TW202309149A - Film-forming composition - Google Patents

Abstract

A film-forming composition that comprises a triazine ring-containing polymer, which contains a repeating unit structure represented by formula (1) and has at least one terminal triazine ring and in which at least a part of the terminal triazine ring is blocked with an amino group having a crosslinking group, a crosslinking agent, inorganic fine particles and an organic solvent. [In formula (1): R and R' independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or an aralkyl group; Q represents a divalent group having a cyclic structure and carrying 3-30 carbon atoms; and the symbol * represents a bond.].

Description

Composition for film formation

The present invention relates to a film-forming composition.

In recent years, liquid crystal displays, organic electroluminescent (EL) elements (organic EL displays or organic EL lighting), touch panels, optical semiconductors (light-emitting diodes (LEDs, etc.) For electronic devices such as batteries, dye-sensitized solar cells, and organic thin-film transistors (TFT), high-performance polymer materials are gradually required. Specific properties required include 1) heat resistance, 2) transparency, 3) high refractive index, 4) high solubility, 5) low volume shrinkage, 6) high temperature and high humidity resistance, 7) high film hardness wait. In view of this, the present applicant has found that a polymer comprising a repeating unit having a triazine ring and an aromatic ring has a high refractive index, and that the polymer alone can achieve high heat resistance, high transparency, high refractive index, high solubility properties, low volume shrinkage, and is suitable as a film-forming composition for the production of electronic devices (Patent Document 1).

However, in general, in the planarization layer or light scattering layer of organic EL lighting, there is a composition that dissolves a high refractive index material in an organic solvent, and the film is made by a coating method, but sometimes due to the transparent conductive Depending on the type of membrane, it is impossible to use a highly polar solvent. Also, after coating a film-forming composition containing a high-refractive polymer using a coating device, as a solvent for cleaning the pipeline of the device, a low-polarity solvent or the like can be used in some cases. If it is a polymer with low solubility in such a solvent , will cause the problem of pipeline blockage. Furthermore, when the thin film is exposed to solvents during the manufacture of electronic devices, cracks may occur in the thin film produced depending on the conditions, and further improvement in durability is required. [Prior Art Literature] [Patent Document]

[Patent Document 1] International Publication No. 2010/128661

[Solving the Problem of Invention]

In view of the above, the present invention aims to provide a film-forming composition capable of forming a thin film having a high refractive index and excellent transparency and solvent resistance (crack resistance). [Means to solve the problem]

In order to achieve the above object, the present inventors conducted careful research and found that by using at least one triazine ring terminal, at least a part of the triazine ring terminal is blocked by an amino group having a crosslinking group. A polymer of triazine rings and inorganic fine particles can form a thin film with a high refractive index and excellent transparency and solvent resistance, thereby completing the present invention.

(式(1)中，R及R’各自獨立表示氫原子、烷基、烷氧基、芳基或芳烷基，Q表示具有環構造之碳數3~30之2價基，*表示鍵結處)。 [2] 如[1]之膜形成用組成物，其中，前述式(1)中之Q表示選自式(2)~(13)及式(102)~(115)所示之群中至少1種。

[式(2)~式(13)中，R ¹~R ⁹²各自獨立表示氫原子、鹵原子、羧基、磺基、碳數1~10之烷基、碳數1~10之鹵素化烷基或碳數1~10之烷氧基， R ⁹³及R ⁹⁴表示氫原子或碳數1~10之烷基， W ¹及W ²各自獨立表示單鍵、CR ⁹⁵R ⁹⁶(R ⁹⁵及R ⁹⁶各自獨立表示氫原子、碳數1~10之烷基(惟，此等亦可一起形成環)，或碳數1~10之鹵素化烷基)、C=O、O、S、SO、SO ₂，或NR ⁹⁷(R ⁹⁷表示氫原子、碳數1~10之烷基或苯基)， X ¹及X ²各自獨立表示單鍵、碳數1~10之伸烷基，或式(14)

(式(14)中，R ⁹⁸~R ¹⁰¹各自獨立表示氫原子、鹵原子、羧基、磺基、碳數1~10之烷基、碳數1~10之鹵素化烷基或碳數1~10之烷氧基， Y ¹及Y ²各自獨立表示單鍵或碳數1~10之伸烷基)所示之基， *表示鍵結處]

(式(102)~式(115)中，R ¹及R ²各自獨立表示亦可具有分枝構造之碳數1~5之伸烷基，*表示鍵結處)。 [3] 如[2]之膜形成用組成物，其中，前述式(2)~(13)中，前述R ¹~R ⁹²及R ⁹⁸~R ¹⁰¹各自獨立為氫原子、鹵原子或碳數1~10之鹵素化烷基。 [4] 如[1]~[3]中任一項之膜形成用組成物，其中，前述具有交聯基之胺基為式(15)所示，

(式(15)中，R ¹⁰²表示交聯基，*表示鍵結處)。 [5] 如[4]之膜形成用組成物，其中，前述具有交聯基之胺基為式(16)所示，

(式(16)中，R ¹⁰²表示與上述相同意義，*表示鍵結處)。 [6] 如[4]或[5]之膜形成用組成物，其中，前述R ¹⁰²為含羥基之基或含(甲基)丙烯醯基之基。 [7] 如[6]之膜形成用組成物，其中，前述R ¹⁰²為羥基烷基、(甲基)丙烯醯基氧基烷基或下述式(i)表示之基，

(式(i)中，A ¹表示碳數1~10之伸烷基，A ²表示單鍵或下述式(j)

表示之基，A ³表示亦可經羥基取代之(a+1)價之脂肪族烴基，A ⁴表示氫原子或甲基，a表示1或2，*表示鍵結處)。 [8] 如[7]之膜形成用組成物，其中，前述R ¹⁰²為選自羥基甲基、2-羥基乙基、(甲基)丙烯醯基氧基甲基、(甲基)丙烯醯基氧基乙基及下述式(i-2)~式(i-5)表示之基中之基，

(式(i-1)~式(i-5)中，*表示鍵結處)。 [9] 如[2]~[8]中任一項之膜形成用組成物，其中，前述式(1)中之Q中至少1個芳香族環中含有至少1個鹵原子或碳數1~10之鹵素化烷基。 [10] 如[1]~[9]中任一項之膜形成用組成物，其中，三嗪環末端之一部份經無取代芳基胺基封止。 [11] 如[10]之膜形成用組成物，其中，前述無取代芳基胺基為式(33)所示，

(式(33)中，*表示鍵結處)。 [12] 如[1]~[11]中任一項之膜形成用組成物，其中，前述式(1)中之Q為式(17)所示，

(式(17)中，*表示鍵結處)。 [13] 如[1]~[12]中任一項之膜形成用組成物，其中，前述式(1)中之Q為式(20)所示，

(式(20)中，*表示鍵結處)。 [14] 如[1]~[13]中任一項之膜形成用組成物，其中，前述交聯劑為多官能(甲基)丙烯酸化合物。 [15] 如[1]~[14]中任一項之膜形成用組成物，其中，前述無機微粒子包含金屬氧化物、金屬硫化物或金屬氮化物。 [16] 如[1]~[15]中任一項之膜形成用組成物，其中，前述有機溶媒包含選自二醇酯系溶媒、酮系溶媒及酯系溶媒中至少1種。 [17] 一種薄膜，其係由如[1]~[16]中任一項之膜形成用組成物而得。 [18] 一種電子裝置，其係具備基材與形成於前述基材上之如[17]之薄膜。 [19] 一種光學構件，其係具備基材與形成於前述基材上之如[17]之薄膜。 [發明效果] That is, the present invention provides the following triazine ring-containing polymer and a film-forming composition comprising the same. [1] A film-forming composition comprising: a repeating unit structure represented by the following formula (1), having at least one triazine ring terminal, and at least a part of the triazine ring terminal having a crosslink Polymers containing triazine rings blocked by amine groups, cross-linking agents, inorganic microparticles, and organic solvents,

(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 with 3 to 30 carbon atoms having a ring structure, and * represents a bond junction). [2] The film-forming composition according to [1], wherein Q in the aforementioned formula (1) represents at least 1 species.

[In formulas (2) to (13), R ¹ to R ⁹² each independently represent a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group with 1 to 10 carbons, or a halogenated alkyl group with 1 to 10 carbons or an alkoxy group with 1 to 10 carbons, R ⁹³ and R ⁹⁴ represent a hydrogen atom or an alkyl group with 1 to 10 carbons, W ¹ and W ² independently represent a single bond, CR ⁹⁵ R ⁹⁶ (R ⁹⁵ and R ⁹⁶ Each independently represents a hydrogen atom, an alkyl group with a carbon number of 1 to 10 (but these can also form a ring together), or a halogenated alkyl group with a carbon number of 1 to 10), C=O, O, S, SO, SO ₂ , or NR ⁹⁷ (R ⁹⁷ represents a hydrogen atom, an alkyl group with 1 to 10 carbons or a phenyl group), X ¹ and X ² each independently represent a single bond, an alkylene group with 1 to 10 carbons, or the formula (14 )

(In formula (14), R ⁹⁸ ~ R ¹⁰¹ each independently represent a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group with 1 to 10 carbons, a halogenated alkyl group with 1 to 10 carbons, or a halogenated alkyl group with 1 to 10 carbons 10 alkoxy, Y ¹ and Y ² each independently represent a single bond or a group represented by an alkylene group with 1 to 10 carbons), * represents a bond]

(In formulas (102) to (115), R ¹ and R ² each independently represent an alkylene group with 1 to 5 carbons that may also have a branched structure, and * represents a bond). [3] The film-forming composition according to [2], wherein, in the aforementioned formulas (2) to (13), the aforementioned R ¹ to R ⁹² and R ⁹⁸ to R ¹⁰¹ are each independently a hydrogen atom, a halogen atom, or a carbon number 1-10 halogenated alkyl groups. [4] The film-forming composition according to any one of [1] to [3], wherein the amino group having a crosslinking group is represented by formula (15),

(In the formula (15), R ¹⁰² represents a crosslinking group, and * represents a bond). [5] The film-forming composition according to [4], wherein the amine group having a crosslinking group is represented by formula (16),

(In the formula (16), R ¹⁰² represents the same meaning as above, and * represents a bond). [6] The film-forming composition according to [4] or [5], wherein the aforementioned R ¹⁰² is a hydroxyl group-containing group or a (meth)acryl group-containing group. [7] The film-forming composition according to [6], wherein the aforementioned R ¹⁰² is a hydroxyalkyl group, a (meth)acryloxyalkyl group, or a group represented by the following formula (i),

(In formula (i), A ¹ represents an alkylene group with 1 to 10 carbon atoms, A ² represents a single bond or the following formula (j)

The group represented by A ³ represents an aliphatic hydrocarbon group with a valence of (a+1) which may also be substituted by a hydroxyl group, A ⁴ represents a hydrogen atom or a methyl group, a represents 1 or 2, and * represents a bond). [8] The film-forming composition according to [7], wherein the ^R102 is selected from hydroxymethyl, 2-hydroxyethyl, (meth)acryloxymethyl, (meth)acryl Base oxyethyl group and the base in the base represented by the following formula (i-2) ~ formula (i-5),

(In the formula (i-1) to the formula (i-5), * represents a bonding position). [9] The film-forming composition according to any one of [2] to [8], wherein at least one aromatic ring in Q in the aforementioned formula (1) contains at least one halogen atom or one carbon number 1 ~10 halogenated alkyl groups. [10] The film-forming composition according to any one of [1] to [9], wherein a part of the terminal of the triazine ring is blocked with an unsubstituted arylamine group. [11] The film-forming composition according to [10], wherein the unsubstituted arylamine group is represented by formula (33),

(In the formula (33), * represents a bonding site). [12] The film-forming composition according to any one of [1] to [11], wherein Q in the aforementioned formula (1) is represented by formula (17),

(In the formula (17), * represents a bonding site). [13] The film-forming composition according to any one of [1] to [12], wherein Q in the aforementioned formula (1) is represented by formula (20),

(In the formula (20), * represents a bonding site). [14] The film-forming composition according to any one of [1] to [13], wherein the crosslinking agent is a polyfunctional (meth)acrylic compound. [15] The film-forming composition according to any one of [1] to [14], wherein the inorganic fine particles include metal oxides, metal sulfides, or metal nitrides. [16] The film-forming composition according to any one of [1] to [15], wherein the organic solvent contains at least one selected from the group consisting of glycol ester-based solvents, ketone-based solvents, and ester-based solvents. [17] A thin film obtained from the film-forming composition according to any one of [1] to [16]. [18] An electronic device comprising a substrate and the thin film according to [17] formed on the substrate. [19] An optical member comprising a substrate and the thin film according to [17] formed on the substrate. [Invention effect]

According to the present invention, it is possible to provide a film-forming composition that forms a thin film having a high refractive index and excellent transparency and solvent resistance. The thin film made of the film-forming composition of the present invention can be suitably utilized in the production of liquid crystal displays, organic ELs, etc. Components (organic EL display or organic EL lighting), touch panels, optical semiconductor components, solid-state imaging components, organic thin-film solar cells, dye-sensitized solar cells, organic thin-film transistors, lenses, lenses, cameras, binoculars, The field of electronic devices or optical materials such as components of microscopes, semiconductor exposure devices, etc. In particular, a thin film made of the film-forming composition of the present invention has high transparency, high refractive index or solvent resistance (crack resistance), and can be used as a planarization layer or a light scattering layer for organic EL lighting. To use, can improve its light extraction efficiency (light diffusion efficiency), and at the same time can improve its durability.

The present invention will be described in more detail below. The film-forming composition related to the present invention includes: a polymer containing a triazine ring, a cross-linking agent, inorganic fine particles, and an organic solvent.

(1). Polymers containing triazine rings The triazine ring-containing polymer includes a repeating unit structure represented by the following formula (1). Polymers containing triazine rings are, for example, so-called hyperbranch polymers. Hyperbranched polymers refer to highly branched polymers with irregular branched structures. Irregular here means that the branched structure of the dendritic polymer is more irregular than that of a hyperbranched polymer having a regular branched structure. For example, in the polymer containing triazine ring of hyperbranch polymer, as a structure larger than the repeating unit structure represented by formula (1), the three bonds of the repeating unit structure represented by formula (1) respectively include formula ( 1) The structure (structure X) bonded by the repeating unit structure represented. In the triazine ring-containing polymer of the hyperbranch, the structure X is distributed over the entirety of the triazine ring-containing polymer except for the terminal. In the triazine ring-containing polymer of the hyperbranch polymer, the repeating unit structure may be substantially only the repeating unit structure represented by formula (1).

*表示鍵結處。

*Indicates a bond.

＜<R and R'>> In the above formula, R and R' each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or an aralkyl group, but they are preferably a hydrogen atom together from the viewpoint of further increasing the refractive index. In the present invention, the carbon number of the alkyl group is not particularly limited, but it is preferably 1 to 20. In consideration of improving the heat resistance of the polymer, the carbon number of the alkyl group is more preferably 1 to 10, which is 1~3 is better. In addition, the structure of the alkyl group is not particularly limited, and may be, for example, any of linear, branched, cyclic, and combinations of two or more of these.

Specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, s-butyl, t-butyl, cyclobutyl Base, 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-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 Base-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl, 2-ethyl-3-methyl-cyclopropyl, etc.

