Kogyo Co., Ltd.), Irgacure 261 (manufactured by BASF), CI-2481, CI-2624, CI-2639, CI-2064 (all manufactured by Nippon Soda Co., Ltd.), CD-1010, CD-1011, CD-1012 (all manufactured by Sartomer Corporation), DS-100, DS-101, DAM-101, DAM-102, DAM-105, DAM-201, DSM-301, NAI-100, NAI-101, NAI-105, NAI-106, SI-100, SI-101, SI-105, SI-106, PI-105, NDI-105, BENZOIN Examples of suitable terpolymers include TOSYLATE, MBZ-101, MBZ-301, PYR-100, PYR-200, DNB-101, NB-101, NB-201, BBI-101, BBI-102, BBI-103, and BBI-109 (all manufactured by Midori Chemical Co., Ltd.), PCI-061T, PCI-062T, PCI-020T, and PCI-022T (all manufactured by Nippon Kayaku Co., Ltd.), IBPF, and IBCF (manufactured by Sanwa Chemical Co., Ltd.).

[0153] On the other hand, the photobase generator may also be appropriately selected from known ones, and examples thereof include Co-amine complex-based, oxime carboxylic acid ester-based, carbamic acid ester-based, and quaternary ammonium salt-based photobase generators. Specific examples thereof include 2-nitrobenzyl cyclohexyl carbamate, triphenylmethanol, O-carbamoylhydroxylamide, O-carbamoyloxime, [[(2,6-dinitrobenzyl)oxy]carbonyl]cyclohexylamine, bis[[(2-nitrobenzyl)oxy]carbonyl]hexane-1,6-diamine, 4-(methylthiobenzoyl)-1-methyl-1-morpholinoethane, and (4-morpholinobenzoyl)-1-benzyl-1-dimethylamine. Examples of the photobase generator include 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, 2,6-dimethyl-3,5-diacetyl-4-(2',4'-dinitrophenyl)-1,4-dihydropyridine, 2,6-dimethyl-3,5-diacetyl-4-(2',4'-dinitrophenyl)-1,4-dihydropyridine, and the like. Furthermore, commercially available photobase generators may be used, and specific examples thereof include TPS-OH, NBC-101, and ANC-101 (all product names, manufactured by Midori Chemical Co., Ltd.).

[0154] When a photoacid or base generator is used, it is preferably used in an amount of 0.1 to 15 parts by mass, more preferably 1 to 10 parts by mass, per 100 parts by mass of the polyfunctional epoxy compound. If necessary, an epoxy resin curing agent may be blended in an amount of 1 to 100 parts by mass per 100 parts by mass of the polyfunctional epoxy compound.

[0155] On the other hand, when a polyfunctional (meth)acrylic compound is used, a photoradical polymerization initiator can be used. The photoradical polymerization initiator may be appropriately selected from known initiators, such as acetophenones, benzophenones, Michler's benzoyl benzoate, amyloxime esters, oxime esters, tetramethylthiuram monosulfide, and thioxanthones. In particular, photocleavage-type photoradical polymerization initiators are preferred. Photocleavage-type photoradical polymerization initiators are described in "Latest UV Curing Technology" (page 159, published by Takasuki Kazuhiro, published by Technical Information Association, Inc., published in 1991). Examples of commercially available photoradical polymerization initiators include trade names of Irgacure 127, 184, 369, 379, 379EG, 651, 500, 754, 819, 903, 907, 784, 2959, CGI1700, CGI1750, CGI1850, CG24-61, OXE01, OXE02, OXE03, OXE04, and Darocur 1116, 1173, and MBF manufactured by BASF, trade name of Lucirin TPO manufactured by BASF, trade name of Ebecryl P36 manufactured by UCB, and trade name of Ezacure manufactured by Fratelli Lamberti. Examples of such photoradical polymerization initiators include KIP150, KIP65LT, KIP100F, KT37, KT55, KTO46, and KIP75 / B. When a photoradical polymerization initiator is used, it is preferably used in an amount of 0.1 to 200 parts by mass, and more preferably 1 to 150 parts by mass, per 100 parts by mass of the polyfunctional (meth)acrylate compound.

[0156] Furthermore, in order to promote the reaction between the triazine ring-containing polymer and the crosslinking agent, a polyfunctional thiol compound having two or more mercapto groups in the molecule may be added to the solventless composition of the present invention. As the polyfunctional thiol compound, for example, a polyfunctional thiol compound represented by the following formula can be used.

[0157]

[0158] The above L represents a divalent to tetravalent organic group, preferably a divalent to tetravalent aliphatic group having 2 to 12 carbon atoms or a divalent to tetravalent heterocycle-containing group, and more preferably a divalent to tetravalent aliphatic group having 2 to 8 carbon atoms or a trivalent group having an isocyanuric acid skeleton (1,3,5-triazine-2,4,6(1H,3H,5H)-trione ring) represented by the following formula: The above n represents an integer of 2 to 4 corresponding to the valence of L.

[0159] (In the formula, "." indicates the bond to the oxygen atom.)

[0160] Examples of polyfunctional thiol compounds include 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, pentaerythritol tetrakis(3-mercaptobutyrate), trimethylolpropane tris(3-mercaptobutyrate), trimethylolethane tris(3-mercaptobutyrate), and the like. These polyfunctional thiol compounds are also commercially available, and examples thereof include Karenz MT-BD1, Karenz MT NR1, Karenz MT PE1, TPMB, and TEMB (all manufactured by Showa Denko K.K.). These polyfunctional thiol compounds may be used alone or in combination of two or more.

[0161] When a polyfunctional thiol compound is used, the amount added is not particularly limited as long as it does not adversely affect the film to be obtained. In the solventless composition of the present invention, the amount is preferably 0.01% by mass to 10% by mass, and more preferably 0.03% by mass to 6% by mass, based on 100% by mass of the solid content.

