TW202309144A - Triazine ring-containing polymer and pattern-forming composition - Google Patents

Abstract

A triazine ring-containing polymer characterized by containing a repeating unit structure represented by formula (1) and having at least one terminal triazine ring wherein at least a part of the terminal triazine ring is blocked with an amino group having a crosslinking group. [In the formula: R and R' independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or an aralkyl group; Ar represents a divalent group having a phenolic hydroxy group; and the symbol * represents a bond.].

Description

Polymer containing three rings, and composition for pattern formation

The present invention relates to a triazine ring-containing polymer and a pattern-forming composition.

In recent years, in the development of liquid crystal displays, organic electroluminescence (EL) displays, touch panels, optical semiconductors (light-emitting diodes (LEDs, etc.) For electronic devices such as organic thin-film transistors (TFTs), high-performance polymer materials have begun to be pursued. 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 membrane hardness, etc. In view of this point of view, 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 the polymer alone can achieve high heat resistance, high transparency, high refractive index, high solubility, It has low volume shrinkage and is suitable as a film-forming composition in the manufacture of electronic devices (Patent Document 1).

However, organic electroluminescent displays generally suffer from a problem of reduced light extraction efficiency, that is, the efficiency of the generated light escapes outside the device. As a method for extracting light to solve this problem, various techniques have been developed conventionally. As one of them, it is known to use a high refractive index layer, a high Refractive index patterning technique. In this high-refractive-index pattern, various negative-type photosensitive compositions have been proposed, and the present applicant has also published various materials that can form negative-type high-refractive-index patterns (see Patent Documents 2 to 4).

However, in the negative type material, the part hardened by the light irradiated from above remains to form a pattern, so in general, the shape after development tends to become an inverted cone and undercut tends to occur. [Prior Art Literature] [Patent Document]

Patent Document 1: International Publication No. 2010/128661 Patent Document 2: International Publication No. 2016/024613 Patent Document 3: International Publication No. 2016/114337 Patent Document 4: International Publication No. 2019/093203

[Problem to be Solved by the Invention]

Furthermore, in the above-mentioned prior art, there is still room for improvement in solvent resistance.

Therefore, a composition capable of forming a negative high-refractive index pattern with excellent solvent resistance is sought. The present invention was made in view of the above circumstances, and an object of the present invention is to provide a triazine ring-containing polymer capable of forming a pattern having excellent solvent resistance, a high refractive index, and excellent transparency. [Means to solve the problem]

As a result of repeated studies by the present inventors in order to achieve the above object, it has been found that a solvent-resistant polymer can be formed by having a triazine ring-containing polymer having a phenolic hydroxyl group and at least a part of the end of the triazine ring blocked by an amine group having a crosslinking group. Fine patterns with excellent properties, high refractive index and excellent transparency.

(式(1)中，R及R’相互獨立地表示氫原子、烷基、烷氧基、芳基或芳烷基，Ar表示具有酚性羥基之2價基。＊表示鍵結鍵。) [2] 如[1]之含三嗪環聚合物，其中前述式(1)中之Ar表示選自以式(2)~(13)所示之群組中之至少1種，

[式(2)~式(13)中，R ¹~R ⁹²相互獨立地表示氫原子、鹵素原子、羥基、羧基、磺基、碳數1~10之烷基、碳數1~10之鹵化烷基或碳數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相互獨立地表示單鍵、CR ⁹⁵R ⁹⁶(R ⁹⁵及R ⁹⁶相互獨立地表示氫原子、碳數1~10之烷基(但該等可一起形成環。)、或碳數1~10之鹵化烷基)、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相互獨立地表示單鍵、碳數1~10之伸烷基、或以式(14)所示之基，

(式(14)中，R ⁹⁸~R ¹⁰¹相互獨立地表示氫原子、鹵素原子、羥基、羧基、磺基、碳數1~10之烷基、碳數1~10之鹵化烷基、或碳數1~10之烷氧基， Y ¹及Y ²相互獨立地表示單鍵或碳數1~10之伸烷基) 但，式(2)~(13)各自具有至少1個酚性羥基， ＊表示鍵結鍵。] [3] 如[1]或[2]之含三嗪環聚合物，其中前述具有交聯基之胺基係以式(15)所示者。