The carbon number of the above-mentioned alkoxy group is not particularly limited, but it is preferably 1 to 20. In consideration of improving the heat resistance of the polymer, the carbon number of the alkoxy group is more preferably 1 to 10, which is 1~3 is better. In addition, the structure of the alkyl moiety is not particularly limited, and may be, for example, any of linear, branched, cyclic, and combinations of two or more of these.

Specific examples of alkoxy include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, s-butoxy, t-butoxy base, n-pentyloxy, 1-methyl-n-butoxy, 2-methyl-n-butoxy, 3-methyl-n-butoxy, 1,1-dimethyl-n -propoxy, 1,2-dimethyl-n-propoxy, 2,2-dimethyl-n-propoxy, 1-ethyl-n-propoxy, n-hexyloxy, 1-methyl-n-pentyloxy, 2-methyl-n-pentyloxy, 3-methyl-n-pentyloxy, 4-methyl-n-pentyloxy, 1, 1-Dimethyl-n-butoxy, 1,2-dimethyl-n-butoxy, 1,3-dimethyl-n-butoxy, 2,2-dimethyl-n- Butoxy, 2,3-dimethyl-n-butoxy, 3,3-dimethyl-n-butoxy, 1-ethyl-n-butoxy, 2-ethyl-n- Butoxy, 1,1,2-trimethyl-n-propoxy, 1,2,2-trimethyl-n-propoxy, 1-ethyl-1-methyl-n-propoxy base, 1-ethyl-2-methyl-n-propoxy, etc.

The carbon number of the above-mentioned aryl group is not particularly limited, but it is preferably 6-40. If considering improving the heat resistance of the polymer, the carbon number of the aryl group is more preferably 6-16, and is 6-40. 13 is more preferably. In the present invention, the above-mentioned 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-biphenyl, m-biphenyl, p-biphenyl , 1-anthracenyl, 2-anthracenyl, 9-anthracenyl, 1-phenanthrenyl, 2-phenanthrenyl, 3-phenanthrenyl, 4-phenanthrenyl, 9-phenanthrenyl, etc.

The number of carbons in the aralkyl group is not particularly limited, but it is preferably 7 to 20 carbons. The structure of the alkyl part is not particularly limited, and it can also be linear, branched, cyclic, and the like. Any one of two or more combinations. In the present invention, an aralkyl group having a substituent is included in the aralkyl group. Examples of the substituent include a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a nitro group, and a cyano group. Specific examples thereof include benzyl, p-methylphenylmethyl, m-methylphenylmethyl, o-ethylphenylmethyl, m-ethylphenylmethyl, p-ethylphenylmethyl, p-ethylphenylmethyl, phenylmethyl, 2-propylphenylmethyl, 4-isopropylphenylmethyl, 4-isobutylphenylmethyl, α-naphthylmethyl, etc.

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

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

*表示鍵結處。

*Indicates a bond.

The above R ¹ ~ R ⁹² each independently represent a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group with 1 to 10 carbons, a halogenated alkyl group with 1 to 10 carbons or an alkoxy group with 1 to 10 carbons, R ⁹³ and R ⁹⁴ represent a hydrogen atom or an alkyl group with a carbon number of 1 to 10, W ¹ and W ² each independently represent a single bond, CR ⁹⁵ R ⁹⁶ (R ⁹⁵ and R ⁹⁶ each independently represent a hydrogen atom with a carbon number of 1 to 10 (However, these can also form a ring together), or a halogenated alkyl group with 1 to 10 carbons), C=O, O, S, SO, SO ₂ , or NR ⁹⁷ (R ⁹⁷ represents a hydrogen atom , alkyl group or phenyl group with 1 to 10 carbon atoms). Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. In addition, examples of the alkyl group and the alkoxy group include the same ones as above.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. In addition, examples of the alkyl group and alkoxy group include the same ones as the alkyl group and alkoxy group in R and R'.

The halogenated alkyl group with 1 to 10 carbons is that at least one hydrogen atom in the above-mentioned alkyl group with 1 to 10 carbons is replaced by a halogen atom. 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-Nafluoropentyl, 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-Nafluorohexyl and Perfluorohexyl. In the present invention, if consideration is given to maintaining the refractive index and improving the solubility of triazine ring-containing polymers to low-polarity solvents, etc., a perfluoroalkyl group with 1 to 10 carbons is preferred, especially a perfluoroalkyl group with 1 to 10 carbons. A perfluoroalkyl group of 1 to 5 is more preferred, and a trifluoromethyl group is still more preferred.

And, each of ^X1 and ^X2 independently represents a single bond, an alkylene group having 1 to 10 carbon atoms, or a group represented by formula (14). The structures of these alkyl groups, halogenated alkyl groups, alkoxy groups, and alkylene groups are not particularly limited, and may be, for example, linear, branched, cyclic, and any combination of two or more of these. one.

*表示鍵結處。

*Indicates a bond.

The above R ⁹⁸ ~ R ¹⁰¹ each independently represent a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group with 1 to 10 carbons, a halogenated alkyl group with 1 to 10 carbons or an alkoxy group with 1 to 10 carbons, Y ¹ and Y ² each independently represent a single bond or an alkylene group having 1 to 10 carbon atoms. Examples of these halogen atoms, alkyl groups, halogenated alkyl groups, and alkoxy groups include the same ones as the halogen atoms, alkyl groups, halogenated alkyl groups, and alkoxy groups in R ¹ to R ⁹² .

Examples of the alkylene group having 1 to 10 carbon atoms include a methylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, and a pentamethylene group. The structure of the alkylene group is not particularly limited, and may be, for example, any of linear, branched, cyclic, and combinations of two or more of these.

Among these, R ¹ to R ⁹² and R ⁹⁸ to R ¹⁰¹ are a hydrogen atom, a halogen atom, a sulfo group, an alkyl group having 1 to 5 carbons, a halogenated alkyl group having 1 to 5 carbons, or a carbon number An alkoxy group of 1-5 is preferable, and a hydrogen atom is more preferable.

In the triazine ring-containing polymer of the present invention, when Q includes an aromatic ring, at least one of the aromatic rings included in Q includes at least one halogen atom or a halogen having 1 to 10 carbon atoms Alkyl groups are preferred. It is generally known that the introduction of fluorine atoms into a compound tends to lower its refractive index, but the triazine ring-containing polymer of the present invention can maintain a refractive index exceeding 1.7 despite the introduction of fluorine atoms. The number of halogen atoms or halogenated alkyl groups in the aromatic ring can be any number that can be substituted on the aromatic ring, but if considering the balance between the maintenance of the refractive index and the solubility of the solvent, it is relatively 1 to 4 Better, 1 to 2 more preferably, 1 more preferably. In addition, when the aromatic ring is a plurality of condensed aromatic rings such as a naphthalene ring, it is only necessary to have at least one of the above-mentioned groups in the whole. Also, when Q contains a plurality of aromatic rings, at least one of the aromatic rings may contain at least one halogen atom or a halogenated alkyl group, but it is preferable that all aromatic rings contain at least one halogen atom or a halogenated alkyl group. , all aromatic rings contain one halogen atom or a halogenated alkyl group is more preferred.

Especially as Q, it is preferably at least one of the formulas (2), (5) to (13), and it is the formula (2), (5), (7), (8), (11) to ( 13) At least one of the above is more preferred. Specific examples of the divalent groups represented by the above formulas (2) to (13) include those represented by the following formulas, but are not limited thereto.

「Ph」表示苯基。*表示鍵結處。

"Ph" means phenyl. *Indicates a bond.

(式中，A各自獨立表示鹵原子或碳數1~10之鹵素化烷基，p各自獨立表示0~4之整數，q各自獨立表示0~3之整數，r各自獨立表示0~2之整數，s各自獨立表示0~5之整數，t表示1~6之整數，u表示1~4之整數。惟，各自基中，p、q、r、s之合計為1以上。「Ph」表示苯基。*表示鍵結處。)

(In the formula, A each independently represents a halogen atom or a halogenated alkyl group with 1 to 10 carbons, p represents an integer of 0 to 4 independently, q represents an integer of 0 to 3 independently, and r independently represents an integer of 0 to 2 For integers, s independently represents an integer from 0 to 5, t represents an integer from 1 to 6, and u represents an integer from 1 to 4. However, in each base, the total of p, q, r, and s is 1 or more. "Ph" Indicates a phenyl group. * Indicates a bond.)

Among these, in order to obtain a polymer with a higher refractive index, Q is more preferably a divalent group represented by the following formula.

「Ph」表示苯基。*表示鍵結處。

"Ph" means phenyl. *Indicates a bond.

(式中，A、p、q、r及u表示與上述相同意義，「Ph」表示苯基。*表示鍵結處。)

(In the formula, A, p, q, r, and u represent the same meanings as above, and "Ph" represents a phenyl group. * represents a bond.)

In particular, in consideration of improving the solubility of triazine ring-containing polymers in organic solvents such as low-polarity solvents, Q is preferably an m-phenylene group represented by formula (17).

(式中，*表示鍵結處。)

(In the formula, * indicates the bonding position.)

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

(式中，A及p表示與上述相同意義，*表示鍵結處。)

(In the formula, A and p represent the same meanings as above, and * represents a bond.)

(式中，A及p表示與上述相同意義，*表示鍵結處。)

(In the formula, A and p represent the same meanings as above, and * represents a bond.)

(式中，*表示鍵結處。)

(In the formula, * indicates the bonding position.)

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

*Indicates a bond.

In the formulas (102) to (115), the above-mentioned R ¹ and R ² each independently represent an alkylene group having 1 to 5 carbon atoms that may have a branched structure, and such an alkylene group includes methylene, Ethylene, propylene, trimethylene, tetramethylene, pentamethylene, etc., but if it is considered to increase the refractive index of the polymer obtained, it is better to be an alkylene group with 1~3 carbons. It is an alkylene group having 1 to 2 carbon atoms, specifically, a methylene group or an ethylene group is more preferable, and a methylene group is most suitable.

＜Amino group with crosslinking group＞ Furthermore, the triazine ring-containing polymer of the present invention has at least one triazine ring terminal, but at least a part of the triazine ring terminal is blocked by an amine group having a crosslinking group. Furthermore, the triazine ring-containing polymer of the present invention has at least one triazine ring terminal, but the triazine ring at the terminal usually has two halogen atoms capable of substituting the above-mentioned amine group having a crosslinking group. Therefore, the above-mentioned amine groups having a crosslinking group may be bonded to the same triazine ring end, or when there are plural triazine ring ends, each may be bonded to a different triazine ring end.

The number of cross-linking groups of amino groups with cross-linking groups is not particularly limited, and can be set to any number, but considering the balance between solvent resistance and solubility in organic solvents, 1-4 is preferred, and 1-2 More preferably one, even more preferably one. When the amine group having a crosslinking group has plural crosslinking groups, the plural crosslinking groups may have the same structure or different structures.

(式中，Z表示具有交聯基之基。*表示鍵結處。) The amino group which has a crosslinking group is represented by following formula (X), for example.

(In the formula, Z represents a group having a crosslinking group. * represents a bond.)

In formula (X), Z may be the crosslinking group itself. The crosslinking group is preferably bonded to the amine group via an aryl group.

(式中，R ¹⁰²表示交聯基，*表示鍵結處。)

(式中，R ¹⁰²表示與上述相同意義，*表示鍵結處。) Furthermore, the amino group having a crosslinking group is more preferably represented by the following formula (15), particularly preferably represented by the following formula (16).

(In the formula, R ¹⁰² represents a crosslinking group, and * represents a bond.)

(In the formula, R ¹⁰² represents the same meaning as above, and * represents a bond.)

Examples of the crosslinking group include hydroxyl-containing groups, vinyl-containing groups, epoxy-containing groups, propylene oxide-containing groups, carboxyl-containing groups, sulfonic acid-containing groups, and sulfhydryl-containing groups. , (meth)acryl group-containing group, etc., if considering improving the heat resistance of the triazine ring-containing polymer and the solvent resistance (crack resistance) of the resulting film, it is a hydroxyl-containing group and a group containing A (meth)acryloyl group is preferred.

As the hydroxyl-containing group, there are hydroxyl group and hydroxyalkyl group, etc., but the hydroxyalkyl group with 1 to 10 carbon atoms is preferred, and the hydroxyalkyl group with 1 to 5 carbon atoms is more preferable, and the hydroxyalkyl group with 1 to 3 carbon atoms is more preferable. A hydroxyalkyl group is even more preferred. Examples of hydroxyalkyl groups having 1 to 10 carbon atoms include hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 5-hydroxypentyl, 6-hydroxyhexyl, and 7-hydroxy Heptyl, 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-hydroxy-1-methylbutyl, 4-hydroxy-2-methylbutyl, 4-hydroxy-3-methylbutyl, etc., the carbon bonded by the hydroxyl group The atom is a primary carbon atom; 1-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 1-hydroxybutyl, 2-hydroxybutyl, 1-hydroxyhexyl, 2-hydroxyhexyl, 1-hydroxy Carbon bonded to hydroxyl groups such as octyl, 2-hydroxyoctyl, 1-hydroxydecyl, 2-hydroxydecyl, 1-hydroxy-1-methylethyl, 2-hydroxy-2-methylpropyl The atoms are secondary or tertiary carbon atoms.

In particular, in consideration of improving heat resistance and high-temperature and high-humidity resistance, the carbon atom bonded to the hydroxyl group is preferably a primary carbon atom, and among them, a hydroxyalkyl group having 1 to 5 carbon atoms is more preferred, and the carbon number is 1 to 3 hydroxyalkyl groups are more preferred, hydroxymethyl and 2-hydroxyethyl are more preferred, and 2-hydroxyethyl is most preferred.

As the group containing a (meth)acryloyl group, there are mentioned a (meth)acryloyl group, a (meth)acryloyloxyalkyl group and a group represented by the following formula (i). The (meth)acryloyloxyalkyl group of the alkylene group having a number of 1 to 10 is preferably a group represented by the following formula (i), and is more preferably a group represented by the following formula (i).

(式中，A ¹表示碳數1~10之伸烷基，A ²表示單鍵或下述式(j)

表示之基，A ³表示亦可經羥基取代之(a+1)價之脂肪族烴基，A ⁴表示氫原子或甲基，a表示1或2，*表示鍵結處。)

(In the formula, A ¹ represents an alkylene group with 1 to 10 carbon atoms, and A ² represents a single bond or the following formula (j)

The group represented by A ³ represents an aliphatic hydrocarbon group with a valence of (a+1) that may also be substituted by a hydroxyl group, A ⁴ represents a hydrogen atom or a methyl group, a represents 1 or 2, and * represents a bond. )

Examples of the alkylene group included in the (meth)acryloxyalkyl 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 group, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, etc. In consideration of improving heat resistance and high-temperature and high-humidity resistance, among these, those with alkylene groups having 1 to 5 carbons are preferred, those with alkylene groups having 1 to 3 carbons are preferred, and those with alkylene groups having 1 to 3 carbons are preferred. An alkylene group having 1 or 2 carbon atoms is more preferred.