[0162] <Other Additives> The solventless composition of the present invention may contain components other than the triazine ring-containing polymer, crosslinking agent, and hollow silica particles, such as leveling agents, surfactants, silane coupling agents, polymerization inhibitors, antioxidants, rust inhibitors, mold release agents, plasticizers, antifoaming agents, thickeners, dispersants, antistatic agents, antisettling agents, pigments, dyes, ultraviolet absorbers, and light stabilizers, as long as the effects of the present invention are not impaired.Examples of surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkyl aryl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether; polyoxyethylene-polyoxypropylene block copolymers; sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate; and nonionic surfactants such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate, including polyoxyethylene sorbitan fatty acid esters, such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate. 01, EF303, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd. (formerly JEMCO Co., Ltd.)), trade names Megafac F171, F173, R-08, R-30, R-40, R-41, F-114, F-410, F-430, F-444, F-477, F-552, F-553, F-554, F-555, F-556, F-557, F-558, F-559, F-561, F-562, F-563, RS-75, RS-72-K, RS-76-E, RS-76NS, RS-77 (manufactured by DIC Corporation), Fluorad FC4 Fluorine-based surfactants such as FC30 and FC431 (manufactured by Sumitomo 3M Limited), and trade names Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, and SC106 (manufactured by AGC Inc.), and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), BYK-302, BYK-307, BYK-322, BYK-323, BYK-330, BYK-333, BYK-370, BYK-375, and BYK-378 (manufactured by BYK Japan KK).

[0163] These surfactants may be used alone or in combination of two or more. The amount of the surfactant used is preferably 0.0001 to 5 parts by mass, more preferably 0.001 to 1 part by mass, and even more preferably 0.01 to 0.5 parts by mass, per 100 parts by mass of the triazine ring-containing polymer.

[0164] (Cured film) In one embodiment of the present invention, a cured film can be obtained using the solventless composition described above. The cured film is a cured film comprising a triazine ring-containing polymer and hollow silica particles. The triazine ring-containing polymer is characterized by including a repeating unit structure represented by the following formula (1), having at least one triazine ring terminal, and at least a portion of the triazine ring terminal being blocked with an amino group having a crosslinking group: (In formula (1), R and R′ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group; Q represents a divalent group having a ring structure and having 3 to 30 carbon atoms; and * represents a bond.) The hollow silica particles are represented by the following formulas (44), (45), and (46): R １０６ ａ Si(R １０７ ) ４－ａ Formula (44) [R １０８ ｂ Si(R １０９ ) ３－ｂ ] ２ Y ｃ Formula (45) R １１０ ｄ Si(R １１１ ) ４－ｄ Formula (46) (In formula (44), R １０６ are each an alkyl group, a halogenated alkyl group, an alkenyl group, an aryl group, or an organic group having an epoxy group, a (meth)acryloyl group, a mercapto group, an amino group, a ureido group, or a cyano group, and are bonded to a silicon atom by a Si—C bond, and R １０７ each represents an alkoxy group, an acyloxy group, or a halogen atom, a represents an integer of 1 to 3, and in formulas (45) and (46), R １０８ and R １１０are each an alkyl group having 1 to 3 carbon atoms or an aryl group having 6 to 30 carbon atoms and bonded to a silicon atom by a Si—C bond, and R １０９ and R １１１ each represents an alkoxy group, an acyloxy group, or a halogen atom; Y represents an alkylene group, an NH group, or an oxygen atom; b is an integer of 1 to 3; c is an integer of 0 or 1; and d is an integer of 1 to 3.

[0165] The cured film of the present invention can be made thick despite containing inorganic particles, and the thickness can be adjusted appropriately depending on the application of the cured film, such as an electronic device.

[0166] In one embodiment of the present invention, the thickness of the cured film may be 1,000 nm or more and 20,000 nm or less, preferably 5,000 nm or more and 20,000 nm or less, more preferably 7,500 nm or more and 20,000 nm or less, and even more preferably 10,000 nm or more and 20,000 nm or less.

[0167] As described above, the cured film of the present invention can be made thicker and have a lower refractive index than conventional cured films. In one embodiment of the present invention, the cured film has a refractive index lower than that of the triazine ring-containing polymer. While the refractive index of a cured film made of a triazine ring-containing polymer is about 1.60, the refractive index of the cured film of the present invention may be, for example, 1.55 or less, preferably 1.50 or less, more preferably 1.45 or less, and particularly preferably 1.40 or less. By reducing the refractive index of the cured film, it can be suitably used in electronic devices and the like that require a low refractive index film.

[0168] A cured film using the above-mentioned solventless composition can be obtained, for example, by the following production method. That is, the pattern-forming composition is applied to a substrate, and then, if necessary, heated to evaporate the solvent, followed by heating or light irradiation to form a desired cured film. When a cured film is produced by light irradiation, the film is irradiated with light through a mask having a desired pattern formed thereon, and then developed with a developer to obtain a cured film having a fine pattern formed thereon. In this case, any method for applying the solventless composition can be used, and for example, methods such as spin coating, dipping, flow coating, inkjet coating, jet dispenser coating, spraying, bar coating, gravure coating, slit coating, roll coating, transfer printing, brush coating, blade coating, and air knife coating can be used.

[0169] Examples of the substrate include silicon, glass coated with indium tin oxide (ITO), glass coated with indium zinc oxide (IZO), metal nanowires, polyethylene terephthalate (PET), plastic, glass, quartz, ceramics, and the like. Flexible substrates can also be used. The baking temperature is not particularly limited and can be, for example, 70°C to 140°C. The baking time is not particularly limited as long as a cured film can be formed, and can be, for example, 1 second to 600 seconds. The baking method is not particularly limited and, for example, evaporation can be performed using a hot plate or oven under an appropriate atmosphere such as air, an inert gas such as nitrogen, or a vacuum. The baking temperature and baking time can be selected according to the processing steps of the target electronic device, and baking conditions can be selected such that the physical properties of the resulting film conform to the required characteristics of the electronic device. The conditions for light irradiation are also not particularly limited, and appropriate irradiation energy and time can be selected depending on the triazine ring-containing polymer and crosslinking agent used.