(式(15)中，R ¹⁰²表示交聯基。＊表示鍵結鍵。) [4] 如[3]之含三嗪環聚合物，其中前述具有交聯基之胺基係以式(16)所示者。

(式(16)中，R ¹⁰²表示與上述相同意義。＊表示鍵結鍵。) [5] 如[3]或[4]之含三嗪環聚合物，其中前述R ¹⁰²為含羥基之基或含(甲基)丙烯醯基之基。 [6] 如[5]之含三嗪環聚合物，其中前述R ¹⁰²為羥烷基、(甲基)丙烯醯氧基烷基或以下述式(i)所示之基。

(式(i)中，A ¹表示碳數1~10之伸烷基，A ²表示單鍵或以下述式(j)所示之基，

A ³表示可被羥基取代之(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，＊表示鍵結鍵。) [7] 如[6]之含三嗪環聚合物，其中前述R ¹⁰²為選自羥基甲基、2-羥基乙基、(甲基)丙烯醯氧基甲基、(甲基)丙烯醯氧基乙基、及以下述式(i-2)~式(i-5)所示基之基。

(式(i-2)~式(i-5)中，＊表示鍵結鍵。) [8] 如[1]~[7]中任一項之含三嗪環聚合物，其中前述式(1)中之Ar具有鹵化烷基。 [9] 如[1]~[8]中任一項之含三嗪環聚合物，其中前述式(1)中之Ar係以式(5A)所示者，

(式(5A)中，＊表示鍵結鍵。) [10] 如[9]之含三嗪環聚合物，其中前述式(1)中之Ar係以式(5B)所示者，

(式(5B)中，＊表示鍵結鍵。) [11] 一種圖型形成用組成物，其包含如[1]~[10]中任一項之含三嗪環聚合物。 [12] 如[11]之圖型形成用組成物，其進而包含有機溶劑。 [13] 如[12]之圖型形成用組成物，其中前述有機溶劑包含選自二醇酯(glycol ester)系溶劑、酮系溶劑及酯系溶劑中之至少1種。 [14] 如[11]~[13]中任一項之圖型形成用組成物，其進而包含交聯劑。 [15] 如[14]之圖型形成用組成物，其中前述交聯劑為多官能(甲基)丙烯酸化合物。 [16] 如[11]~[15]中任一項之圖型形成用組成物，其進而包含無機微粒子。 [17] 如[16]之圖型形成用組成物，其中前述無機微粒子於表面具有鹼反應性基。 [18] 如[11]~[17]中任一項之圖型形成用組成物，其用於有機電致發光元件之光取出層。 [19] 一種硬化物，其係由如[11]~[18]中任一項之圖型形成用組成物製作而成者。 [20] 一種電子裝置，其具備基材與形成於前述基材上之如[19]之硬化物。 [21] 如[20]之電子裝置，其係有機電致發光。 [22] 一種光學構件，其具備基材與形成於前述基材上之如[19]之硬化物。 [23] 一種圖型之製作方法，其特徵為將如[11]~[18]中任一項之圖型形成用組成物塗佈於基材上，使有機溶劑蒸發，介隔形成有圖型之遮罩進行光照射後，進行顯影並進一步燒成。 [發明的效果] That is, the present invention is as follows. [1] A triazine ring-containing polymer characterized by comprising a repeating unit structure represented by the following formula (1) and having at least one triazine ring terminal. At least a part of the end of the oxazine ring is blocked by an amine group having a crosslinking group,

(In formula (1), R and R' independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or an aralkyl group, and Ar represents a divalent group having a phenolic hydroxyl group. * represents a bond.) [2] The triazine ring-containing polymer according to [1], wherein Ar in the aforementioned formula (1) represents at least one selected from the group represented by formulas (2) to (13),