Specific examples of the aforementioned (meth)acryloxyalkyl groups include (meth)acryloxymethyl, 2-(meth)acryloxyethyl, 3-(methyl) base) acryloxypropyl, 4-(meth)acryloxybutyl.

In formula (i), A ¹ is 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 or an ethylene group. Examples of the alkylene group having 1 to 10 carbon atoms include the same ones included in the above-mentioned (meth)acryloxyalkyl group.

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

(式中，*與上述相同。) 表示之基，為碳數1~5之伸烷基較佳，為碳數1~3之伸烷基再較佳，為亞甲基及伸乙基再更較佳。作為A ³之伸烷基，A ¹所例示之伸烷基中，能夠舉出碳數1~5之伸烷基。 ^A3 is a (a+1) valent aliphatic hydrocarbon group that may also be substituted by a hydroxyl group, but as its specific example, there are for example an alkylene group with 1 to 5 carbon atoms and the following formulas (k-1)~(k- 3)

(In the formula, * is the same as above.) The base represented is preferably an alkylene group having 1 to 5 carbon atoms, more preferably an alkylene group having 1 to 3 carbon atoms, and is further preferably a methylene group or an ethylene group. better. As the alkylene group of ^A3 , among the alkylene groups exemplified in ^A1 , alkylene groups having 1 to 5 carbon atoms can be mentioned.

a represents 1 or 2, but 1 is preferred.

Examples of suitable forms of the group represented by the formula (i) include those represented by the following formula (i-1).

(式中，A ¹、A ³、A ⁴及*與上述相同。)

(In the formula, A ¹ , A ³ , A ⁴ and * are the same as above.)

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

(式中，*與上述相同。)

(In the formula, * is the same as above.)

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

Epoxy, glycidyl, glycidyloxy etc. are mentioned as an epoxy-containing group. Specific examples include glycidylmethyl, 2-glycidylethyl, 3-glycidylpropyl, 4-glycidylbutyl, and the like.

As the group containing propylene oxide, there are propylene oxide-3-yl, (propylene oxide-3-yl)methyl, 2-(propylene oxide-3-yl)ethyl, 3-(epoxypropylene-3-yl)ethyl, propan-3-yl)propyl, 4-(epoxypropan-3-yl)butyl and the like.

Examples of the carboxyl group-containing group include a carboxyl group and a carboxyalkyl group having 2 to 10 carbon atoms. As a carboxyalkyl group with 2 to 10 carbons, the carbon atom to which the carboxyl group is bonded is preferably a secondary carbon atom. As specific examples, there are carboxymethyl, 2-carboxyethyl, and 3-carboxypropyl groups. And 4-carboxybutyl etc.

Examples of the sulfonic acid group-containing group include a sulfonic acid group, a sulfonic acid alkyl group having 1 to 10 carbon atoms, and the like. As a sulfoalkyl group with 1 to 10 carbons, the carbon atom to which the sulfo group is bonded is preferably a primary carbon atom. Specific examples include sulfomethyl, 2-sulfoethyl , 3-sulfopropyl and 4-sulfobutyl, etc.

Examples of the mercapto group-containing group include mercapto and mercaptoalkyl groups having 1 to 10 carbon atoms. As a mercaptoalkyl group having 1 to 10 carbons, the carbon atom to which the mercapto group is bonded is preferably a primary carbon atom. Specific examples include mercaptomethyl, 2-mercaptoethyl base, 3-mercaptopropyl and 4-mercaptobutyl, etc.

Specific examples of the amino group having a crosslinking group include those represented by the following formulas, but are not limited thereto.

式中，*表示鍵結處。

In the formula, * represents the bonding position.

In addition, the arylamine group having a hydroxyalkyl group can be introduced using a corresponding hydroxyalkyl-substituted arylamine group in the production method described later. Specific examples of the hydroxyalkyl-substituted arylamino compound include (4-aminophenyl)methanol and 2-(4-aminophenyl)ethanol.

Arylamine groups having (meth)acryloxyalkyl groups can use the corresponding (meth)acryloxyalkyl groups to replace arylamine compounds, or polymers containing triazine rings After introducing an arylamine group having a hydroxyalkyl group, it is further introduced by a method in which the hydroxyl group contained in the hydroxyalkyl group reacts with a halogenated (meth)acrylate or glycidyl (meth)acrylate.

The arylamine group having a group represented by the formula (i) can use the method of using an arylamine compound having a desired crosslinking group, or after introducing an arylamine group having a hydroxyalkyl group to a polymer containing a triazine ring , and further introduced by a method of causing the hydroxyl group contained in the above-mentioned hydroxyalkyl group to act on a (meth)acrylate compound having an isocyanate group represented by the following formula (i′).

(式中，A ³、A ⁴及a與上述相同。)

(In the formula, A ³ , A ⁴ and a are the same as above.)

As a specific example of the (meth)acryloxyalkyl substituted arylamine compound, for example, the hydroxyl group of the above-mentioned hydroxyalkyl substituted arylamine compound is mixed with a halogenated (meth)acrylate or (methyl) ) Ester compounds obtained by the action of glycidyl acrylate. Chlorinated (meth)acrylate, brominated (meth)acrylate, and iodized (meth)acrylate are mentioned as said halogenated (meth)acrylate. Specific examples of (meth)acrylate compounds having isocyanate groups represented by the above formula (i') include 2-isocyanate ethyl acrylate, 2-isocyanate ethyl methacrylate and 1,1-( Bisacryloxymethyl)ethyl isocyanate. In the present invention, 2-isocyanate ethyl acrylate is preferable from the viewpoint of a simple synthesis method.

In the present invention, examples of particularly suitable triazine ring-containing polymers include repeating units represented by formulas (21) to (28).

(式中，R、R’、R ¹~R ⁴及R ¹⁰²表示與上述相同意義)

(In the formula, R, R', R ¹ ~ R ⁴ and R ¹⁰² represent the same meaning as above)

(式中，R ¹~R ⁴及R ¹⁰²表示與上述相同意義)

(In the formula, R ¹ ~ R ⁴ and R ¹⁰² represent the same meaning as above)

(式中，R ¹⁰²表示與上述相同意義)

(In the formula, R ¹⁰² represents the same meaning as above)

(式中，R ¹⁰²表示與上述相同意義)

(In the formula, R ¹⁰² represents the same meaning as above)

(式中，R、R’、R ¹⁶~R ²³及R ¹⁰²表示與上述相同意義)

(In the formula, R, R', R ¹⁶ ~ R ²³ and R ¹⁰² represent the same meaning as above)

(式中，R ¹⁶~R ²³及R ¹⁰²表示與上述相同意義)

(In the formula, R ¹⁶ ~ R ²³ and R ¹⁰² represent the same meaning as above)

(式中，R ¹⁰²表示與上述相同意義)

(In the formula, R ¹⁰² represents the same meaning as above)

(式中，R ¹⁰²表示與上述相同意義)

(In the formula, R ¹⁰² represents the same meaning as above)

The weight average molecular weight of the polymer in the present invention is not particularly limited, but it is preferably 500-500,000, more preferably 500-100,000, and more preferably 2,000 or more from the viewpoint of improving heat resistance and reducing shrinkage. , from the viewpoint of improving the solubility and reducing the viscosity of the resulting composition, it is preferably 50,000 or less, more preferably 30,000 or less, more preferably 25,000 or less, most preferably 10,000 or less. In addition, in the present invention, the weight average molecular weight is an average molecular weight obtained by analyzing gel permeation chromatography (hereinafter referred to as GPC) and converted to standard polystyrene.

The triazine ring-containing polymer (hyperbranch polymer) of the present invention can be produced according to the method disclosed in the aforementioned International Publication No. 2010/128661. That is, after reacting a trihalogenated triazine compound and an aryl diamine compound in an organic solvent, for example, making it react with an amine having a hydroxyalkyl group (hydroxyl-containing group) with a terminal blocking agent At least one amine group in the amino compound having an acryloxyalkyl group (acrylyl group-containing group) and the amino compound having a group represented by formula (i) (acrylyl group-containing group) The compounds are reacted to obtain the triazine ring-containing polymer of the present invention.

For example, as shown in the following Scheme 1, the triazine ring-containing polymer (23) can be obtained by reacting a triazine compound (29) and an aryl diamine compound (30) in a suitable organic solvent, and then making it It is obtained by reacting with at least one arylamine compound (31) selected from the group consisting of arylamine compounds having a hydroxyalkyl group and arylamine compounds having a group represented by formula (i) as a terminal blocking agent.

(式中，X各自獨立表示鹵原子，R ^a表示羥基烷基或式(i)表示之基。)

(In the formula, X each independently represents a halogen atom, and R ^a represents a hydroxyalkyl group or a group represented by formula (i).)

And, for example, as shown in the following scheme 2, the triazine ring-containing polymer (27) can be obtained by reacting a triazine compound (29) and an aryl diamine compound (32) in a suitable organic solvent, It is obtained by reacting at least one arylamine compound (31) selected from the group consisting of arylamine compounds having a hydroxyalkyl group and arylamine compounds having a group represented by formula (i) as a terminal blocking agent .

(式中，X各自獨立表示鹵原子，R ^a表示羥基烷基或式(i)表示之基。)

(In the formula, X each independently represents a halogen atom, and R ^a represents a hydroxyalkyl group or a group represented by formula (i).)

In the above scheme 1 or scheme 2, the addition ratio of the aryl diamine compound (30) or (32) can be arbitrary as long as the target polymer can be obtained, but relative to 1 equivalent of the triazine compound (29), the aryl diamine The amino compound (30) or (32) is preferably 0.01-10 equivalents, more preferably 0.7-5 equivalents. The aryl diamine compound (30) or (32) can also be added directly or dissolved in an organic solvent solution, but considering the ease of operation and the ease of control of the reaction, the latter method is more suitable. The reaction temperature may be appropriately set within the range from the melting point of the solvent used to the boiling point of the solvent, but it is preferably about -30 to 150°C, and more preferably -10 to 100°C.

As another mode, there is a method shown in Flow 3 below. In this method, the triazine ring-containing polymer (23) can be prepared by reacting the triazine compound (29) and the aryldiamine compound (30) in an appropriate organic solvent, and then reacting it with a terminal blocking agent. The arylamino compound (31') having a hydroxyalkyl group reacts to obtain a triazine ring-containing polymer (23') (the first stage), and then the triazine ring-containing polymer (23' ) and the hydroxyl group of the hydroxyalkyl group contained in ) react with the (meth)acrylate compound having an isocyanate group represented by formula (i') (second stage). In addition, when the triazine ring-containing polymer (23') is used as the target object, the reaction in the second stage is not carried out, and the reaction in the first stage may be completed.

(式中，R ^a1表示羥基烷基，X、A ³、A ⁴、R ^a及a表示與上述相同意義)

(In the formula, R ^a1 represents a hydroxyalkyl group, and X, A ³ , A ⁴ , R ^a and a represent the same meanings as above)

In addition, as another mode, there is a technique shown in Flowchart 4 below. In this method, the triazine ring-containing polymer (27) can be prepared by reacting the triazine compound (29) and the aryl diamine compound (32) in an appropriate organic solvent, and then reacting it with a terminal blocking agent. The arylamino compound (31') having a hydroxyalkyl group reacts to obtain a triazine ring-containing polymer (27') (the first stage), and then the triazine ring-containing polymer (27' ) and the alkyl group of the hydroxyalkyl group contained in ) react with the (meth)acrylate compound having an isocyanate group represented by the formula (i') (the second stage). In addition, when the triazine ring-containing polymer (27') is used as the target object, the reaction in the second stage is not carried out, and the reaction in the first stage may be completed.

(式中，R ^a1表示羥基烷基，X、A ³、A ⁴、R ^a及a表示與上述相同意義)

(In the formula, R ^a1 represents a hydroxyalkyl group, and X, A ³ , A ⁴ , R ^a and a represent the same meanings as above)

In the above scheme 3, the addition ratio and addition method of the aryl diamine compound (30) in the first stage, and the reaction temperature in the reaction until the triazine ring-containing polymer (23') can be obtained can be compared with those of the scheme 1. The instructions are the same. And, in the second stage, relative to the triazine ring-containing polymer (23'), the addition ratio of the (meth)acrylate compound having an isocyanate group represented by the formula (i') can be adjusted according to the ratio of the hydroxyalkyl group to the formula ( The ratio of the groups represented by i) is set arbitrarily, preferably 0.1 to 10 equivalents, more preferably 0.5 to 5 equivalents, and even more preferably 1 equivalent of the arylamino compound having a hydroxyalkyl group used. Preferably it is 0.7-3 equivalents, more preferably 0.9-1.5 equivalents. For example, when all the hydroxyalkyl groups contained in the triazine ring-containing polymer (23') are used as groups represented by the formula (i), the addition ratio is 1 equivalent of the arylamino compound having a hydroxyalkyl group used. , the above-mentioned (meth)acrylate compound is preferably 1.0-10 equivalents, more preferably 1.0-5 equivalents, still more preferably 1.0-3 equivalents, still more preferably 1.0-1.5 equivalents. The reaction temperature in this reaction is the same as the reaction temperature in the reaction to obtain the triazine ring-containing polymer (23'), but considering that polymerization of (meth)acryl groups does not occur during the reaction, it is 30 to 80°C. Preferably, it is more preferably 40~70°C, and even more preferably 50~60°C.

In the above scheme 4, the addition ratio, addition method, and reaction temperature of the aryl diamine compound (32) can be the same as those described in scheme 2. And, in the second stage, relative to the triazine ring-containing polymer (27'), the addition ratio of the (meth)acrylate compound having an isocyanate group represented by the formula (i') can be adjusted according to the ratio of the hydroxyalkyl group and the formula ( The ratio of the groups represented by i) is set arbitrarily, preferably 0.1-10 equivalents, more preferably 0.5-5 equivalents, and still more preferably 1 equivalent of the arylamino compound having a hydroxyalkyl group used. 0.7-3 equivalents, more preferably 0.9-1.5 equivalents. For example, when all the hydroxyalkyl groups contained in the triazine ring-containing polymer (22') are used as groups represented by the formula (i), the addition ratio is 1 equivalent of the arylamino compound having a hydroxyalkyl group used, The above-mentioned (meth)acrylate compound is preferably 1.0-10 equivalents, more preferably 1.0-5 equivalents, still more preferably 1.0-3 equivalents, still more preferably 1.0-1.05 equivalents. The reaction temperature in this reaction is the same, but in consideration of not causing (meth)acryl group polymerization during the reaction, it is preferably 30 to 80°C, more preferably 40 to 70°C, and still more preferably 50 to 60°C. good.

In the second stage of scheme 3 and scheme 4, in order not to cause (meth)acryl group polymerization during the reaction, the reaction can also be carried out in the presence of a polymerization inhibitor. Examples of the polymerization inhibitor include N-methyl-N-nitrosoaniline, N-nitrosophenylhydroxylamine or salts thereof, benzoquinones, phenolic polymerization inhibitors, and phenothiazines. Among them, N-nitrosophenylhydroxylamine or a salt thereof is preferable from the viewpoint of excellent polymerization inhibition effect. Examples of N-nitrosophenylhydroxylamine salts include N-nitrosophenylhydroxylamine ammonium salt and N-nitrosophenylhydroxylamine aluminum salt. Examples of benzoquinones include p-benzoquinone, 2-methyl-1,4-benzoquinone, and the like. Examples of phenolic polymerization inhibitors include hydroquinone, p-methoxyphenol, 4-t-butylbenzenediol, 2-t-butylhydroquinone, 2,6-di-t-butyl- 4-Methylphenol etc. The usage amount of the polymerization inhibitor is not particularly limited, but for example, the mass ratio may be 1~200ppm or 10~100ppm relative to the (meth)acrylate compound having isocyanate group represented by formula (i'). By using a polymerization inhibitor, even if the reaction temperature is increased to about 60~80°C, the polymerization of (meth)acryloyl groups can be inhibited, and the second-stage reaction can proceed.