[0170] The cured film of the present invention obtained as described above can achieve properties not found in conventional cured films, namely, a high film thickness and a low refractive index, and can therefore be suitably used in the fields of electronic devices and optical materials, such as a part of the materials used in producing liquid crystal displays, organic electroluminescence (EL) displays, touch panels, optical semiconductor (LED) elements, solid-state imaging elements, organic thin-film solar cells, dye-sensitized solar cells, organic thin-film transistors (TFTs), lenses, prism cameras, binoculars, microscopes, semiconductor exposure devices, etc.

[0171] The solventless composition of the present invention may be the following: A solventless composition comprising a monomer having an acrylamide skeleton, a crosslinking agent, and hollow silica particles having a space inside an outer shell, and containing no organic solvent, wherein the hollow silica particles are represented by the following formulas (44), (45), and (46): R １０６ ａ Si(R １０７ ) ４－ａ Formula (44) [R １０８ ｂ Si(R １０９ ) ３－ｂ ] ２ Y ｃ Formula (45) R １１０ ｄ Si(R １１１ ) ４－ｄ Formula (46) (In formula (44), R １０６ are each an alkyl group, a halogenated alkyl group, an alkenyl group, an aryl group, or an organic group having an epoxy group, a (meth)acryloyl group, a mercapto group, an amino group, a ureido group, or a cyano group, and are bonded to a silicon atom by a Si—C bond, and R １０７ each represents an alkoxy group, an acyloxy group, or a halogen atom, a represents an integer of 1 to 3, and in formulas (45) and (46), R １０８ and R １１０ are each an alkyl group having 1 to 3 carbon atoms or an aryl group having 6 to 30 carbon atoms and bonded to a silicon atom by a Si—C bond, and R １０９ and R １１１each represents an alkoxy group, an acyloxy group, or a halogen atom; Y represents an alkylene group, an NH group, or an oxygen atom; b is an integer of 1 to 3; c is an integer of 0 or 1; and d is an integer of 1 to 3.

[0172] The monomer contained in the solventless composition of the present invention is not particularly limited as long as it has an acrylamide skeleton, and may have a branched structure due to the N atom in the acrylamide skeleton, or may have a ring structure containing the N atom in the acrylamide skeleton.

[0173] Examples of monomers having an acrylamide skeleton include acrylamide (monomer), N,N-dimethylacrylamide, N-(hydroxymethyl)acrylamide, N,N-dimethylmethacrylamide, N-methylmethacrylamide, N-propylacrylamide, N-isopropylacrylamide, N-isopropylmethacrylamide, N-tert-butylacrylamide, N-butylacrylamide, N-[2-(dimethylamino)ethyl]acrylamide, N-[3-(dimethylamino)propyl]acrylamide, N,N'-ethylenebisacrylamide, N-[2-(diethylamino)ethyl]acrylamide, 1,4-bis(acryloyl)piperazine, and acroylmorpholine.

[0174] The crosslinking agent and the hollow silica particles having a space inside the outer shell are as described above. The solventless composition of the present invention may further contain the reactive diluent, initiator, and other additives described above.

[0175] The solventless composition of the present invention can form a cured film in the same manner as the above-mentioned solventless composition containing a triazine ring-containing polymer.

[0176] The present invention will be explained in more detail below with reference to synthesis examples and examples, but the present invention is not limited to the following examples.

[0177] The measuring devices used in the examples are as follows: １H-NMR] Apparatus: Bruker NMR System AVANCE III HD 500 (500 MHz) Measurement solvent: deuterated dimethyl sulfoxide (DMSO-d ６ ) Reference substance: tetramethylsilane (TMS) (δ 0.0 ppm) [GPC] Apparatus: HLC-8200 manufactured by Tosoh Corporation GPC Column: Tosoh TSKgel α-3000 + Tosoh TSKgel α-4000 Column temperature: 40°C Solvent: dimethylformamide (DMF) Detector: UV (271 nm) Detection line: standard polystyrene [Optical microscope] Apparatus: Evident Co., Ltd., upright microscope system BX53M [Exposure] Apparatus: Nitride Semiconductor Co., Ltd., compact UVLED irradiator NS365-CLT-100W3020 [Reliability test] Apparatus: Espec Corporation, small environmental tester SH-221 [Turbidity meter] Apparatus: Nippon Denshoku Industries Co., Ltd., HAZE METER NDH 5000 [Spectrophotometer] Device: CM-3700A manufactured by Konica Minolta [Ultraviolet-visible-near-infrared spectrophotometer] Device: V-670 manufactured by JASCO Corporation

[0178] [1] Synthesis of triazine ring-containing polymer [Synthesis Example 1-1] Synthesis of polymer compound [4] Into a 3,000 mL four-neck flask, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane [2] (78.7 g, 0.152 mol, manufactured by Wakayama Seika Kogyo Co., Ltd.) and 3-methoxy-N,N-dimethylpropanamide (605.5 g, KJCMPA-100, manufactured by KJ Chemicals Co., Ltd.) were added, and the atmosphere was replaced with nitrogen. After that, the mixture was stirred to dissolve 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane [2] in the KJCMPA-100. The mixture was then cooled to -5°C in an ethanol-dry ice bath, and 2,4,6-trichloro-1,3,5-triazine [1] (40.00 g, 0.217 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) was added while ensuring that the internal temperature did not exceed 5°C. Finally, the mixture was washed with KJCMPA-100 (71.2 g). After stirring for 30 minutes, 2-aminoethanol [3] (23.8 g, 0.390 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise, and the mixture was washed with KJCMPA-100 (35.6 g), followed by stirring for 3 hours. Thereafter, 2-aminoethanol (39.7 g, manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise, and the mixture was stirred for 30 minutes, after which the stirring was stopped. Tetrahydrofuran (THF, 358 g, manufactured by Junsei Chemical Co., Ltd.), ammonium acetate (402.6 g), and ion-exchanged water (402.6 g) were added to the reaction solution and stirred for 30 minutes. After stirring was stopped, the solution was transferred to a separatory funnel and separated into an organic layer and an aqueous layer, and the organic layer was recovered. To the recovered organic layer, ammonium acetate (402.6 g) and ion-exchanged water (402.6 g) were added again, and the mixture was stirred for 30 minutes. After stirring was stopped, the solution was transferred to a separatory funnel and separated into an organic layer and an aqueous layer, and the organic layer was recovered again. The recovered organic layer was added dropwise to methanol (895 g) and ion-exchanged water (1789 g) to cause reprecipitation. The resulting precipitate was filtered and dried in a vacuum dryer at 80°C for 8 hours, yielding 114.3 g of the target polymer compound [4] (hereinafter referred to as P-1).