[In formulas (2) to (13), R ¹ to R ⁹² independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, a sulfo group, an alkyl group with 1 to 10 carbons, and a halogenated group with 1 to 10 carbons. An alkyl group 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 ^R96 independently represent a hydrogen atom, an alkyl group with 1 to 10 carbons (but these can 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, an alkyl group with 1 to 10 carbons or a phenyl group), X ¹ and X ² independently represent a single bond, an alkylene group with 1 to 10 carbons, or The basis shown in formula (14),

(In formula (14), R ⁹⁸ to R ¹⁰¹ independently represent a hydrogen atom, a halogen atom, a hydroxyl group, 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 carbon An alkoxy group with a number of 1 to 10, Y1 ^{and Y2} independently represent a single bond or an alkylene group with a carbon number of 1 to 10) However, each of the formulas (2) to (13) has at least one phenolic hydroxyl group, ＊Indicates a bonding key. ] [3] The triazine ring-containing polymer according to [1] or [2], wherein the aforementioned amino group having a crosslinking group is represented by formula (15).

(In the formula (15), R ¹⁰² represents a crosslinking group. * represents a bond.) [4] The triazine ring-containing polymer as in [3], wherein the aforementioned amino group with a crosslinking group is represented by the formula (16 ) shown.

(In formula (16), R ¹⁰² represents the same meaning as above. * Represents a bond.) [5] The triazine ring-containing polymer as in [3] or [4], wherein the aforementioned R ¹⁰² is a hydroxyl-containing group Or a base containing a (meth)acryloyl group. [6] The triazine ring-containing polymer according to [5], wherein the aforementioned R ¹⁰² is a hydroxyalkyl group, a (meth)acryloyloxyalkyl group, or a group represented by the following formula (i).

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

A ³ represents an aliphatic hydrocarbon group with a valence of (a+1) which may 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. ) [7] The triazine ring-containing polymer as in [6], wherein the aforementioned R ¹⁰² is selected from the group consisting of hydroxymethyl, 2-hydroxyethyl, (meth)acryloxymethyl, (meth)acryl Oxyethyl group, and a group represented by the following formula (i-2) to formula (i-5).

(In formula (i-2) to formula (i-5), * represents a bond.) [8] The triazine ring-containing polymer as in any one of [1] to [7], wherein the aforementioned formula ( Ar in 1) has a halogenated alkyl group. [9] The triazine ring-containing polymer according to any one of [1] to [8], wherein Ar in the aforementioned formula (1) is represented by formula (5A),

(In the formula (5A), * represents a bond.) [10] The triazine ring-containing polymer as described in [9], wherein Ar in the aforementioned formula (1) is represented by the formula (5B),

(In the formula (5B), * represents a bond.) [11] A pattern-forming composition comprising the triazine ring-containing polymer according to any one of [1] to [10]. [12] The pattern-forming composition according to [11], further comprising an organic solvent. [13] The pattern-forming composition according to [12], wherein the organic solvent contains at least one selected from the group consisting of glycol ester solvents, ketone solvents, and ester solvents. [14] The pattern-forming composition according to any one of [11] to [13], further comprising a crosslinking agent. [15] The pattern-forming composition according to [14], wherein the crosslinking agent is a polyfunctional (meth)acrylic compound. [16] The composition for pattern formation according to any one of [11] to [15], further comprising inorganic fine particles. [17] The pattern-forming composition according to [16], wherein the inorganic fine particles have alkali-reactive groups on their surfaces. [18] The pattern-forming composition according to any one of [11] to [17], which is used for a light extraction layer of an organic electroluminescence device. [19] A hardened product made of the pattern-forming composition according to any one of [11] to [18]. [20] An electronic device comprising a substrate and the cured product described in [19] formed on the substrate. [21] The electronic device of [20], which is an organic electroluminescent device. [22] An optical member comprising a substrate and the cured product described in [19] formed on the substrate. [23] A method for making a pattern, characterized in that the pattern-forming composition according to any one of [11] to [18] is coated on a substrate, and the organic solvent is evaporated to form a pattern After the mask of the type is irradiated with light, it is developed and further fired. [Effect of the invention]