As the organic solvent, various solvents commonly used in this reaction can be used, such as tetrahydrofuran (THF), dioxane, dimethylsulfoxide; 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'-Dimethylethylenylurea, N,N,N',N'-Tetramethylpropane Diacidamide, N-methylcaprolactam, N-acetylpyrrolidine, N,N-diethylacetamide, N-ethyl-2-pyrrolidone, N,N-dimethylpropane Amide-based solvents such as amide, N,N-dimethylisobutylamide, N-methylformamide, N,N'-dimethylpropylidene urea, and their mixed solvents. Among them, N,N-dimethylformamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, 3-methoxy-N,N- Dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide and mixtures thereof are preferred, especially N,N-dimethylacetamide, N-methyl- 2-pyrrolidone, 3-methoxy-N,N-dimethylpropanamide, and 3-butoxy-N,N-dimethylpropanamide are more suitable.

In addition, in the reaction of the first stage of the above-mentioned Scheme 1 or Scheme 2, various salt groups 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, calcium oxide, barium hydroxide, trilithium phosphate, trisodium phosphate, tripotassium phosphate, cesium fluoride, aluminum oxide, ammonium, n-propylamine, trimethylamine, triethylamine, diisopropylamine Amine, diisopropylethylamine, N-methylpiperidine, 2,2,6,6-tetramethyl-N-methylpiperidine, pyridine, 4-dimethylaminopyridine, N-methylpiperidine Morphofurin, 2-aminoethanol, ethyldiethanolamine, diethylaminoethanol, etc. The amount of the base added is preferably 1 to 100 equivalents, more preferably 1 to 10 equivalents, relative to 1 equivalent of the triazine compound (29). Moreover, these bases can also be used as an aqueous solution. It is preferable that no raw material components remain in the obtained polymer, but a part of the raw materials may remain as long as the effect of the present invention is not impaired. After the reaction, the product can be easily purified by reprecipitation or the like.

A known method may be used as a terminal-blocking method using an amino compound having a crosslinking group. At this time, the amount of the end-blocking agent is preferably about 0.05-10 equivalents, more preferably 0.1-5 equivalents, and 0.5 equivalents relative to 1 equivalent of halogen atoms from the remaining triazine compound not used in the polymerization reaction ~2 equiv is even better. As the reaction medium or reaction temperature, the same conditions as those described in the first stage of the above-mentioned scheme 1 or scheme 2 are mentioned, and the terminal blocking agent can also be mixed with the aryl diamine compound (30) or (32) Also added. In addition, an unsubstituted arylamino compound having no crosslinking group may be used to end-cap with two or more types of groups. Examples of the aryl group of the unsubstituted arylamino compound include the same ones as above.

Specific examples of unsubstituted arylamine groups include those represented by the following formula (33), but are not limited thereto.

*表示鍵結處。

*Indicates a bond.

Also, the unsubstituted arylamine group can be introduced using a corresponding unsubstituted arylamine compound. Aniline etc. are mentioned as a specific example of an unsubstituted aryl amino compound.

Moreover, when introducing an unsubstituted arylamine group, the ratio of the amino compound having a crosslinking group to the unsubstituted arylamine compound is relatively good in terms of exhibiting a good balance of solubility in organic solvents and yellowing resistance. 0.1-1.0 mole of the unsubstituted aryl amino compound is preferably 0.1-0.5 mole, still more preferably 0.1-0.3 mole, based on 1 mole of the amino compound having a crosslinking group.

Also, in addition to the end-capping using an amine compound having a crosslinking group, an arylamine compound having a substituent containing a specific heteroatom can also be used for terminal capping. The refractive index of the resulting film can be further increased by end-capping with an arylamine group having a substituent containing a specific heteroatom. Examples of substituents containing specific heteroatoms include cyano, alkylamino, arylamino, nitro, alkylsulfhydryl, arylsulfhydryl, alkoxycarbonyl, alkoxycarbonyloxy base. Examples of the arylamine group having a substituent containing a specific heteroatom include those represented by the following formula (34).

式中，Y為「含特定雜原子之取代基」，且表示氰基、烷基胺基、芳基胺基、硝基、烷基氫硫基、芳基氫硫基、烷氧基羰基或烷氧基羰基氧基。m表示1~5之整數。m為2以上時，Y亦可相同或相異。*表示鍵結處。

In the formula, Y is a "substituent containing a specific heteroatom" and represents a cyano group, an alkylamino group, an arylamino group, a nitro group, an alkylsulfhydryl group, an arylsulfhydryl group, an alkoxycarbonyl group or Alkoxycarbonyloxy. m represents an integer from 1 to 5. When m is 2 or more, Y may be the same or different. *Indicates a bond.

Among these, Y is preferably a cyano group or a nitro group. m is preferably 1. When m is 1, Y is preferably a substituent para-position or meta-position.

Also, when introducing an arylamine group having a substituent containing a specific heteroatom, the ratio of the amine compound having a crosslinking group to the arylamine compound having a substituent containing a specific heteroatom is well balanced to exhibit good resistance. From the viewpoint of solubility and high refractive index, relative to 1 mole of the amino compound having a crosslinking group, the arylamine compound having a substituent containing a specific heteroatom is preferably 0.1 to 1.0 mole, which is 0.1~0.5 mole is more preferable, and 0.1~0.3 mole is still more preferable.

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

(2).Crosslinking agent The crosslinking agent is not particularly limited as long as it is a compound having two or more substituents capable of reacting with the crosslinking group of the triazine ring-containing polymer. Examples of such compounds include melamine-based compounds (such as phenolic plastic compounds, amine plastic compounds, etc.), substituted urea-based compounds, epoxy group-containing Or cross-linked propylene oxide groups to form substituent compounds (such as polyfunctional epoxy compounds, polyfunctional propylene oxide compounds, etc.), compounds containing blocked isocyanate groups, compounds with acid anhydride groups, compounds with (methyl) Compounds with acrylic groups, etc., but from the viewpoint of heat resistance and storage stability, compounds containing epoxy groups, blocked isocyanate groups, and (meth)acrylic groups are preferred, especially those with blocked isocyanate groups Compounds, or polyfunctional epoxy compounds and/or polyfunctional (meth)acrylic compounds capable of imparting a photocurable composition without using an initiator are preferred.

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 ginseng (2,3-epoxypropyl) polyisocyanate, 1,4-butanediol diglycidyl ether, 1,2-epoxy-4-(ethylene oxide) base) cyclohexane, glycerol triglycidyl ether, diethylene glycol diglycidyl ether, 2,6-diglycidyl phenyl glycidyl ether, 1,1,3-reference [ p-(2,3-Epoxypropoxy)phenyl]propane, Diglycidyl 1,2-cyclohexanedicarboxylate, 4,4'-methylenebis(N,N-di Epoxypropylaniline), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, trimethylolethane triglycidyl ether, bisphenol-A-di Glycidyl ether, pentaerythritol polyglycidyl ether, etc.

In addition, as commercially available products, YH-434 and YH434L (manufactured by NIPPON STEEL Chemical & Material Co., Ltd.) of epoxy resins having at least two epoxy groups, and epoxy resins having an epoxycyclohexane structure can be used. Epolead GT-401, same GT-403, same GT-301, same GT-302, Celoxide 2021, same 3000 (made by Daicel), jER1001 of bisphenol A type epoxy resin, same 1002, same 1003, same 1004, same as 1007, same as 1009, same as 1010, same as 828 (manufactured by Mitsubishi Chemical Co., Ltd. above), jER807 of bisphenol F type epoxy resin (manufactured by Mitsubishi Chemical Co., Ltd.), of phenol novolac resin type epoxy resin jER152, Tong 154 (the above are manufactured by Mitsubishi Chemical Co., Ltd.), EPPN201, Tong 202 (the above are manufactured by Nippon Kayaku Co., Ltd.), EOCN-102 of cresol phenolic resin type epoxy resin, Tong 103S, Tong 104S, Same 1020, Same 1025, Same 1027 (manufactured by Nippon Kayaku Co., Ltd. above), jER180S75 (manufactured by Mitsubishi Chemical Co., Ltd.), Denacol EX-252 of alicyclic epoxy resin (manufactured by Nagase ChemteX Co., Ltd.), CY175, CY177, CY179 (the above are manufactured by CIBA-GEIGY A.G), Araldite CY-182, the same as CY-192, the same as CY-184 (the above are manufactured by CIBA-GEIGY A.G), Epiclon 200, the same as 400 (the above are DIC (shares) )), jER871, Tong 872 (the above are manufactured by Mitsubishi Chemical Co., Ltd.), ED-5661, ED-5662 (the above are manufactured by Celanese Coating Co., Ltd.), Denacol EX-611 of aliphatic polyglycidyl ether , Same as EX-612, Same as EX-614, Same as EX-622, Same as EX-411, Same as EX-512, Same as EX-522, Same as EX-421, Same as EX-313, Same as EX-314, Same as EX-321 (manufactured by Nagase ChemteX Co., Ltd.), etc.

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, and ethoxylated bisphenol A diacrylate. , Ethoxylated Bisphenol A Dimethacrylate, Ethoxylated Trimethylolpropane Triacrylate, Ethoxylated Trimethylolpropane Trimethacrylate, Ethoxylated Glycerol Triacrylate, Ethoxylated Glycerol Trimethacrylate, Ethoxylated Pentaerythritol Tetraacrylate, Ethoxylated Pentaerythritol Tetramethacrylate, Ethoxylated Dipentaerythritol Hexaacrylate, Polyglycerol Monooxide Polyacrylate, Polyglycerol Polyethylene Glycol Polyacrylate , dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, trimethylolpropane Triacrylate, trimethylolpropane trimethacrylate, tricyclodecane dimethanol diacrylate, tricyclodecane dimethanol dimethacrylate, 1,6-hexanediol diacrylate, 1 , 6-hexanediol dimethacrylate, polybasic acid denatured acrylic oligomer, etc.

In addition, the polyfunctional (meth)acrylic compound can be obtained as a commercial item, and its specific examples include NK ester A-200, TO A-400, TO A-600, TO A-1000, TO A-9300 (isocyanuric acid ginseng (2-acryloxyethyl ester)), same A-9300-1CL, same A-TMPT, same UA-53H, same 1G, same 2G, same 3G, same 4G, same 9G, same 14G, same 23G, same ABE-300, same A-BPE-4, same A-BPE-6, same A-BPE-10, same A-BPE-20, same A-BPE-30, same BPE -80N, Same as BPE-100N, Same as BPE-200, Same as BPE-500, Same as BPE-900, Same as BPE-1300N, Same as A-GLY-3E, Same as A-GLY-9E, Same as A-GLY-20E, Same as A-TMPT-3EO, same as A-TMPT-9EO, same as AT-20E, same as ATM-4E, same as ATM-35E, APG-100, APG-200 (the above are manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), KAYARAD ( Registered trademark) DPEA-12, same as PEG400DA, same as THE-330, same as RP-1040 (manufactured by Nippon Kayaku Co., Ltd. above), ARONIX M-210, M-350 (manufactured by Toagosei Co., Ltd. above), KAYARAD (registered trademark) DPHA, same NPGDA, same PET30 (the above are made by Nippon Kayaku Co., Ltd.), NK ester A-DPH, same A-TMPT, same A-DCP, same A-HD-N, same TMPT, Same as DCP, same NPG, same HD-N (manufactured by New Nakamura Chemical Co., Ltd. above), NK OLIGO U-15HA (manufactured by New Nakamura Chemical Co., Ltd.), NK Polymers VANARESIN GH-1203 (manufactured by New Nakamura Chemical Co., Ltd. (Co., Ltd.), DN-0075 (Nippon Kayaku Co., Ltd.), etc. The above-mentioned polybasic acid-denatured acrylic oligomer can also be obtained as a commercial item, and its specific example includes ARONIX M-510, 520 (the above are manufactured by Toagosei Co., Ltd.).

The compound having an acid anhydride group is not particularly limited as long as it is a carboxylic anhydride obtained by dehydrating and condensing two molecules of carboxylic acid. Hydrophthalic anhydride, methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, tetrahydrophthalic anhydride, endomethylene tetrahydrophthalic anhydride, maleic anhydride, succinic anhydride, octylbutane Acid anhydride, dodecenylsuccinic anhydride, etc. have an acid anhydride group in the molecule; 1,2,3,4-cyclobutanetetracarboxylic dianhydride, pyromellitic anhydride, 3,4-dicarboxy-1, 2,3,4-tetrahydro-1-naphthalene dianhydride, bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic dianhydride, 5-(2,5-dioxo Tetrahydro-3-furyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 1,2,3,4-butanetetracarboxylic dianhydride, 3,3', 4,4'-Benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoro Those having two acid anhydride groups in the molecule, such as propane dianhydride and 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, etc.

As a compound containing a blocked isocyanate group, as long as it has two or more isocyanate groups (-NCO) blocked by an appropriate protecting group in one molecule, and is exposed to high temperature during thermal curing, the protecting group ( block part) will thermally dissociate and separate, and the resulting isocyanate group will cause a crosslinking reaction between the crosslinking groups (for example, hydroxyl group-containing groups) of the triazine ring-containing polymer of the present invention, and there is no Particularly limited examples include compounds having two or more groups represented by the following formula (and these groups may be the same or different) in one molecule.

(式中，R _b表示嵌段部之有機基。)

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

Such a compound can be obtained, for example, by reacting a compound having two or more isocyanate groups in one molecule with an appropriate blocking agent. Examples of compounds having two or more isocyanate groups in one molecule include isophorone diisocyanate, 1,6-hexamethylene diisocyanate, methylene bis(4-cyclohexyl isocyanate), trimethylhexa Polyisocyanate of methylene diisocyanate, or its dimers, trimers, and their reactants with diols, triols, diamines or triamines, etc. Examples of blocking agents include methanol, ethanol, isopropanol, n-butanol, 2-ethoxyhexanol, 2-N,N-dimethylaminoethanol, 2-ethoxyethanol, cyclohexanol Alcohols such as phenol, o-nitrophenol, p-chlorophenol, o-, m- or p-cresol and other phenols; ε-caprolactam and other lactams, acetone oxime, formazan Oximes such as ethyl ethyl ketone oxime, methyl isobutyl ketone oxime, cyclohexanone oxime, acetophenone oxime, benzophenone oxime, etc.; pyrazole, 3,5-dimethylpyrazole, 3-methyl Pyrazoles such as pyrazole; Thiols such as dodecanethiol and benzenethiol, etc.