[0179] The weight average molecular weight Mw of Compound P-1 measured by GPC in terms of polystyrene was 2,451, and the polydispersity Mw / Mn was 2.0. １ The results of the H-NMR spectrum are shown in FIG.

[0180] [Synthesis Example 1-2] Synthesis of polymer compound [5] A 300 mL four-neck flask was charged with P-1[4] (20.0 g) obtained in Synthesis Example 1-1 and PGMEA (62.12 g), and the mixture was purged with nitrogen and stirred to dissolve. The solution was then heated to an internal temperature of 65°C, and N-nitrosophenylhydroxyamine aluminum salt (0.0020 g, Q-1301, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 2-isocyanatoethyl acrylate (6.62 g, AOI-VM, manufactured by Showa Denko K.K.) were added dropwise. The internal temperature was maintained at 65°C and the mixture was stirred for 3 hours to obtain a 30% by mass PGMEA solution (hereinafter referred to as P-1-1 solution).

[0181] [Synthesis Example 2-1] Synthesis of polymer compound [8] A 3,000 mL four-neck flask was charged with 2,2-bis[4-(4-aminophenoxy)phenyl]propane [6] (77.9 g, 0.190 mol, manufactured by Wakayama Seika Kogyo Co., Ltd.) and KJCMPA-100 (767.5 g). The flask was purged with nitrogen and then stirred to dissolve 2,2-bis[4-(4-aminophenoxy)phenyl]propane [6] in KJCMPA-100. The flask was then cooled to -5 ° C in an ethanol-dry ice bath, and 2,4,6-trichloro-1,3,5-triazine [1] (50.00 g, 0.271 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) was added, ensuring that the internal temperature did not exceed 5 ° C. Finally, the flask was rinsed with KJCMPA-100 (30.7 g). After stirring for 30 minutes, 4-aminophenethyl alcohol [7] (66.9 g, 0.488 mol, manufactured by Oakwood) dissolved in KJCMPA-100 (204.7 g) was added dropwise, washed with KJCMPA-100 (20.5 g), and stirred for 3 hours. N,N-Diethylethanolamine (85.5 g, manufactured by Kanto Chemical Co., Inc.) was then added dropwise, and after stirring for 30 minutes, stirring was stopped. THF (521 g), ammonium acetate (586.7 g), and ion-exchanged water (586.7 g) were added to the reaction solution, and the mixture was stirred for 30 minutes. After stirring was stopped, the solution was transferred to a separatory funnel, separated into an organic layer and an aqueous layer, and the organic layer was recovered. Ammonium acetate (586.7 g) and ion-exchanged water (586.7 g) were added again to the recovered organic layer, and the mixture was stirred for 30 minutes. After stirring was stopped, the solution was transferred to a separatory funnel and separated into an organic layer and an aqueous layer, and the organic layer was recovered again. The recovered organic layer was added dropwise to methanol (1,304 g) and ion-exchanged water (2,607 g) to cause reprecipitation. The resulting precipitate was filtered and dried in a vacuum dryer at 80°C for 8 hours, yielding 162.0 g of the target polymer compound [8] (hereinafter referred to as P-2).

[0182] The weight average molecular weight Mw of Compound P-2 measured by GPC in terms of polystyrene was 2,942, and the polydispersity Mw / Mn was 2.5. １ The results of the H-NMR spectrum are shown in FIG.

[0183] [Synthesis Example 2-2] Synthesis of polymer compound [9] A 300 mL four-neck flask was charged with P-2[8] (20.0 g) obtained in Synthesis Example 2-1 and PGMEA (59.89 g), and the flask was purged with nitrogen and then stirred to dissolve. The solution was then heated to an internal temperature of 65°C, and Q-1301 (0.0020 g) and AOI-VM (5.67 g) were added dropwise. The internal temperature was maintained at 65°C and the mixture was stirred for 3 hours to obtain a 30 mass% PGMEA solution (hereinafter referred to as P-2-1 solution).

[0184] [Comparative Example 1-1] To the P-1-1 solution (4.995 g) obtained in Synthesis Example 1-2, a 10% by mass PGMEA solution of Megafac R-40 (0.015 g, manufactured by DIC Corporation) as a surfactant and PGMEA (4.99 g) as an additional solvent were added, and the solution was visually confirmed to have dissolved, to prepare a solution (hereinafter referred to as P-1-2 solution). This P-1-2 solution was spin-coated onto a 50 mm x 50 mm x 0.7 mm alkali-free glass substrate using a spin coater at 200 rpm for 5 seconds and 1000 rpm for 30 seconds, and then dried on a hot plate at 100 ° C. for 1 minute to obtain a cured film (hereinafter referred to as P-1-2 film).

[0185] A solution (hereinafter referred to as P-2-2 solution) was prepared in the same manner as in Comparative Example 1-1, except that the P-2-1 solution obtained in Synthesis Example 2-2 was used instead. A cured film (hereinafter referred to as P-2-2 film) was obtained in the same manner as in Comparative Example 1-1, except that the P-2-2 solution was used instead.

[0186] The refractive index and film thickness of the cured film obtained above were measured. The results are shown in Table 1.

[0187] These results show that the polymer films obtained from the P-1-1 solution and the P-2-1 solution have high refractive indices.