The triazine ring-containing polymer of the present invention imparts fine patterns with excellent solvent resistance, high refractive index and excellent transparency. After the composition of the present invention is masked, exposed and hardened, it is developed by alkali and then fired to provide a fine pattern with excellent solvent resistance, high refractive index and excellent transparency. The pattern produced by the composition of the present invention can be suitably used in the manufacture of liquid crystal displays because of the solvent resistance, high heat resistance, high refractive index, and low volume shrinkage characteristics of triazine ring-containing polymers. , organic electroluminescent (EL) displays, touch panels, optical semiconductor elements, solid-state imaging elements, organic thin-film solar cells, dye-sensitized solar cells, organic thin-film transistors, lenses, EL, cameras, binoculars, microscopes In the field of electronic devices and optical materials such as materials that are part of semiconductor exposure devices, etc.

Hereinafter, the present invention will be described in more detail. (polymer containing triazine ring) The triazine ring-containing polymer of the present invention has a repeating unit structure represented by the following formula (1). The triazine ring-containing polymer is, for example, a so-called hyperbranched polymer. A hyperbranched polymer means a highly branched polymer having an irregular branched structure. Irregular here means more irregular than the branched structure of the dendritic polymer which is a hyperbranched polymer having a regular branched structure. For example, a triazine ring-containing polymer as a hyperbranched polymer, as a structure larger than the repeating unit structure shown in formula (1), includes 3 bonding bonds of the repeating unit structure shown in formula (1), respectively The bond has a structure (structure A) composed of repeating units represented by formula (1). In the triazine ring-containing polymer that is a hyperbranched polymer, the structure A is distributed throughout the entirety of the triazine ring-containing polymer except for the terminal of the triazine ring-containing polymer. In the triazine ring-containing polymer that is a hyperbranched polymer, the repeating unit structure can essentially consist of only the repeating unit structure represented by formula (1).

＊表示鍵結鍵。 ＜Equation (1)＞

＊Indicates a bonding key.

＜<R and R'>> In the above formula, R and R' independently represent a hydrogen atom, and an alkyl group, an alkoxy group, an aryl group, or an aralkyl group are all preferably hydrogen atoms from the viewpoint of increasing the refractive index. In the present invention, the carbon number of the alkyl group is not particularly limited, and is preferably 1-20. In consideration of further improving the heat resistance of the polymer, the carbon number of the alkyl group is more preferably 1-10, and more preferably 1-20. 3. Moreover, the structure of an alkyl group is not specifically limited, For example, it may be linear, branched, cyclic, and any combination 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, 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 Base-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 Base, 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-di Methyl-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-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl -cyclopropyl, 2-ethyl-3-methyl-cyclopropyl and the like.

The number of carbons in the alkoxy group is not particularly limited, preferably 1-20, and in consideration of further improving the heat resistance of the polymer, the number of carbons in the alkoxy group is more preferably 1-10, and more preferably 1-3 . Also, 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 the alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, s-butoxy, t-butoxy , 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 Base-n-butoxy, 1-ethyl-n-butoxy, 2-ethyl-n-butoxy, 1,1,2-trimethyl-n-propoxy, 1,2,2-trimethyl Base-n-propoxy, 1-ethyl-1-methyl-n-propoxy, 1-ethyl-2-methyl-n-propoxy, etc.

The carbon number of the aryl group is not particularly limited, and is preferably 6-40. In consideration of further improving the heat resistance of the polymer, the carbon number of the aryl group is more preferably 6-16, and more preferably 6-13. The above-mentioned aryl group in the present invention 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, a cyano group, and the like. Specific examples of the aryl group include phenyl, o-chlorophenyl, m-chlorophenyl, p-chlorophenyl, o-fluorophenyl, p-fluorophenyl, o-methoxyphenyl, p-methoxyphenyl Base, 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 carbon number of the aralkyl group is not particularly limited, preferably 7 to 20 carbons, and the structure of the alkyl part is not particularly limited, for example, it can be straight chain, branched, cyclic, and two or more of these any combination. The aralkyl group in the present invention includes an aralkyl group having a substituent. Examples of the substituent include a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, and the like. Specific examples thereof include benzyl, p-methylphenylmethyl, m-methylphenylmethyl, o-ethylphenylmethyl, m-ethylphenylmethyl, p-ethylphenylmethyl , 2-propylphenylmethyl, 4-isopropylphenylmethyl, 4-isobutylphenylmethyl, α-naphthylmethyl, etc.