Compounds containing blocked isocyanate groups are commercially available, and specific examples thereof include Takenate (registered trademark) B-830, B-815N, B-842N, B-870N, B-874N, and B-882N , B-7005, B-7030, B-7075, B-5010 (the above are manufactured by Mitsui Chemicals Co., Ltd.), Duranate (registered trademark) 17B-60PX, same as TPA-B80E, same as MF-B60X, same as MF-K60X , Same as E402-B80T (manufactured by Asahi Kasei Co., Ltd. above), Karenz MOI-BM (registered trademark) (manufactured by Showa Denko Co., Ltd. above), TRIXENE (registered trademark) BI-7950, BI-7951, BI-7960 , BI-7961, BI-7963, BI-7982, BI-7991, BI-7992 (manufactured by Baxenden Chemicals LTD), etc.

The amine plastic compound is not particularly limited as long as it has two or more methoxymethyl groups in one molecule, and examples include hexamethoxymethylmelamine CYMEL (registered trademark) 303, tetrabutoxymethyl Acetylene carbamide Tong 1170, Tetramethoxymethylbenzoguanamine Tong 1123 (the above are Cytec Industries Co., Ltd., Japan) and other Cymel series, methylated melamine resin NIKALAC (registered trademark) MW-30HM, Tong MW- 390, same MW-100LM, same MX-750LM, methylated urea resin same as MX-270, same MX-280, same MX-290 (the above are manufactured by Sanwa Chemical) and other melamine Department of compounds. The polyfunctional propylene oxide compound is not particularly limited as long as it has two or more propylene oxide groups in one molecule. Examples include OXT-221, OX-SQ-H, and OX that contain propylene oxide groups. -SC (the above are manufactured by Toa Gosei Co., Ltd.), etc.

Bakelite compounds have more than 2 hydroxymethyl groups in one molecule, and when exposed to high temperature during thermosetting, the cross-linking groups of the triazine ring-containing polymer of the present invention can be dehydrated and condensed for cross-linking reactions. Examples of phenoplast compounds include 2,6-dihydroxymethyl-4-methylphenol, 2,4-dihydroxymethyl-6-methylphenol, bis(2-hydroxy-3-hydroxymethyl- 5-methylphenyl)methane, bis(4-hydroxy-3-hydroxymethyl-5-methylphenyl)methane, 2,2-bis(4-hydroxy-3,5-dihydroxymethylphenyl) ) propane, bis(3-formyl-4-hydroxyphenyl)methane, bis(4-hydroxy-2,5-dimethylphenyl)formylmethane, α,α-bis(4-hydroxy- 2,5-Dimethylphenyl)-4-formyltoluene, etc. The phenolic plastic compound can be obtained as a commercial product, and its specific examples include 26DMPC, 46DMOC, DM-BIPC-F, DM-BIOC-F, TM-BIP-A, BISA-F, BI25X-DF, BI25X -TPA (the above are manufactured by Asahi Organic Materials Co., Ltd.), etc.

Among these, polyfunctional (meth)acrylic compounds are suitable from the viewpoint of suppressing the decrease in the refractive index caused by the blending of the crosslinking agent and at the same time rapidly advancing the curing reaction. From the viewpoint of excellent compatibility of polymers of triazine rings, polyfunctional (meth)acrylic compounds having the following isocyanuric acid skeleton are more preferable. Examples of the polyfunctional (meth)acrylic compound having such a skeleton include NK ester A-9300 and Tong A-9300-1CL (both are manufactured by Shin-Nakamura Chemical Co., Ltd.).

(式中，R ¹¹¹~R ¹¹³各自獨立為末端具有至少1個(甲基)丙烯酸基之一價有機基。)

(In the formula, R ¹¹¹ to R ¹¹³ are each independently a valent organic group having at least one (meth)acrylic group at the end.)

And, from the point of view of increasing the curing speed and improving the solvent resistance, acid resistance and alkali resistance of the obtained cured film at the same time, it is liquid at 25°C, and its viscosity is 5,000mPa･s or less, preferably 1~3,000mPa･s, more preferably 1~1,000mPa･s, more preferably 1~500mPa･s multifunctional (meth)acrylic compound (hereinafter referred to as low viscosity crosslinking agent) alone or It is suitable to use in combination of 2 or more types, or to use in combination with the said polyfunctional (meth)acrylic compound which has an isocyanuric acid skeleton. Such a low-viscosity crosslinking agent can also be obtained as a commercial product, for example, among the above-mentioned polyfunctional (meth)acrylic compounds, NK esterA-GLY-3E (85mPa･s, 25°C), same as A-GLY-9E (95mPa･s, 25℃), same as A-GLY-20E (200mPa･s, 25℃), same as A-TMPT-3EO (60mPa･s, 25℃), same as A-TMPT-9EO, same as ATM-4E (150mPa･s, 25°C), and ATM-35E (350mPa･s, 25°C) (the above are manufactured by Shin-Nakamura Chemical Co., Ltd.) agent.

Furthermore, in consideration of improving the alkali resistance of the resulting cured film, at least one of NK esterA-GLY-20E (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) and ATM-35E (manufactured by Shin-Nakamura Chemical Co., Ltd.) It is suitable to be used in combination with the polyfunctional (meth)acrylic compound having the above-mentioned isocyanuric acid skeleton.

In addition, when a film formed by laminating the triazine ring-containing polymer of the present invention on a protective film such as PET or polyolefin film is irradiated with light through the protective film, the film laminated film can also be free from oxygen hindrance and Get good hardenability. At this time, since the protective film must be peeled off after hardening, it is preferable to use a polybasic acid-denatured acrylic oligomer that imparts a film with good peelability.

The above-mentioned crosslinking agents may be used alone or in combination of two or more. The content of the crosslinking agent in the film-forming composition is preferably 1 to 500 parts by mass relative to 100 parts by mass of the triazine ring-containing polymer, but in consideration of controlling the refractive index, it is preferably 30 to 300 parts by mass. More preferably, it is 50-100 mass parts.

(3). Inorganic microparticles. Inorganic microparticles contain, for example, Be, Al, Si, Ti, V, Fe, Cu, Zn, Y, Zr, Nb, Mo, In, Sn, Sb, Ta, W, Pb, Oxides, sulfides, or nitrides of one or more metals in the group consisting of Bi and Ce, especially metal oxides containing these are suitable. In addition, the inorganic fine particles may be used alone, or may be used in combination of two or more. Specific examples of metal oxides include Al ₂ O ₃ , ZnO, TiO ₂ , ZrO ₂ , Fe ₂ O ₃ , Sb ₂ O ₅ , BeO, ZnO, SnO ₂ , CeO ₂ , SiO ₂ , WO ₃ wait. Furthermore, it is most effective to use a plurality of metal oxides as composite oxides. The composite oxide refers to a mixture of two or more inorganic oxides in the production stage of fine particles. Examples include composite oxides of TiO ₂ and ZrO ₂ , composite oxides of TiO ₂ and ZrO ₂ and SnO ₂ , composite oxides of ZrO ₂ and SnO ₂ , and the like. Furthermore, compounds of the above-mentioned metals may also be used. Examples include ZnSb ₂ O ₆ , BaTiO ₃ , SrTiO ₃ , SrSnO ₃ and the like. These compounds can be used individually or in mixture of 2 or more types, and can also be used in mixture with the said oxide.

In addition, the inorganic fine particles used in the present invention may be surface-modified inorganic fine particles. Such inorganic fine particles may have at least any one of a hydrophilic group and a crosslinkable group on the surface. Inorganic microparticles having at least any one of a hydrophilic group and a crosslinking group on the surface (hereinafter also sometimes referred to as "surface-modified inorganic microparticles") can, for example, use the above-mentioned inorganic microparticles as core particles, and have hydrophilic Obtained by modifying the surface of the core particle by at least any one of the organosilicon compound having a sex group and the organosilicon compound having a cross-linking group. By using the surface-modified inorganic fine particles as the inorganic fine particles, the dispersion stability in the resin can be improved, and the HAZE of the cured film can be further suppressed. Organosilicon compounds have hydrolyzable groups that generate Si-OH groups by hydrolysis. Examples of the hydrolyzable group include an alkoxy group bonded to a silicon atom, an acetyloxy group bonded to a silicon atom, and the like. The number of hydrolyzable groups in the organosilicon compound is not particularly limited, but there are, for example, 1 to 3 groups.

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

Examples of organosilicon compounds having hydrophilic groups include [methoxy(polyethyleneoxy)n-propyl]trimethoxysilane, [methoxy(polyethyleneoxy)n-propyl]triethyl Oxysilane, [methoxy(polyethyleneoxy) n-propyl]tripropropoxysilane, [methoxy(polyethyleneoxy)n-propyl]triacetyloxysilane, [methoxy (Polypropyleneoxy)n-Propyl]Trimethoxysilane, [Methoxy(Polypropyleneoxy)n-Propyl]Triethoxysilane, [Methoxy(Polypropyleneoxy)n-Propyl] ]Tripropoxysilane, "Methoxy(polypropyleneoxy) n-propyl" triacetyloxysilane, [methoxy(polybutenyloxy) n-propyl]trimethoxysilane, [Methoxy(polybutenyloxy) n-propyl]tripropropoxysilane, [methoxy(polybutenyloxy)n-propyl]triacetyloxysilane, [methoxy( Polyvinyloxy)n-propyl]dimethoxymethylsilane, [methoxy(polyethyleneoxy)n-propyl]diethoxymethylsilane, [methoxy(polyethyleneoxy) n-propyl]dipropoxymethylsilane, [methoxy(polyethyleneoxy)n-propyl]diacetyloxymethylsilane,[methoxy(polypropyleneoxy)n-propyl base] dimethoxymethylsilane, [methoxy(polypropyleneoxy) n-propyl]diethoxymethylsilane, [methoxy(polypropyleneoxy)n-propyl]dipropoxy Dimethoxymethylsilane, [methoxy(polypropyleneoxy) n-propyl]diethyloxymethylsilane, [methoxy(polybutenyloxy)n-propyl]dimethoxymethylsilane Diethoxymethylsilane, [methoxy(polybutenyloxy) n-propyl]diethoxymethylsilane, [methoxy(polybutenyloxy)n-propyl]dipropoxymethylsilane, [Methoxy(polybutenyloxy)n-propyl]diacetyloxymethylsilane, etc.

The crosslinkable group is not particularly limited as long as it can react with a crosslinking agent to form a crosslinked structure, and examples thereof include radical polymerizable groups, epoxy groups, and amine groups. As a radical polymerizable group, an allyl group, a (meth)acryloxy group, etc. are mentioned, for example.

Examples of organosilicon compounds having radically polymerizable groups include 3-acryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyl oxypropylmethyldiethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryl Oxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 8-methacryloxyoctyl Trimethoxysilane, 10-methacryloxydecyltrimethoxysilane, etc. Examples of organosilicon compounds having epoxy groups include 3-glycidyloxypropyltrimethoxysilane and 8-glycidyloxyoctyltrimethoxysilane. Examples of organosilicon compounds with amino groups include N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3- Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, etc. These may be used individually by 1 type, and may use it in combination of 2 or more types.

The bonding amount of the organosilicon compound on the surface of the core particle is not particularly limited, but is preferably 0.1 to 30% by mass, more preferably 1 to 15% by mass, relative to the core particle.

The primary particle diameter (observed by a transmission electron microscope) of the inorganic fine particles or surface-modified inorganic fine particles is preferably 20 nm or less from the viewpoints of dispersion stability, refractive index and transparency of the resulting film. The secondary particle size (by dynamic light scattering method) of inorganic fine particles or surface-modified inorganic fine particles is preferably 2-100nm, and 5-50nm from the perspective of dispersion stability, refractive index and transparency of the resulting film. More preferably, it is more preferably 5-20nm.

For example, surface-modified inorganic microparticles can add a specific amount of organosilicon compound to the aqueous dispersion of core particles or hydrophilic organic solvent dispersion, and use a catalyst such as dilute hydrochloric acid to hydrolyze the organosilicon compound to bond to the nucleus. obtained from the surface of the particle.

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

The organic solvent dispersion of the aforementioned core particles may contain optional components. In particular, by containing phosphoric acid, phosphoric acid derivatives, phosphoric acid-based surfactants, oxycarboxylic acids, etc., the dispersibility of the above-mentioned core particles can be further improved. Examples of phosphoric acid derivatives include phenylphosphonic acid and metal salts thereof. Examples of the phosphoric acid-based surfactant include Disperbyk (manufactured by BYK), Phospharol (manufactured by Toho Chemical Industry Co., Ltd.), and Nikkol (manufactured by Nikko Chemicals Co., Ltd.). Examples of oxycarboxylic acids include lactic acid, tartaric acid, citric acid, gluconic acid, malic acid and glycolic acid. The content of these optional components is preferably about 30% by mass or less with respect to the full metal oxide of the above-mentioned core particles.

The concentration of the above-mentioned organic solvent dispersion of the core particles is preferably 10 to 60% by mass, more preferably 30 to 50% by mass, in consideration of the dispersion stability.

In addition, the surface-modified inorganic fine particles of the core particles of inorganic fine particles may be, for example, a third metal oxide particle in which the surface of the first metal oxide particle (A) is coated with the second metal oxide particle (B). matter particles (C).

The first metal oxide particles (A) can be produced by known methods such as ion exchange method, peptization method, hydrolysis method, and reaction method. As an example of the ion exchange method, there are examples of the ion exchange method in which at least 1 A method of treating an acidic salt of a metal with a hydrogen-type ion-exchange resin, or a method of treating a basic salt of the above metal with a hydroxyl-type anion-exchange resin. As an example of the degumming method, there are examples of neutralizing the acidic salt of the above-mentioned metals with a base, or neutralizing the basic salts of the above-mentioned metals with an acid, and then washing the resulting colloid with an acid or The method of dissolving gel by base. Examples of the hydrolysis method include a method of hydrolyzing an alkoxide of the above-mentioned metal, or a method of removing unnecessary acid after hydrolyzing a basic salt of the above-mentioned metal under heating. As an example of the reaction method, there is a method of reacting the powder of the above-mentioned metal with an acid.

The first metal oxide particle (A) is preferably an oxide of a metal having an atomic valence of 2 to 6, and is selected from Ti, Fe, Cu, Zn, Y, Zr, Nb, Mo, In, Sn, Sb, Ta, An oxide of at least one metal in the group consisting of W, Pb, Bi, Ba, Al, Sr, Hf, and Ce is more preferred. The forms of metal oxides include, for example, TiO ₂ , Fe ₂ O ₃ , CuO, ZnO, Y ₂ O ₃ , ZrO ₂ , Nb ₂ O ₅ , MoO ₃ , In ₂ O ₃ , SnO ₂ , Sb ₂ O ₅ , Ta ₂ O ₅ , WO ₃ , PbO, Bi ₂ O ₃ , BaO, Al ₂ O ₃ , SrO, HfO ₂ , CeO ₂ , etc. These metal oxides may be used alone or in combination of two or more. As a method of combining the above-mentioned metal oxides, there are, for example, a method of mixing several types of the above-mentioned metal oxides, a method of compounding the above-mentioned metal oxides, or a method of forming a solid solution of the above-mentioned metal oxides at the atomic level.