[0188] [2] Production of Surface-Modified Hollow Silica Particles and Dispersion [2-1] Production of Surface-Modified Hollow Silica Particles [Production Example 1]: Production of Surface-Modified Hollow Silica Particles (D1) (1) Preparation of Aluminum-Containing Hollow Silica Aqueous Dispersion Sol (a) A commercially available hollow silica aqueous sol (2500.0 g, manufactured by Ningbo Dilato Co., Ltd., HKT-A20-40D) was placed in a container as a starting material, stirred, and diluted sodium aluminate (42.5 g, Al ２ O ３ A 1.0% by mass aqueous solution (equivalent to a concentration of 1.0% by mass) was added dropwise over 1 minute and stirred for 60 minutes. 2537.6 g of the mixture was placed in a 3 L SUS autoclave vessel, heated at 150°C for 5 hours, and cooled to room temperature. 8% sulfuric acid (6.1 g) was then added under stirring, and the mixture was stirred for 1 hour. The mixture was then passed through a column packed with cation exchange resin (H-type Amberlite IR-120B) at a space velocity (SV) of 5 / hour to obtain SiO ２ Aqueous sol A having a sol content of 18.9% by mass and a pH of 2.4 was obtained. Aqueous sol A was subjected to a heat treatment at 80°C for 10 hours, cooled to room temperature, and then passed through a cation exchange resin (H-type Amberlite IR-120B) packed in a column at a space velocity (SV) of 5 / hour to obtain an aqueous dispersion sol (g) of aluminum-containing hollow silica particles. The physical properties of the aqueous dispersion sol were as follows: SiO ２ 17.0% by mass, pH 2.3, average particle size by DLS method 54 nm, specific surface area by BET method (C) 116 m ２ / g, the amount of aluminum bound to the particle surface (A) was 1500 ppm, the amount of aluminum present in the whole particle (B) was 2500 ppm, (A / B ratio) was 0.60, the average primary particle diameter by TEM observation was 43 nm, and the TEM-equivalent specific surface area (D) was 63 m ２ / g, specific surface area ratio (C / D ratio) 1.8, particle refractive index 1.27, and shell thickness 6.0 nm.

[0189] (2) Preparation of Methanol Dispersion Sol (a1) of Aluminum-Containing Hollow Silica Particles In a 2 L recovery flask, 690.4 g of the water dispersion sol (a) of aluminum-containing hollow silica particles was placed, and 68.1 g of methanol was added. The pressure was reduced to 580 Torr in a rotary evaporator, and the mixture was heated to 120°C to perform methanol substitution, thereby obtaining a methanol dispersion sol (a1) of aluminum-containing hollow silica particles. The physical properties of the sol were pH 3.5, an average particle size of 72 nm by DLS method, and SiO ２ 23.5% by mass, moisture 0.4% by mass, viscosity 1.3 mPa sec, SiO of hollow silica particles ２ The surface charge amount calculated per 1 g of SiO was 52 μeq / g. ２ The physical properties of the solution, adjusted to 20.5% by mass, were pH 3.6, water content 0.3% by mass, and viscosity 1.2 mPa·sec.

[0190] (3) Preparation of silane-treated aluminum-containing hollow silica particle methanol dispersion sol (a2) 151.2 g of aluminum-containing hollow silica particle methanol dispersion sol (a1) (SiO ２ 20.5% by mass of silane-treated aluminum-containing hollow silica particles was placed in a 500 mL recovery flask, 45.9 g of methanol and 1.55 g of water were added and stirred, and 1.35 g of 3-(acryloyloxy)propyltrimethoxysilane (AcPS, manufactured by Shin-Etsu Chemical Co., Ltd., product name KBM-5103) was further added, followed by refluxing at 72°C for 5 hours with stirring. The mixture was then cooled to room temperature to prepare a methanol-dispersed sol (a2) of silane-treated aluminum-containing hollow silica particles. Its physical properties were pH 3.7, average particle size by DLS method 72 nm, SiO ２ 15.6% by mass, moisture 1.0% by mass, viscosity 1.1 mPa sec, SiO of hollow silica particles ２ The surface charge amount calculated per gram of the powder was 56 μeq / g.

[0191] [2-2] Production of Surface-Modified Hollow Silica Particle Dispersion [Production Example 2-1]: Production of Precursor of Solventless Composition of the Present Invention (T-1 Solution) To a 200 mL recovery flask were added 2.31 g of the P-1-1 solution obtained in Synthesis Example 1-2, 22.1 g of the methanol dispersion of surface-modified hollow silica particles (D1) obtained in Production Example 1 (total metal oxide concentration 18.4% by mass), and 10.9 g of tetrahydrofurfuryl acrylate (THFA, manufactured by Osaka Organic Chemical Industry Ltd.), and the PGMEA and methanol were completely distilled off using an evaporator to obtain a 30% by mass THFA solution (hereinafter referred to as T-1 solution).

[0192] [Production Example 2-2]: Production of precursor (T-2 solution) of solventless composition of the present invention To a 200 mL recovery flask were added 3.3 g of the P-2-1 solution obtained in Synthesis Example 2-2, 38.3 g of the methanol dispersion of the surface-modified hollow silica particles (D1) obtained in Production Example 1 (total metal oxide concentration: 18.4% by mass), and 17.5 g of THFA, and the PGMEA and methanol were completely distilled off using an evaporator to obtain a 30% by mass THFA solution (hereinafter referred to as T-2 solution).

[0193] Comparative Example 2-1 To a 200 mL recovery flask were added 0.75 g of DN-0075 (manufactured by Nippon Kayaku Co., Ltd.), 29.9 g of the methanol dispersion of the surface-modified hollow silica particles (D1) obtained in Production Example 1 (total metal oxide concentration: 18.4% by mass), and 14.0 g of THFA, and the methanol was completely distilled off using an evaporator to prepare a 30% by mass THFA solution, which gelled.

[0194] These results demonstrate that the P-1-1 solution and P-2-1 solution obtained in Synthesis Examples 1-2 and 2-2 contribute to the dispersibility of the surface-modified hollow silica particles.