＜＜Ar＞＞ Ar in formula (1) is not particularly limited as long as it is a divalent group having a phenolic hydroxyl group. Since Ar has a phenolic hydroxyl group, the solubility to an alkaline developing solution is improved. The number of phenolic hydroxyl groups in Ar is not particularly limited, and may be 1 or more, preferably 1-5, more preferably 1-4. In addition, the phenolic hydroxyl group may be a hydroxyl group directly bonded to a benzene ring, or may be a hydroxyl group directly bonded to a naphthalene ring.

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

＊表示鍵結鍵。

＊Indicates a bonding key.

The above R ¹ ~ R ⁹² independently represent a hydrogen atom, a halogen atom, a hydroxyl group, 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 1 to 10 carbons, W ¹ and W ² independently represent a single bond, CR ⁹⁵ R ⁹⁶ (R ⁹⁵ and R ⁹⁶ independently represent a hydrogen atom, a carbon An alkyl group with a number of 1~10 (but these can form a ring together.), or a halogenated alkyl group with a carbon number of 1~10.), C=O, O, S, SO, SO ₂ or NR ⁹⁷ (R ⁹⁷ represents A hydrogen atom, an 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. However, each of the formulas (2) to (13) has at least one phenolic hydroxyl group.

The halogenated alkyl group having 1 to 10 carbon atoms is one in which at least one of the hydrogen atoms in the above-mentioned alkyl group having 1 to 10 carbon atoms 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 Fluoropropyl, 2,2,2-trifluoro-1-(trifluoromethyl)ethyl, perfluoropropyl, 4,4,4-trifluorobutyl, 3,3,4,4,4- Pentafluorobutyl, 2,2,3,3,4,4,4-heptafluorobutyl, perfluorobutyl, 2,2,3,3,4,4,5,5,5-nonafluoropentyl 2,2,3,3,4,4,5,5-octafluoropentyl, perfluoropentyl, 2,2,3,3,4,4,5,5,6,6,6- Undecafluorohexyl, 2,2,3,3, 4,4,5,5,6,6-decafluorohexyl, 3,3,4,4,5,5,6,6,6-nonafluorohexyl and perfluorohexyl. In the present invention, if consideration is given to improving the solubility of triazine ring-containing polymers to low-polarity solvents while maintaining the refractive index, it is preferably a perfluoroalkyl group with 1 to 10 carbon atoms, especially preferably a perfluoroalkyl group with 1 to 10 carbon atoms. 1-5 perfluoroalkyl, more preferably trifluoromethyl.

In addition, ^X1 and ^X2 independently represent 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, for example, they may be linear, branched, cyclic, or any combination of two or more of these .

＊表示鍵結鍵。

＊Indicates a bonding key.

The above R ⁹⁸ ~ R ¹⁰¹ 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 independently represent a single bond or an alkylene group having 1 to 10 carbon atoms. Examples of these halogen atoms, alkyl groups, alkyl halides, and alkoxy groups include the same ones as those for the halogen atoms, alkyl groups, alkyl halides, and alkoxy groups in R ¹ to R ⁹² . The structures of the alkyl and alkoxy groups in R ⁹⁸ to R ¹⁰¹ are not particularly limited, for example, they may be linear, branched, cyclic, or any combination of two or more of these. The structure of the alkylene group in ^Y1 and ^Y2 is not particularly limited, for example, it may be linear, branched, cyclic, or any combination of two or more of these. 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 above-mentioned alkylene group is not particularly limited, and may be, for example, any of linear, branched, cyclic, and combinations of two or more of these.