As a combination of the above-mentioned metal oxides, there are, for example, SnO ₂ -TiO _{2 composite particles in which SnO 2 particles and TiO 2 particles are} chemically bonded at the interface, and SnO ₂ particles and WO ₃ particles are chemically bonded at the interface. SnO ₂ -WO ₃ composite particles that are chemically bonded and composited, SnO ₂ -ZrO ₂ composite particles that are chemically bonded and composited at the interface between SnO ₂ particles and ZrO ₂ particles, TiO ₂ and ZrO ₂ and SnO ₂ TiO ₂ -ZrO ₂ -SnO ₂ composite particles obtained by forming a solid solution at the atomic level, etc.

Furthermore, the first metal oxide particle (A) can be used as a compound due to the combination of metal components, such as ZnSb ₂ O ₆ , InSbO ₄ , ZnSnO ₃ , tin-doped indium oxide (ITO), In ₂ O ₃ -ZnO, BaTiO ₃ , SrTiO ₃ , aluminum-doped zinc oxide, etc.

When the first metal oxide particles (A) contain TiO ₂ , the TiO ₂ contained in the particles may have anatase type, rutile type, anatase/rutile mixed type, or brookite type. Any type of crystal structure, but among these, the rutile type is preferable in consideration of the refractive index and transparency of the obtained thin film.

Furthermore, the above-mentioned first metal oxide particle (A), from the viewpoint of suppressing its activity (such as photocatalytic performance), may also form a thin film layer containing metal oxides such as zirconia, silicon oxide, aluminum oxide, etc. on its surface . The above-mentioned thin film layer can be formed, for example, by adding a zirconium compound to an aqueous dispersion of the first metal oxide particle (A) and heating at 40 to 200°C. Examples of the aforementioned zirconium compounds include zirconium oxychloride, zirconium chloride, zirconium hydroxide, zirconium sulfate, zirconium nitrate, zirconium oxynitrate, zirconium acetate, zirconium carbonate, ammonium zirconium carbonate, potassium zirconium carbonate, ethylhexyl Zirconium alkanoate, zirconium stearate, zirconium octylate, zirconium ethoxide, n-propoxide, zirconium isopropoxide, zirconium n-butoxide, zirconium isopropoxide, zirconium t-butoxide, zirconium tetraacetyl oxypyruvate, etc., preferably zirconium oxychloride. The usage-amount of the said zirconia compound is preferably 3-50 mass % with respect to the 1st metal oxide particle (A) used as zirconia.

The primary particle size of the first metal oxide particle (A) (observed by a transmission electron microscope) is preferably 2 to 60 nm from the viewpoint of dispersion stability, refractive index and transparency of the obtained thin film, and is 2 ~30nm is even better, especially 2~20nm. The dynamic light scattering method particle size (by dynamic light scattering method) of the secondary particle size of the first metal oxide particle (A) is 5 from the viewpoint of dispersion stability, refractive index and transparency of the obtained thin film. ~100nm is better, 5~50nm is more preferable, and 5~30nm is especially preferable.

In addition, the first metal oxide particles (A) can be synthesized by, for example, the method described in International Publication No. 2013/081136.

The second metal oxide particles (B) are preferably oxide particles of at least one metal selected from the group consisting of Si, Al, Sn, Zr, Mo, Sb, and W. The second metal oxide particle (B) may, for example, be SiO ₂ , Al ₂ O ₃ , SnO ₂ , ZrO ₂ , MoO ₃ , Sb ₂ O ₅ , WO ₃ or the like as the form of the metal oxide. In addition, these metal oxides may be used alone or in combination of two or more. As a method of combining the above-mentioned metal oxides, there are, for example, a method of mixing several types of the above-mentioned metal oxides, a method of compounding the above-mentioned metal oxides, or a method of forming a solid solution of the above-mentioned metal oxides at the atomic level.

Specific examples of the second metal oxide particles (B) include SnO ₂ -WO ₃ composite particles in which SnO ₂ particles and WO ₃ particles are chemically bonded at the interface, and SnO ₂ particles and SiO ₂ SnO _{2 -SiO 2} composite particles that are chemically _{bonded at} the interface of the particles, SnO ₂ -WO ₃ - SiO ₂ composite particles, SnO ₂ -MoO 3 -SiO 2 composite particles, SnO ₂ -MoO ₃ -SiO ₂ composite particles, Sb ₂ O ₅ particles and SiO ₂ particles in which chemical bonding occurs between SnO ₂ particles and MoO 3 particles and SiO ₂ particles Sb ₂ O ₅ -SiO ₂ composite particles that are chemically bonded and composited at the interface.

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

The second metal oxide particle (B) can be produced by a known method, for example, an ion exchange method, a peptization method, or an oxidation method. As an example of the ion exchange method, there is a method of treating an acidic salt of the above-mentioned metal with a hydrogen-form ion exchange resin. As an example of the oxidation method, there is a method of reacting the powder of the above-mentioned metal or the oxide of the above-mentioned metal with hydrogen peroxide.

The primary particle size of the second metal oxide particle (B) (observed by a transmission electron microscope) is preferably 5 nm or less from the viewpoint of dispersion stability, refractive index and transparency of the obtained thin film, and is 1 to 5 nm. 5nm is even better.

The third metal oxide particle (C) is a metal oxide particle obtained by coating the surface of the first metal oxide particle (A) with the second metal oxide particle (B). As its production method, there are, for example, the following first method and second method.

The first method is to mix the aqueous dispersion containing the first metal oxide particles (A) with the aqueous dispersion containing the second metal oxide particles (B), so that the mass ratio represented by (B)/(A) (metal A method of heating the aqueous dispersion after the oxide conversion value) becomes 0.05~0.5. For example, an aqueous dispersion containing the first metal oxide particles (A) and Sb ₂ O ₅ -SiO ₂ composite particles (Sb ₂ O ₅ /SiO ₂ =0.1~5 ) water dispersion, so that the above mass ratio becomes 0.05~0.5, and by heating the mixed aqueous dispersion to 70~350°C, the surface of the first metal oxide particle (A) is coated with Sb ₂ O ₅ - an aqueous dispersion of the third metal oxide particles (C) coated with SiO ₂ composite particles.

The second method is to mix the aqueous dispersion containing the first metal oxide particles (A) with the water-soluble alkali salt of tin oxide and alkali salt of silicon oxide as the second metal oxide particles (B), and make the SnO ₂ /SiO ₂ After the expressed mass ratio (converted value of metal oxide) becomes 0.1~5, perform cation exchange to remove alkali metal ions, and mix with the obtained aqueous dispersion of SnO ₂ -SiO ₂ composite particles to express (B)/(A) After the mass ratio (converted value of metal oxide) becomes 0.05~0.5, the method of heating the aqueous dispersion obtained by mixing. The aqueous solution of the water-soluble alkali salt used in this second method can preferably use the aqueous solution of the sodium salt. For example, after mixing the aqueous dispersion containing the first metal oxide particles (A) and the aqueous solution of sodium stannate and sodium silicate as the second metal oxide particles (B), cation exchange is performed, and the obtained SnO ₂ - The aqueous dispersion of SiO ₂ composite particles is mixed so that the above-mentioned mass ratio becomes 0.05~0.5, and the aqueous dispersion is heated at 70~350°C to obtain the first metal oxide particle (A) as the nucleus, and its surface is treated with Aqueous dispersion of third metal oxide particles (C) coated with second metal oxide particles (B) containing SnO ₂ -SiO ₂ composite particles.

The temperature for mixing the first metal oxide particles (A) and the second metal oxide particles (B) is usually 1 to 100°C, preferably 20 to 60°C. Moreover, the heating temperature after mixing is preferably 70-350°C, more preferably 70-150°C. Moreover, the heating time after mixing is usually 10 minutes to 5 hours, preferably 30 minutes to 4 hours.

The aqueous dispersion of the third metal oxide particles (C) may contain optional components. In particular, by including oxycarboxylic acids, intellectual properties such as dispersibility of the third metal oxide particles (C) can be further improved. Examples of the oxycarboxylic acid include lactic acid, tartaric acid, citric acid, gluconic acid, malic acid and glycolic acid. The content of the above-mentioned oxycarboxylic acids is preferably about 30% by mass or less with respect to the total metal oxide of the third metal oxide particle (C).

Moreover, as a dispersion liquid of the 3rd metal oxide particle (C), you may contain an alkali component. As the above-mentioned alkali component, there are alkali metal hydroxides such as Li, Na, K, Rb, Cs, etc.; ammonium; ethylamine, isopropylamine, n-propylamine, n-butylamine, diethylamine, Amine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, triethylamine, tripropylamine, tributylamine, triisobutylamine , tripentylamine (tri-n-pentylamine), tri-n-hexylamine, tri-n-octylamine, dimethylpropylamine, dimethylbutylamine, dimethylhexylamine, etc. Primary, secondary and tertiary alkylamines; aralkylamines such as benzylamine and dimethylbenzylamine; alicyclic amines such as piperidine; alkanolamines such as monoethanolamine and triethanolamine; Quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, etc. These can also be used individually by 1 type, or in combination of 2 or more types. The content of the alkali component is preferably about 30% by mass or less with respect to the total metal oxide of the third metal oxide particle (C). And, these alkali components can be used together with the above-mentioned oxycarboxylic acid.

When it is desired to further increase the concentration of the aqueous dispersion of the third metal oxide particles (C), it can be concentrated to a maximum of about 65% by mass by a common method. As the method, there are, for example, an evaporation method and an ultrafiltration method. And, when it is desired to adjust the pH of the aqueous dispersion, the above-mentioned alkali metal hydroxides, amines, quaternary ammonium salts, oxycarboxylic acids, etc. may be added. The concentration of all metal oxides in the solvent dispersion liquid of the third metal oxide particle (C) is preferably 10 to 60% by mass, more preferably 20 to 50% by mass.

An organic solvent dispersion of the third metal oxide particles (C) can be obtained by substituting the aqueous medium for the aqueous dispersion of the third metal oxide particles (C) with a hydrophilic organic solvent. This substitution can be performed by ordinary methods such as distillation and ultrafiltration. Examples of the above-mentioned hydrophilic organic solvent include lower alcohols such as methanol, ethanol, isopropanol, and 1-propanol, ethers such as propylene glycol monomethyl ether, dimethylformamide, and N,N'-dimethoxy Straight-chain amides such as methylacetamide, cyclic amides such as N-methyl-2-pyrrolidone, diols such as ethyl cellophane and ethylene glycol.

The primary particle size (observed by a transmission electron microscope) of the third metal oxide particles (C) is preferably 20 nm or less from the viewpoints of dispersion stability, refractive index and transparency of the obtained film. The dynamic light scattering method particle size (by dynamic light scattering method) of the secondary particle size of the third metal oxide particle (C) is 2 from the viewpoint of dispersion stability, refractive index and transparency of the obtained thin film. ~100nm is preferred.

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

The content of inorganic fine particles in the composition can be controlled in accordance with the target refractive index, transmittance, heat resistance, etc. of the film to be produced as long as it is within the range that does not impair the dispersibility of the final composition obtained. For example, it can be added in the range of 0.1 to 1,000 parts by mass, preferably 1 to 500 parts by mass, relative to 100 parts by mass of the triazine ring-containing polymer, in order to maintain film quality and obtain stable refractive index and solvent resistance. From the point of view, it is more preferably 10 to 300 parts by mass.

(4).Organic solvent Examples of organic solvents include toluene, p-xylene, o-xylene, m-xylene, ethylbenzene, styrene, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, and Ethyl 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 Alcohol 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 Glycol monomethyl ether, dipropylene glycol monoethyl ether, diethylene glycol monoethyl ether, triethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol, 1 -octanol, ethylene glycol, pentylene 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, 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 , N-dimethylformamide, N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone, 1,3-dimethyl-2-tetrahydroimidazolone, dimethyl Gyridine, N-cyclohexyl-2-pyrrolidone, and the like may be used alone or in combination of two or more.

As mentioned above, the triazine ring-containing polymer of the present invention has excellent solubility in organic solvents, so it is fully soluble in ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, and diethylene glycol monomethyl ether acetate. Glycol ester solvents such as alcohol monobutyl ether acetate and diethylene glycol monoethyl ether acetate; acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclic Ketone-based solvents such as pentanone, cyclohexanone, and diacetone alcohol; ethyl acetate, methyl acetate, butyl acetate, methoxybutyl acetate, celloxuloacetate, amyl acetate, n-propyl acetate, Ester-based solvents such as isopropyl acetate, methyl lactate, ethyl lactate, and butyl lactate are especially suitable for forming films on parts that require such solvents.

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

Initiators corresponding to respective crosslinking agents can also be blended into the composition of the present invention. And, as mentioned above, when a multifunctional epoxy compound and/or a multifunctional (meth)acrylic compound is used as a crosslinking agent, photocuring can be performed without using an initiator, and a cured film can be provided. The starter is okay too.

When using a polyfunctional epoxy compound as a crosslinking agent, a photoacid generator or a photobase generator can be used. As a photoacid generator, what is necessary is just to select and use from well-known thing suitably, for example, the onium salt derivatives, such as a diazonium salt, a permeicium salt, or an indium salt, can be used. Specific examples thereof include aryl diazonium diazides such as phenyldiazohexafluorophosphate, 4-methoxyphenyldiazohexafluoroantimonate, and 4-methylphenyldiazohexafluorophosphate. Salt; Diaryl of diphenyliodonium hexafluoroantimonate, bis(4-methylphenyl)iodonium hexafluorophosphate, bis(4-tert-butylphenyl)iodonium hexafluorophosphate, etc. Base salt; triphenyl percited hexafluoroantimonate, ginseng (4-methoxyphenyl) percited hexafluorophosphate, diphenyl-4-thiophenoxyphenyl percited hexafluoroantimonate, Diphenyl-4-thiophenoxyphenyl percolium hexafluorophosphate, 4,4'-bis(diphenyldihydrothio)phenylsulfide-bishexafluoroantimonate, 4,4' -Bis(diphenylthio)phenylsulfide-bishexafluorophosphate, 4,4'-bis[bis(β-hydroxyethoxy)phenylthio]phenylsulfide-bis Hexafluoroantimonate, 4,4'-bis[bis(β-hydroxyethoxy)phenyldihydrothio]phenylsulfide-bis-hexafluorophosphate, 4-[4'-(benzoyl Base) phenylthio] phenyl-bis(4-fluorophenyl) percite hexafluoroantimonate, 4-[4'-(benzoyl)phenylthio]phenyl-bis(4-fluoro Phenyl) percited hexafluorophosphate and other triaryl percited salts, etc.

These onium salts can also be commercially available, and specific examples thereof include SAN-AID SI-60, SI-80, SI-100, SI-60L, SI-80L, SI-100L, and SI-L145 . Made by Union Carbide Co., Ltd.), CPI-100P, CPI-100A, CPI-200K, CPI-200S (the above are made by SAN-APRO Co., Ltd.), Adekaoptomer SP-150, SP-151, SP-170, SP-171 (The above are made by Asahi Denka Co., Ltd.), Irgacure 261 (manufactured by BASF Corporation), CI-2481, CI-2624, CI-2639, CI-2064 (the above are made by Nippon Soda Co., Ltd.), CD-1010, CD-1011, CD-1012 (the above are made by SARTOMER), DS-100, DS-101, DAM-101, DAM-102, DAM-105, DAM-201, DSM-301, NAI-100, NAI-101 , NAI-105, NAI-106, SI-100, SI-101, SI-105, SI-106, PI-105, NDI-105, BENZOIN TOSYLATE, MBZ-101, MBZ-301, PYR-100, PYR- 200, DNB-101, NB-101, NB-201, BBI-101, BBI-102, BBI-103, BBI-109 (the above are made by Midori Chemical Co., Ltd.), PCI-061T, PCI-062T, PCI- 020T, PCI-022T (manufactured by Nippon Kayaku Co., Ltd.), IBPF, IBCF (manufactured by Sanwa Chemical Co., Ltd.), etc.