[0195] [3] Preparation of Solvent-Free Composition and Fabrication of Cured Film [Example 1-1]: Solvent-Free Composition (NP-1 Solution) and Cured Film (NP-1 Film) To the T-1 solution (14.901 g) obtained in Production Example 2-1, DN-0075 (manufactured by Nippon Kayaku Co., Ltd.) (1.296 g) as a crosslinking agent, pentaerythritol tetrakis(3-mercaptobutyrate, Karenz MT PE1, manufactured by Showa Denko K.K.) (1.080 g) as a 10% by mass THFA solution as a UV radical curing aid, and Omnirad 819 (IGM Resins) as a UV radical generator were added. B.V. (0.108 g), KBM-5103 (Shin-Etsu Chemical Co., Ltd.) (0.54 g) as a silane coupling agent, Megafac F-563 (DIC Corporation) (0.043 g) of a 10% by mass THFA solution as a surfactant, and THFA (2.517 g) as an additional dilution monomer were added and visually confirmed to have dissolved, and a solution was prepared (hereinafter referred to as NP-1 solution). This NP-1 solution was applied to a 50 mm x 50 mm x 0.7 t alkali-free glass substrate with a bar coater to a wet film thickness of 52 μm at a speed of 70 mm / sec., and then pre-dried at 100 ° C. for 2 minutes using a hot plate, and then irradiated with a UV-LED irradiation device at a wavelength of 365 nm and 900 mJ / cm ２ The resulting film was exposed to an exposure dose of 100 ppm under nitrogen to obtain a cured film (hereinafter referred to as NP-1 film).

[0196] [Example 1-2]: Solventless composition (NP-2 solution) and cured film (NP-2 film) To the T-2 solution (7.477 g) obtained in Production Example 2-2, DN-0075 (0.6486 g) as a crosslinking agent, Karenz MT PE1 (0.540 g) of a 10 mass% THFA solution as a UV radical curing aid, Omnirad 819 (0.054 g) as a UV radical generator, X-12-1333A (manufactured by Shin-Etsu Chemical Co., Ltd.) (0.027 g) as a silane coupling agent, Megafac EFS-521 (manufactured by DIC Corporation) (0.030 g) of a 10 mass% THFA solution as a surfactant, and THFA (1.224 g) as an additional diluent monomer were added, and the solution was confirmed to have dissolved visually to prepare a solution (hereinafter referred to as NP-2 solution). This NP-2 solution was applied to a 50 mm x 50 mm x 0.7 mm alkali-free glass substrate using a bar coater at a speed of 70 mm / sec so that the wet film thickness was 52 μm, and after pre-drying at 100°C for 2 minutes using a hot plate, it was irradiated with 900 mJ / cm at a wavelength of 365 nm using a UV-LED irradiation device. ２ The resulting film was exposed to an exposure dose of 100 ppm under nitrogen to obtain a cured film (hereinafter referred to as NP-2 film).

[0197] The refractive index, film thickness, b ＊ The transmittance from 400 to 800 nm and haze were measured. The results are shown in Table 2. The average transmittance from 400 to 800 nm was calculated and shown in Table 2.

[0198] These results show that although the polymer used in the single film has a high refractive index, the cured films (NP-1 film and NP-2 film) obtained from the T-1 solution and T-2 solution have a low refractive index.

[0199] [4] Confirmation of Physical Properties of Cured Film [Solvent Resistance (Crack Resistance)] [Example 2-1-1] The NP-1 film obtained in Example 1-1 was set on a spin coater, and 1 mL of propylene glycol monomethyl ether (PGME) was applied. Next, the cured film was exposed to the solvent by rotating at 50 rpm for 60 seconds to prevent the liquid from splashing from the substrate. Thereafter, the solvent was removed from the substrate by rotating at 1,000 rpm for 30 seconds. Finally, the film was dried at 85°C for 10 seconds using a hot plate, after which the refractive index and film thickness were measured, the residual film ratio was calculated, and the film surface was observed using an optical microscope. The residual film ratio was calculated using the following formula: Residual film ratio (%) = (film thickness before solvent exposure) ÷ (film thickness after solvent exposure) × 100

[0200] Example 2-1-2 A solvent resistance test was carried out in the same manner as in Example 2-1-1, except that the solvent to be applied was changed to propylene glycol monomethyl ether acetate (PGMEA).

[0201] Example 2-2-1 A solvent resistance test was carried out in the same manner as in Example 2-1-1, except that the membrane used was changed to the NP-2 membrane.

[0202] Example 2-2-2 A solvent resistance test was carried out in the same manner as in Example 2-1-2, except that the membrane used was changed to the NP-2 membrane.

[0203] The results of film thickness measurements and film remaining rates for Examples 2-1-1 to 2-1-2 and 2-2-1 to 2-2-2 are shown in Table 3. Micrographs of the cured films after exposure to the solvent are shown in Figures 3 to 6, respectively.

[0204] All of the films prepared using the solventless composition of the present invention had excellent solvent resistance (cracking resistance).

[0205] [5-1] Production of Surface-Modified Hollow Silica Particle Dispersion [Production Example 5-1]: Production of Precursor of Solventless Composition of the Present Invention (T-2 Solution) To a 200 mL recovery flask were added 49.3 g of the methanol dispersion of the surface-modified hollow silica particles (D1) obtained in Production Example 1 (total metal oxide concentration: 16.2% by mass) and 12.0 g of N,N-diethylacrylamide (DEAA, manufactured by KJ Chemicals Co., Ltd.), and the methanol was completely removed using an evaporator to obtain a 40% by mass DEAA solution (hereinafter referred to as T-2 solution).

[0206] [Production Example 5-2]: Production of a precursor (T-3 solution) of the solventless composition of the present invention In the same manner as in Example 5-1, 12.0 g of acryloylmorpholine (ACMO, manufactured by KJ Chemicals Co., Ltd.) was added as the acrylic monomer to be dispersed, and the methanol was completely removed using an evaporator to obtain a 40 mass % ACMO solution (hereinafter referred to as T-3 solution).

[0207] Comparative Example 5-1 In the same manner as in Example 5-1, 12.0 g of tetrahydrofurfuryl acrylate (THFA, manufactured by Osaka Organic Chemical Industry Co., Ltd.) was added as the acrylic monomer to be dispersed, and the methanol was completely removed using an evaporator in an attempt to obtain a 40% by mass THFA solution, but gelation occurred and dispersion was not possible.

[0208] Comparative Example 5-2 In the same manner as in Example 5-1, an attempt was made to obtain a 40% by mass NOAA solution using 12.0 g of n-octyl acrylate (NOAA, manufactured by Osaka Organic Chemical Industry Ltd.) as the acrylic monomer to be dispersed, but gelation occurred and dispersion was not possible.

[0209] Comparative Example 5-3 In the same manner as in Comparative Example 5-1, an attempt was made to obtain a 40% by mass Viscoat 8F solution using 12.0 g of 1H,1H,5H-octafluoropentyl acrylate (Viscoat 8F, manufactured by Osaka Organic Chemical Industry Ltd.) as the acrylic monomer to be dispersed, but gelation occurred and dispersion was not possible.

[0210] Comparative Example 5-4 In the same manner as in Comparative Example 5-1, an attempt was made to obtain a 40% by mass solution of polyethylene glycol #200 diacrylate (A-200, manufactured by Shin-Nakamura Chemical Co., Ltd.) using 12.0 g of polyethylene glycol #200 diacrylate as the bifunctional acrylate to be dispersed, but gelation occurred and dispersion was not possible.

[0211] Comparative Example 5-5 In the same manner as in Comparative Example 5-1, an attempt was made to obtain a 40% by mass A-200 solution using 12.0 g of tripropylene glycol diacrylate (APG-200, manufactured by Shin-Nakamura Chemical Co., Ltd.) as the bifunctional acrylate to be dispersed, but gelation occurred and dispersion was not possible.

[0212] Comparative Example 5-6 In the same manner as in Comparative Example 5-1, an attempt was made to obtain a 40% by mass A-200 solution using 12.0 g of 1,6-hexanediol diacrylate (A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.) as the bifunctional acrylate to be dispersed, but gelation occurred and dispersion was not possible.

[0213] These results indicate that when DEAA or ACMO was used as the dispersion solution, the use of a monomer having an acrylamide skeleton caused charge imbalance due to the polar structure of the nitrogen-containing solvent, which contributed to the dispersibility of the surface-modified hollow silica particles.

[0214] [6] Preparation of Solvent-Free Composition and Fabrication of Cured Film [Example 6-1] Solvent-Free Composition (NP-3 Solution) and Cured Film (NP-3 Film) To the T-2 solution (7.525 g) obtained in Example 5-1, DN-0075 (manufactured by Nippon Kayaku Co., Ltd.) (0.467 g) as a crosslinking agent, pentaerythritol tetrakis(3-mercaptobutyrate, Karenz MT PE1, manufactured by Showa Denko K.K.) (20 mass % DEAA solution) (0.275 g) as a UV radical curing aid, and Omnirad 819 (IGM Resins) as a UV radical generator were added. B.V. (manufactured by Shin-Etsu Chemical Co., Ltd.) (0.028 g) as a silane coupling agent, X-12-1333A (manufactured by Shin-Etsu Chemical Co., Ltd.) (0.014 g), a 16.8 mass% DEAA solution of EFS-521 (manufactured by DIC Corporation) (0.008 g) as a surfactant, and DEAA (1.683 g) as an additional dilution monomer were added and visually confirmed to have dissolved, to prepare a solution (hereinafter referred to as NP-3 solution). This NP-3 solution was spin-coated on a 50 mm x 50 mm x 0.7 t alkali-free glass substrate at 200 rpm for 5 seconds and 610 rpm for 30 seconds, and at a wavelength of 395 nm with a UV-LED irradiation device, 1500 mJ / cm ２ After irradiating the film with an exposure dose of 1000 ppm under nitrogen, the film was dried on a hot plate at 85° C. for 30 minutes to obtain a cured film (hereinafter referred to as NP-3 film).

[0215] The refractive index, film thickness, and b ＊ The transmittance from 400 to 800 nm and haze were measured. The results are shown in Table 4. The average transmittance from 400 to 800 nm was calculated and shown in Table 4.

[0216] These results show that by using a monomer having an acrylamide skeleton, the cured film (NP-3 film) obtained from the T-3 solution has a low refractive index, high transmittance, and low haze.

[0217] [7] Reliability test of cured film [Example 7-1] The NP-3 film was stored in a thermostatic chamber at 65°C and 90% humidity for 1000 hours, and the film properties were measured before and after storage. The physical properties were the refractive index, film thickness, b ＊, transmittance at 400 to 800 nm, and haze. The results are shown in Table 5.

[0218] From these results, the refractive index of the NP-3 film before and after the reliability test, b ＊ There was no change in the transmittance or haze, and it was found that the film was highly reliable.

[0219] According to the present invention, it is possible to provide a solventless composition that can form a cured film having a large thickness and a low refractive index. Therefore, the present invention will greatly contribute to the development of the manufacturing industry of film-forming compositions for producing electronic devices and related industries.

Claims

1. A solvent-free composition comprising a triazine ring-containing polymer, a crosslinking agent, and hollow silica particles having a space inside the outer shell, and containing no organic solvent, wherein the triazine ring-containing polymer comprises a repeating unit structure represented by the following formula (1), has at least one triazine ring terminal, and at least a portion of the triazine ring terminal is blocked with an amino group having a crosslinking group: (In formula (1), R and R′ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group; Q represents a divalent group having a ring structure and having 3 to 30 carbon atoms; and * represents a bond.) The hollow silica particles are represented by the following formulas (44), (45), and (46): R １０６ ａ Si(R １０７ ) ４－ａ Formula (44) [R １０８ ｂ Si(R １０９ ) ３－ｂ ] ２ Y ｃ Formula (45) R １１０ ｄ Si(R １１１ ) ４－ｄ Formula (46) (In formula (44), R １０６ are each an alkyl group, a halogenated alkyl group, an alkenyl group, an aryl group, or an organic group having an epoxy group, a (meth)acryloyl group, a mercapto group, an amino group, a ureido group, or a cyano group, and are bonded to a silicon atom by a Si—C bond, and R １０７ each represents an alkoxy group, an acyloxy group, or a halogen atom, a represents an integer of 1 to 3, and in formula (45) and formula (46), R １０８ and R １１０ are each an alkyl group having 1 to 3 carbon atoms or an aryl group having 6 to 30 carbon atoms and bonded to a silicon atom by a Si—C bond, and R １０９ and R １１１ each represents an alkoxy group, an acyloxy group, or a halogen atom; Y represents an alkylene group, an NH group, or an oxygen atom; b is an integer of 1 to 3; c is an integer of 0 or 1; and d is an integer of 1 to 3.