On the other hand, what is necessary is just to use as a photobase generator suitably selected from well-known persons, for example, can use Co-amine complex system, oxime carboxylate system, carbamate system, quaternary ammonium salt It is a photobase generator, etc. Specific examples thereof include 2-nitrobenzylcyclohexyl carbamate, triphenylmethanol, O-carbamoyl hydroxyamide, O-carbamoyl oxime, [[(2,6 -Dinitrobenzyl)oxy]carbonyl]cyclohexylamine, bis[[(2-nitrobenzyl)oxy]carbonyl]hexane 1,6-diamine, 4-(methylthiobenzyl Acyl)-1-methyl-1-morpholinoethane, (4-morpholinobenzoyl)-1-benzyl-1-dimethylaminopropane, N-(2-nitro Benzyloxycarbonyl)pyrrolidine, hexaammonocobalt (III) ginseng (triphenylmethyl borate), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl )-butanone, 2,6-dimethyl-3,5-diacetyl-4-(2'-nitrophenyl)-1,4-dihydropyridine, 2,6-dimethyl- 3,5-Diacetyl-4-(2',4'-dinitrophenyl)-1,4-dihydropyridine, etc. Moreover, a commercial item can also be used for a photobase generator, and TPS-OH, NBC-101, ANC-101 (all are product names, manufactured by Midori Chemical Co., Ltd.) etc. are mentioned as a specific example.

When using a photoacid or a base generating agent, it is preferable to use it in the range of 0.1-15 mass parts with respect to 100 mass parts of polyfunctional epoxy compounds, and it is more preferable to use it in the range of 1-10 mass parts. Furthermore, if necessary, you may mix|blend an epoxy resin hardening agent in the quantity of 1-100 mass parts with respect to 100 mass parts of polyfunctional epoxy compounds.

On the other hand, when using a polyfunctional (meth)acrylic compound, a photoradical polymerization initiator can be used. As a photoradical polymerization initiator, what is necessary is just to select and use from well-known ones suitably, for example, there are acetophenones, benzophenones, Mie's benzoyl benzoate, valeroxime ester , oxime esters, tetramethylthiuram monosulfide and thioxanthones, etc. In particular, a photocleavage-type photoradical polymerization initiator is preferable. About the photocleavage-type photoradical polymerization initiator, it is described in the latest UV curing technology (159 pages, issuer: Kazuhiro Takamasu, issuer: Technical Information Association, issued in 1991). Examples of commercially available photoradical polymerization initiators include trade names manufactured by BASF Corporation: Irgacure 127, 184, 369, 379, 379EG, 651, 500, 754, 819, 903, 907, 784, 2959, CGI1700, CGI1750, CGI1850, CG24-61, OXE01, OXE02, Darocur 1116, 1173, MBF, BASF product name: Lucirin TPO, UCB company product name: EBECRYL P36, Fratelli Lamberti company product name: Esacure KIP150, KIP65LT, KIP100F , KT37, KT55, KTO46, KIP75/B, etc. When using a photoradical polymerization initiator, it is better to use it in the range of 0.1 to 200 parts by mass, and to use it in the range of 1 to 150 parts by mass relative to 100 parts by mass of the polyfunctional (meth)acrylate compound. good.

Furthermore, in the composition of the present invention, for the purpose of accelerating the reaction between the triazine ring-containing polymer and the crosslinking agent, etc., a polyfunctional mercapto compound having 2 or more mercapto groups in the molecule may be added. Specifically, it is preferably a polyfunctional mercapto compound represented by the following formula.

The above-mentioned L represents a 2-4 valent organic group, but it is preferably a 2-4 valent aliphatic group with 2-12 carbons or a 2-4 valent heterocycle-containing group, and it is a 2-4 valent carbon number 2 ~8 aliphatic groups, or 3 with isocyanuric acid skeleton (1,3,5-triazine-2,4,6(1H,3H,5H)-trione ring) represented by the following formula The price base is even better. The above-mentioned n represents an integer of 2 to 4 corresponding to the valence of L.

(式中，「･」表示與氧原子之鍵結部。)

(In the formula, "･" represents the bonding part with the oxygen atom.)

Specific compounds include 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-para(3-mercaptobutyryloxyethyl)-1,3, 5-triazine-2,4,6-(1H,3H,5H)-trione, pentaerythritol (3-mercaptobutyrate), trimethylolpropane ginseng (3-mercaptobutyrate ), trimethylolethane ginseng (3-hydrogen thiobutyrate), etc. These polyfunctional mercapto compounds can be obtained as commercial items, and examples thereof include Karenz MT-BD1, Karenz MT NR1, Karenz MT PE1, TPMB, and TEMB (manufactured by Showa Denko Co., Ltd.). These polyfunctional thiol compounds may be used alone or in combination of two or more.

When a polyfunctional mercapto compound is used, the amount added is not particularly limited as long as it does not adversely affect the obtained film, but in the present invention, it is 0.01 to 10% by mass based on 100% by mass of the solid content More preferably, it is 0.03 to 6% by mass, more preferably.

In the composition of the present invention, as long as the effects of the present invention are not impaired, other components other than polymers containing triazine rings, crosslinking agents, inorganic particles and organic solvents, such as leveling agents, surfactants, and silanes, may also be included. Additives such as coupling agent. As the surfactant, there are polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, etc.; Polyoxyethylene alkyl allyl ethers such as ethylene octylphenol ether and polyoxyethylene nonylphenol ether; polyoxyethylene and polyoxypropylene block copolymers; sorbitol monolaurate, sorbose Alcohol monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate and other sorbitol fatty acid esters; polyoxygen Ethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan trioleate Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as stearate, trade names F-top EF301, EF303, EF352 (manufactured by Mitsubishi Material Electronics Co., Ltd. (formerly) Gemco )), trade name MEGAFAC F171, F173, R-08, R-30, R-40, F-553, F-554, RS-75, RS-72-K (manufactured by DIC), FLUORAD FC430, Fluorinated surfactants such as FC431 (manufactured by Sumitomo 3M Co., Ltd.), product name Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Co., Ltd.), and organosiloxane Alkane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), BYK-302, BYK-307, BYK-322, BYK-323, BYK-330, BYK-333, BYK-370, BYK-375, BYK-378 ( BYK･Japan Co., Ltd.), etc.

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

The film-forming composition of the present invention can form a desired cured film by applying the composition for film formation of the present invention to a substrate, heating as necessary to evaporate the solvent, and then performing heating or light irradiation. The coating method of the composition is optional, and for example, spin coating method, dipping method, flow coating method, inkjet method, jet dispensing method, spray method, bar coating method, gravure coating method, slit coating method, and roll coating method can be used. method, transfer printing method, brush coating, blade coating method, air knife coating method and other methods.

In addition, as substrates, silicon oxide, indium tin oxide (ITO) film-formed glass, indium zinc oxide (IZO) film-formed glass, metal nanowires, polyethylene terephthalic acid For substrates made of polyester (PET), plastic, glass, quartz, ceramics, etc., flexible substrates with flexibility can be used. The firing temperature is not particularly limited as long as the purpose is to evaporate the solvent, and it can be performed at, for example, 110 to 400°C. The firing method is not particularly limited, and for example, it may be evaporated in an appropriate environment such as the air, an inert gas such as nitrogen, or a vacuum using a hot plate or an oven. As for the firing temperature and firing time, it is only necessary to select the conditions suitable for the process steps of the electronic device for the purpose, and select the firing conditions so that the physical properties of the obtained film are suitable for the characteristics required by the electronic device. The conditions of light irradiation are not particularly limited, and appropriate irradiation energy and time can be adopted according to the triazine ring-containing polymer and crosslinking agent used.

The thin film or cured film of the present invention obtained as above can be used in the production of liquid crystal displays, organic EL elements (organic EL displays or organic EL lighting), touch panels, A component of optical semiconductor (LED) elements, solid-state imaging elements, organic thin-film solar cells, dye-sensitized solar cells, organic thin-film transistors (TFT), lenses, cameras, binoculars, microscopes, semiconductor exposure devices, etc. It is more suitable in the field of electronic devices or optical materials. In particular, the thin film or cured film made of the composition of the present invention has high transparency and high refractive index, so when used as a planarizing film or light scattering layer for organic EL lighting, its light extraction efficiency can be improved ( Light diffusion efficiency), but also can improve its durability.

Furthermore, when the composition of the present invention is used in the light scattering layer of an organic EL element, known organic-inorganic composite light-diffusing agents, organic light-diffusing agents, and inorganic light-diffusing agents can be used as the light-diffusing agent, and are not particularly limited. These may be used alone, respectively, may be used in combination of two or more of the same kind, or may be used in combination of two or more of different kinds.

Examples of the organic-inorganic composite light-diffusing agent include melamine resin-silica composite particles and the like. Examples of organic light diffusing agents include cross-linked polymethylmethacrylate (PMMA) particles, cross-linked polymethacrylate particles, cross-linked polystyrene particles, cross-linked styrene-acrylic acid copolymer particles, melamine- Formaldehyde particles, silicone resin particles, silicone-acrylic composite particles, nylon particles, benzoguanamine-formaldehyde particles, benzoguanamine-melamine-formaldehyde particles, fluororesin particles, epoxy resin particles, polyphenylene sulfide resin Particles, polyether resin particles, polyacrylonitrile particles, polyurethane particles, etc. Examples of inorganic light diffusing agents include calcium carbonate (CaCO ₃ ), titanium oxide (TiO ₂ ), barium sulfate (BaSO ₄ ), aluminum hydroxide (Al(OH) ₃ ), silicon (SiO ₂ ), and talc. However, from the viewpoint of further improving the light diffusibility of the resulting cured film, titanium oxide (TiO ₂ ) or aggregated silicon particles are preferred, and non-aggregated titanium oxide (TiO ₂ ) is even more preferred. These light diffusing agents may also be surface-treated with an appropriate surface modifier. [Example]

Hereinafter, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to a following example. In addition, each measuring device used in the examples is as follows. [ ¹ H-NMR] Apparatus: Bruker NMR System AVANCE III HD 500 (500MHz) Measurement solvent: DMSO-d6 Reference material: Tetramethylsilane (TMS) (δ0.0ppm) [GPC] Apparatus: HLC manufactured by TOSOH Co., Ltd. -8200 GPC column: TOSOH TSKgel α-3000 +TOSOH TSKgel α-4000 Column temperature: 40℃ Solvent: Dimethylformamide (DMF) Detector: UV (271nm) Calibration line: Standard polystyrene [Ellipsometer] Device: Multi-incident Angle Spectroscopic Ellipsometer VASE made by JA Woollam･Japan [Spectrophotometer] Device: CM-3700A made by Konica Minolta

[1] Synthesis of Polymers Containing Triazine Rings [Synthesis Example 1-1] Synthesis of High Molecular Compounds [5]

Add 2,2'-bis(trifluoromethyl)-4,4'-diamine diphenyl ether [2] (218.79 g, 0.651 mol, manufactured by Wuhan Sunshine Co., Ltd.) and dimethyl 1,693.96 g of acetylacetamide (DMAc, manufactured by Kanto Chemical Co., Ltd.), after nitrogen substitution, stirred to make 2,2'-bis(trifluoromethyl)-4,4'-diamine diphenyl ether [2 ] dissolved in DMAc. After that, cool to -10°C in an ethanol-dry ice bath, and add 2,4,6-trichloro-1,3,5-triazine[1] (120.00g , 0.651mol, produced by Tokyo Chemical Industry Co., Ltd.). After stirring for 30 minutes, drop the reaction solution into a 5,000mL four-neck flask with DMAc1,693.96g added in advance and nitrogen substitution, set the oil pool to 90~100°C, and make the internal temperature 75°C±5°C. After stirring at an internal temperature of 75° C. for 1 hour, aniline [3] (73.39 g, 0.456 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) and 2-(4-aminophenyl) ethanol [4] (62.49 g, 0.456 mol) were prepared in advance. mol, manufactured by Oakwood Company) was dissolved in DMAc124.97g and added dropwise, followed by stirring for 3 hours. Thereafter, the temperature was lowered to room temperature, n-propylamine (115.39 g, manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise, and stirring was stopped after stirring for 30 minutes. THF (2,051g), ammonium acetate (1,846g), and ion exchanged water (1,846g) were added to the reaction solution, and it stirred for 30 minutes. After the stirring stopped, the solution was transferred to a separatory funnel, separated into an organic layer and an aqueous layer, and the organic layer was recovered. The recovered organic layer was dropped into methanol (3,282 g) and ion-exchanged water (8,206 g), and reprecipitated. The obtained precipitate was filtered and dried at 120° C. for 8 hours with a vacuum drier to obtain 235.51 g of the target polymer compound [5] (hereinafter referred to as P-1). The measurement results of the ¹ H-NMR spectrum of Compound P-1 are shown in FIG. 1 . Compound P-1 had a weight average molecular weight Mw of 6,070 and a polydispersity Mw/Mn of 2.6 as measured in terms of polystyrene by GPC.

Compound P-1 (3.0 g) was dissolved in propylene glycol monomethyl ether (hereinafter abbreviated as PGME) (7.0 g), propylene glycol monomethyl ether acetate (hereinafter abbreviated as PGMEA) (7.0 g), cyclopentanone (hereinafter abbreviated as CPN) (7.0 g), all were dissolved in all solvents, and a uniform varnish of 30% by mass was obtained.

[2] Preparation of surface-treated inorganic fine particles The methods and measuring devices for measuring physical properties implemented in Production Examples 1 to 4 below are as follows. (1) Moisture content: determined by Karl Fischer titration. (2) Primary particle diameter: The dispersion liquid was dried on a copper mesh, observed with a transmission electron microscope, and 100 particle diameters were measured, and the average value was determined as the primary particle diameter. (3) Specific gravity: Calculated by floating method (20°C). (4) Viscosity: Calculated with an Oswald viscometer (20°C). (5) Particle size by dynamic light scattering method: determined by measurement with a Zetasizer Nano manufactured by Malvern. (6) Solid content concentration: Calculated from the residual solid content when fired at 500°C. (7) Binding amount of organosilane compound: The amount of organosilane compound bound to denatured metal oxide colloidal particles was determined by elemental analysis. Device: Made by PerkinElmer, Series II CHNS/O Analyzer 2400

Production Example 1: Production of the first metal oxide particle (nuclear particle) (A1) Add 126.2 g of pure water to a 1-liter container, add 17.8 g of metastannic acid (contains 15 g in terms of SnO _{2 )} under stirring, Showa Chemical Industry Co., Ltd.), titanium tetraisopropoxide 284g (80g in TiO2 conversion, A- ₁ manufactured by Nippon Soda Co., Ltd.), oxalic acid dihydrate Wamono 98 (70g in oxalic acid conversion, Ube Industries Co., Ltd. 438 g (manufactured by Sechem Japan) and 35 mass % tetraethylammonium hydroxide aqueous solution. In the obtained mixed solution, the molar ratio of oxalic acid/titanium atom was 0.78, and the molar ratio of tetraethylammonium hydroxide/titanium atom was 1.04. 950 g of this mixed solution was kept at 80° C. for 2 hours, and then the pressure was reduced to 580 Torr, and kept for 2 hours to prepare a titanium mixed solution. The pH of the prepared titanium mixed solution was 4.7, the electrical conductivity was 27.2 mS/cm, and the metal oxide concentration was 10.0% by mass. 950 g of the titanium mixed solution and 950 g of pure water were added to a 3-liter glass-lined autoclave container, and hydrothermal treatment was performed at 140° C. for 5 hours. After cooling to room temperature, the taken out solution after hydrothermal treatment is a pale milky white aqueous dispersion of colloidal particles containing titanium oxide. The resulting dispersion had a pH of 3.9, an electrical conductivity of 19.7 mS/cm, a _TiO concentration of 4.2% by mass, a hydroxylated tetraethylammonium concentration of 8.0% by mass, and an oxalic acid concentration of 3.7% by mass. The diameter is 16nm. When observed by a transmission electron microscope, elliptical particles with a primary particle diameter of 5-15nm will be observed. The resulting dispersion liquid was dried at 110°C for X-ray retroreflection analysis, and it was confirmed to be rutile crystals. The obtained colloidal particles containing titanium oxide were used as core particles (A). Next, 70.8 g of zirconium oxychloride (containing 21.19% by mass as ZrO ₂ , manufactured by Daiichi Razor Chemical Co., Ltd.) was diluted with 429.2 g of pure water, and 500 g of an aqueous solution of zirconium oxychloride (as ZrO 2 ₂ , containing 3.0% by mass), 1,000 g of the dispersion liquid (water dispersion sol) of the core particle (A) was added here under stirring. Then, it was heated to 95°C and hydrolyzed to obtain a water-dispersed sol of titanium oxide-containing core particles (A1) (hereinafter referred to as first metal oxide particles (A1)) having a thin film layer of zirconium oxide formed on the surface. The pH value of the obtained water-dispersed sol was 1.2, and the concentration of all metal oxides was 20% by mass. When observed with a transmission electron microscope, colloidal particles with a primary particle size of 4-8 nm were observed.

Production Example 2: Production of Second Metal Oxide Particles (B1) 77.2 g of JIS No. 3 sodium silicate (containing 29.8% by mass as SiO ₂ , manufactured by Fuji Chemical Co., Ltd.) was dissolved in 1,282 g of pure water, and then, 20.9 g of sodium stannate NaSnO ₃ ·H ₂ O (55.1% by mass as SnO ₂ , produced by Showa Chemical Co., Ltd.) was dissolved. By passing the resulting aqueous solution into a column filled with hydrogen-type cation exchange resin (Amberlite (registered trademark) IR-120B), the aqueous dispersion of acidic silica-second tin oxide composite colloidal particles (B1) was obtained Sol (pH 2.4, contains 0.44 mass % as SnO ₂ , contains 0.87 mass % as SiO ₂ , SiO ₂ /SnO ₂ mass ratio is 2.0) 2,634 g. Next, 6.9 g of diisopropylamine was added to the obtained water dispersion sol. The obtained sol is a water-dispersed sol of alkaline silicon dioxide-second tin oxide composite colloidal particles (B1) (hereinafter referred to as the second metal oxide particles (B1)), with a pH value of 8.0. Colloidal particles with a primary particle size of 5 nm or less can be observed in the water-dispersed sol by a transmission electron microscope.

Production Example 3: Production of the third metal oxide particle (C1) 1,455 g of the water-dispersed sol of the first metal oxide particle (A1) obtained in Production Example 1 was added to 2,634 g of the water-dispersed sol of the second metal oxide particle (B1) prepared in Production Example 2 under stirring. Next, the liquid was passed to a column filled with 500 ml of anion exchange resin (Amberlite (registered trademark) IRA-410, manufactured by Orgaho Co., Ltd.). Next, after heating the water-dispersed sol at 95° C. for 3 hours, pass the liquid into a column filled with a hydrogen-type cation exchange resin (Amberlite (registered trademark) IR-120B), and replace it with tri-n-pentyl The amine is stabilized and concentrated by the ultrafiltration membrane method to obtain the silica- Aqueous dispersion sol of titanium oxide-containing colloidal particles (C1) (hereinafter referred to as third metal oxide particles (C1)) coated with the second tin oxide composite oxide. The total metal oxide concentration of the obtained water-dispersed sol was 20% by mass, and the primary particle diameter of the sol observed by a transmission electron microscope was 4-10 nm. Next, the dispersion medium of the obtained water-dispersed sol was replaced with methanol using a rotary evaporator to obtain a methanol-dispersed sol of the third metal oxide particle (C1). The total metal oxide concentration of this methanol dispersion sol is 30% by mass, the viscosity is 1.5mPa･s, the particle size is 18nm according to the dynamic light scattering method, and the water content is 1.0% by mass.

Production Example 4: Production of Surface Modified Inorganic Microparticles (D1) Add 8.0 g of polyether denatured silane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: X-12-641) to 533 g of methanol dispersion sol of the third metal oxide particle (C1) obtained in Production Example 3, and heat at 70°C Refluxing heating was carried out for 5 hours. Next, 6.4 g of 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-503) was added, and reflux heating was carried out at 70° C. for 5 hours to obtain polyether-modified silane The hydrolyzate of 3-methacryloxypropyltrimethoxysilane and the hydrolyzate of 3-methacryloxypropyltrimethoxysilane are bound to the methanol dispersion of surface-modified colloidal particles (D1) (hereinafter referred to as surface-modified metal oxide particles (D1)). Next, using an evaporator, methanol was distilled off while adding propylene glycol monomethyl ether at 80 Torr, and methanol was replaced with propylene glycol monomethyl ether to obtain propylene glycol monomethyl ether of surface-modified metal oxide particles (D1) Dispersion liquid 530g. The specific gravity of the obtained dispersion was 1.209, the viscosity was 3.6mPa･s, the total metal oxide concentration was 30.0% by mass, the primary particle size observed by transmission electron microscope was 5-10nm, and the particle size by dynamic light scattering method was 11nm. In the obtained surface-modified metal oxide particle (D1), the hydrolyzate of polyether-modified silane bonded to the surface of the third metal oxide particle (C1) is compared to the full metal oxide of the third metal oxide particle (C1) , is 4.0% by mass, the hydrolyzate of 3-methacryloxypropyltrimethoxysilane bonded to the surface of the third metal oxide particle (C1) relative to the total amount of the third metal oxide particle (C1) A metal oxide is 2.5% by mass.

[3] Preparation of film-forming composition and production of cured film [Reference example 1-1] Compound P-1 (1.0 g) obtained in Synthesis Example 1-1 was dissolved in PGME (9.0 g) to prepare a 10% by mass uniform and transparent varnish (hereinafter referred to as P-1 solution). Spin-coat the resulting P-1 solution on a 50mm×50mm×0.7mm alkali-free glass substrate to a thickness of 500nm using a spin coater, heat it on a hot plate at 100°C for 1 minute, and then bake it at 250°C for 5 minutes. Minutes to obtain a cured film (hereinafter referred to as P-1 film).

Table 1 shows the refractive index and film thickness of the cured film prepared in Reference Example 1-1 above.

It can be seen from Table 1 that the film produced by using the polymer compound obtained in Synthesis Example 1-1 can improve the solubility to organic solvents, and at the same time have a refractive index exceeding 1.64.

[4] Preparation of cross-linking agent added film-forming composition and production of cured film [Example 1-1] To compound P-1 (1.521 g) synthesized in Synthesis Example 1-1, D1 (15.214 g) as a 30% by mass PGME solution of inorganic fine particles, and blocked isocyanate as a 70% by mass PGME solution as a crosslinking agent were added (BI-7992, 1,500mPa･s, manufactured by BAXENDEN Co., Ltd.) 1.304g, MEGAFAC F-563 (manufactured by DIC Co., Ltd.) 0.152g of a 1% by mass PGME solution as a surfactant, and 1.808g of PGME were visually confirmed. Dissolve and prepare a varnish with a solid content of 35% by mass (hereinafter referred to as SP-1 solution). Spin-coat this SP-1 solution on a 50mm×50mm×0.7mm alkali-free glass substrate with a spin coater at 200rpm for 5 seconds and 1,000rpm for 30 seconds, and use a hot plate at 100°C for 1 minute. After drying, true firing was performed at 200° C. for 5 minutes to obtain a cured film (hereinafter referred to as SP-1 film).

[Comparative Example 1-1] Add D1 (20.285g) of 30% by mass PGME solution as inorganic fine particles, 1.304g of blocked isocyanate (BI-7992, 1,500mPa･s, manufactured by BAXENDEN Co., Ltd.) as a crosslinking agent, and as an interface Dissolution of 0.152 g of MEGAFAC F-563 (manufactured by DIC Co., Ltd.) of 1 mass % PGME solution of the active agent was visually confirmed, and a varnish with a solid content of about 35 mass % was prepared (hereinafter referred to as SP-1 solution). Using this SP-1 solution, a cured film (hereinafter referred to as S-1 film) was obtained in the same procedure as in Example 1-1.

Regarding the cured film obtained above, the refractive index, film thickness, b*, transmittance at 400 to 800 nm, and HAZE were measured. The results are shown in Table 2 and Fig. 2 . Regarding the transmittance, the average transmittance of 400~800nm was calculated and shown in the table.

From these results, it can be seen that the cured film produced by using the polymer compound obtained in Synthesis Example 1-1 can maintain a high refractive index, and at the same time have excellent effects of reducing b* and HAZE or increasing transmittance.

[ Fig. 1 ] ¹ H-NMR spectrum chart of the polymer compound [5] obtained in Synthesis Example 1-1. [ Fig. 2 ] A graph showing the transmittance of the cured films prepared in Example 1-1 and Comparative Example 1-1.

Claims (19)

A film-forming composition comprising: a repeating unit structure represented by the following formula (1), having at least one triazine ring terminal, and at least a part of the triazine ring terminal having a crosslinking group Polymers containing triazine rings blocked by amine groups, crosslinking agents, inorganic microparticles, and organic solvents,

(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 with 3 to 30 carbon atoms having a ring structure, and * represents a bond junction). The film-forming composition according to claim 1, wherein Q in the aforementioned formula (1) represents at least one selected from the group represented by formulas (2)-(13) and formulas (102)-(115),

[In formulas (2) to (13), R ¹ to R ⁹² each independently represent a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group with 1 to 10 carbons, or a halogenated alkyl group with 1 to 10 carbons or an alkoxy group with 1 to 10 carbons, R ⁹³ and R ⁹⁴ represent a hydrogen atom or an alkyl group with 1 to 10 carbons, W ¹ and W ² independently represent a single bond, CR ⁹⁵ R ⁹⁶ (R ⁹⁵ and R ⁹⁶ Each independently represents a hydrogen atom, an alkyl group with a carbon number of 1 to 10 (but these can also form a ring together), or a halogenated alkyl group with a carbon number of 1 to 10), C=O, O, S, SO, SO ₂ , or NR ⁹⁷ (R ⁹⁷ represents a hydrogen atom, an alkyl group with 1 to 10 carbons or a phenyl group), X ¹ and X ² each independently represent a single bond, an alkylene group with 1 to 10 carbons, or the formula (14 )

(In formula (14), R ⁹⁸ ~ R ¹⁰¹ each independently represent a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group with 1 to 10 carbons, a halogenated alkyl group with 1 to 10 carbons, or a halogenated alkyl group with 1 to 10 carbons 10 alkoxy, Y ¹ and Y ² each independently represent a single bond or a group represented by an alkylene group with 1 to 10 carbons), * represents a bond]

(In formulas (102) to (115), R ¹ and R ² each independently represent an alkylene group with 1 to 5 carbons that may also have a branched structure, and * represents a bond). Such as the composition for lipid film formation in claim item 2, wherein, in the aforementioned formulas (2) to (13), the aforementioned R ¹ to R ⁹² and R ⁹⁸ to R ¹⁰¹ are each independently a hydrogen atom, a halogen atom, or a carbon number of 1 to 10 halogenated alkyl. The film-forming composition according to claim 1, wherein the aforementioned amino group having a crosslinking group is represented by formula (15),

(In the formula (15), R ¹⁰² represents a crosslinking group, and * represents a bond). The film-forming composition according to Claim 4, wherein the aforementioned amine group having a crosslinking group is represented by formula (16),

(In the formula (16), R ¹⁰² represents the same meaning as above, and * represents a bond). The film-forming composition according to claim 4, wherein the aforementioned R ¹⁰² is a group containing a hydroxyl group or a group containing a (meth)acryl group. The film-forming composition according to claim 6, wherein the aforementioned R ¹⁰² is a hydroxyalkyl group, a (meth)acryloxyalkyl group, or a group represented by the following formula (i),

(In formula (i), A ¹ represents an alkylene group with 1 to 10 carbon atoms, A ² represents a single bond or the following formula (j)

The group represented by A ³ represents an aliphatic hydrocarbon group with a valence of (a+1) which may also be substituted by a hydroxyl group, A ⁴ represents a hydrogen atom or a methyl group, a represents 1 or 2, and * represents a bond). The composition for film formation as claimed in item 7, wherein, the aforementioned R ¹⁰² is selected from hydroxymethyl, 2-hydroxyethyl, (meth)acryloxymethyl, (meth)acryloxy Ethyl group and the group represented by the following formula (i-2) ~ formula (i-5),

(In the formula (i-1) to the formula (i-5), * represents a bonding position). The film-forming composition according to claim 2, wherein at least one aromatic ring in Q in the aforementioned formula (1) contains at least one halogen atom or a halogenated alkyl group having 1 to 10 carbon atoms. The film-forming composition according to claim 1, wherein a part of the end of the triazine ring is blocked by an unsubstituted arylamine group. The film-forming composition according to Claim 10, wherein the aforementioned unsubstituted arylamine group is represented by formula (33),

(In the formula (33), * represents a bonding site). The film-forming composition according to claim 1, wherein Q in the aforementioned formula (1) is represented by formula (17),

(In the formula (17), * represents a bonding site). The film-forming composition according to claim 1, wherein Q in the aforementioned formula (1) is represented by formula (20),

(In the formula (20), * represents a bonding site). The film-forming composition according to claim 1, wherein the crosslinking agent is a polyfunctional (meth)acrylic compound. The film-forming composition according to claim 1, wherein the inorganic fine particles include metal oxides, metal sulfides, or metal nitrides. The film-forming composition according to claim 1, wherein the organic solvent contains at least one selected from glycol ester-based solvents, ketone-based solvents, and ester-based solvents. A thin film obtained from the film-forming composition according to any one of claims 1 to 16. An electronic device comprising a substrate and the thin film according to claim 17 formed on the substrate. An optical member comprising a substrate and the thin film according to claim 17 formed on the substrate.

Images