2. The solventless composition according to claim 1, wherein Q in formula (1) is a group having a structure in which at least two diphenyl ether skeletons represented by formula (16) below are bonded to each other via a substituted or unsubstituted alkyl group. (In formula (16), each A independently represents a halogen atom or a halogenated alkyl group having 1 to 10 carbon atoms, and each p independently represents an integer of 0 to 4. * represents a bond.) 3. The solventless composition according to claim 2, wherein Q in formula (1) is represented by the following formula (1-2): (In formula (1-2), R″ represents hydrogen or halogen, and * represents a bond.) 4. The solventless composition according to claim 3, wherein Q in formula (1) is represented by the following formula (1-3): (In formula (1-3), * represents a bond.) 5. The amino group having a crosslinking group is —NH—R １０２ or the solventless composition according to claim 1, represented by the following formula (1-4): (In formula (1-4), R １０２ represents a bridging group, and * represents a bond.

6. The above R １０２ The solventless composition according to claim 5, wherein is a hydroxyalkyl group, a (meth)acryloyloxyalkyl group, or a group represented by the following formula (1-5): (In the formula, A １ represents an alkylene group having 1 to 10 carbon atoms; ２ represents a single bond or the following formula (1-6): A represents a group represented by ３ represents an (a+1)-valent aliphatic hydrocarbon group which may be substituted with a hydroxy group, A ４ represents a hydrogen atom or a methyl group, a represents 1 or 2, and * represents a bond.

7. The above R １０２ is a group selected from a hydroxymethyl group, a 2-hydroxyethyl group, a (meth)acryloyloxymethyl group, a (meth)acryloyloxyethyl group, and groups represented by the following formulas (1-5-1) to (1-5-4): (In the formula, * represents a bond.) 8. The hollow silica particles contain aluminum atoms that form aluminosilicate sites, and when measured by a leaching method, Al is present on the surface of the hollow silica particles. ２ O ３ Converted to SiO ２ The aluminum atoms are 100 to 20,000 ppm / SiO per 1 g ２ 2. The solventless composition of claim 1, wherein the hydroxyl group is hydroxypropyl methylcellulose.

9. A cured film comprising a triazine ring-containing polymer and hollow silica particles, wherein the triazine ring-containing polymer contains a repeating unit structure represented by the following formula (1), has at least one triazine ring terminal, and at least a portion of the triazine ring terminal is blocked with an amino group having a crosslinking group: (In formula (1), R and R′ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group; Q represents a divalent group having a ring structure and having 3 to 30 carbon atoms; and * represents a bond.) The hollow silica particles are represented by the following formulas (44), (45), and (46): R １０６ ａ Si(R １０７ ) ４－ａ Formula (44) [R １０８ ｂ Si(R １０９ ) ３－ｂ ] ２ Y ｃ Formula (45) R １１０ ｄ Si(R １１１ ) ４－ｄ Formula (46) (In formula (44), R １０６ are each an alkyl group, a halogenated alkyl group, an alkenyl group, an aryl group, or an organic group having an epoxy group, a (meth)acryloyl group, a mercapto group, an amino group, a ureido group, or a cyano group, and are bonded to a silicon atom by a Si—C bond, and R １０７ each represents an alkoxy group, an acyloxy group, or a halogen atom, a represents an integer of 1 to 3, and in formula (45) and formula (46), R １０８ and R １１０ are each an alkyl group having 1 to 3 carbon atoms or an aryl group having 6 to 30 carbon atoms and bonded to a silicon atom by a Si—C bond, and R １０９ and R １１１ each represents an alkoxy group, an acyloxy group, or a halogen atom; Y represents an alkylene group, an NH group, or an oxygen atom; b is an integer of 1 to 3; c is an integer of 0 or 1; and d is an integer of 1 to 3.

10. The cured film according to claim 9, having a film thickness of 1,000 nm or more and 20,000 nm or less.

11. The cured film according to claim 9, which has a refractive index lower than that of the triazine ring-containing polymer.

12. A solventless composition comprising: a monomer having an acrylamide skeleton; a crosslinking agent; and hollow silica particles having a space inside an outer shell, wherein the hollow silica particles are represented by the following formulas (44), (45), and (46): R １０６ ａ Si(R １０７ ) ４－ａ Formula (44) [R １０８ ｂ Si(R １０９ ) ３－ｂ ] ２ Y ｃ Formula (45) R １１０ ｄ Si(R １１１ ) ４－ｄ Formula (46) (In formula (44), R １０６ are each an alkyl group, a halogenated alkyl group, an alkenyl group, an aryl group, or an organic group having an epoxy group, a (meth)acryloyl group, a mercapto group, an amino group, a ureido group, or a cyano group, and are bonded to a silicon atom by a Si—C bond, and R １０７ each represents an alkoxy group, an acyloxy group, or a halogen atom, a represents an integer of 1 to 3, and in formula (45) and formula (46), R １０８ and R １１０ are each an alkyl group having 1 to 3 carbon atoms or an aryl group having 6 to 30 carbon atoms and bonded to a silicon atom by a Si—C bond, and R １０９ and R １１１ each represents an alkoxy group, an acyloxy group, or a halogen atom; Y represents an alkylene group, an NH group, or an oxygen atom; b is an integer of 1 to 3; c is an integer of 0 or 1; and d is an integer of 1 to 3.

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