From the viewpoint of improving the compatibility between the triazine ring-containing polymer and the inorganic microparticles described later, Ar preferably has a halogenated alkyl group, more preferably has a halogenated alkyl group with 1 to 10 carbon atoms, and particularly preferably has a halogenated alkyl group with 1 to 10 carbon atoms. Fluorinated Alkyl. The number of halogenated alkyl groups in Ar is not particularly limited, but is preferably 1-4.

＊表示鍵結鍵。

＊表示鍵結鍵。 Ar is preferably represented by formula (5A), more preferably represented by formula (5B).

＊Indicates a bonding key.

＊Indicates a bonding key.

＜Amino group with crosslinking group＞ Also, the triazine ring-containing polymer of the present invention has at least one triazine ring terminal, and at least a part of the triazine ring terminal is blocked by an amine group having a crosslinking group. The triazine ring-containing polymer of the present invention has at least one triazine ring terminal, but the terminal triazine ring usually has two halogen atoms that can be substituted with the above-mentioned amino group having a crosslinking group. Therefore, the above-mentioned amine group having a crosslinking group may be bonded to the same triazine ring terminal, and, when there are plural triazine ring terminals, may be bonded to other triazine ring terminals, respectively.

The number of crosslinking groups in the amine group with crosslinking groups is not particularly limited, and can be set to any number. Considering the balance between solvent resistance and solubility in organic solvents, it is preferably 1 to 4, more preferably 1 to 2, more preferably 1. 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。＊表示鍵結鍵。) 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 bonding bond.)

(式中，R ¹⁰²表示交聯基。＊表示鍵結鍵。)

(式中，R ¹⁰²表示與上述相同意義。＊表示鍵結鍵。) In formula (X), Z may be the crosslinking group itself. The crosslinking group is preferably bonded to the amine group through an aryl group. Next, the amine 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. * represents a bond.)

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

Examples of the crosslinking group include hydroxyl-containing groups, vinyl-containing groups, epoxy-containing groups, oxetane-containing groups, carboxyl-containing groups, sulfo-containing groups, and thiol-containing groups. base, (meth)acryl group-containing base, etc., if consideration is given to improving the heat resistance of the triazine ring-containing polymer and the solvent resistance (crack resistance) of the obtained film, then preferably containing (meth)acryl group base) the base of the acryl group.

As the hydroxyl-containing group, hydroxyl group and hydroxyalkyl group can be mentioned, preferably a hydroxyalkyl group with 1 to 10 carbon atoms, more preferably a hydroxyalkyl group with 1 to 5 carbon atoms, and more preferably a hydroxyalkyl group with 1 to 5 carbon atoms. 3 Hydroxyalkyl. 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 and other carbon atoms bonded by hydroxyl groups Those who are primary carbon atoms; 1-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 1-hydroxybutyl, 2-hydroxybutyl, 1-hydroxyhexyl, 2-hydroxyhexyl, 1-hydroxyoctyl The carbon atoms bonded by hydroxyl groups such as hydroxy-group, 2-hydroxyoctyl group, 1-hydroxydecyl group, 2-hydroxydecyl group, 1-hydroxy-1-methylethyl group and 2-hydroxy-2-methylpropyl group are Those with secondary or tertiary carbon atoms.

Especially in consideration of improving heat resistance and high-temperature and high-humidity resistance, the carbon atom to which the hydroxyl group is bonded is preferably a primary carbon atom, and among them, a hydroxyalkyl group with 1 to 5 carbons is more preferred, and a carbon number 1 is more preferred. ~3 hydroxyalkyl groups, more preferably hydroxymethyl and 2-hydroxyethyl, most preferably 2-hydroxyethyl.

Examples of the (meth)acryl group-containing group include a (meth)acryl group, a (meth)acryloxyalkyl group, and a group represented by the following formula (i), preferably having The (meth)acryloyloxyalkyl group of the alkylene group having 1 to 10 carbon atoms and the group represented by the following formula (i), more preferably the group represented by the following formula (i).

(式中，A ¹表示碳數1~10之伸烷基，A ²表示單鍵或以下述式(j)所示之基，

A ³表示可被羥基取代之(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，＊表示鍵結鍵。)

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

A ³ represents an aliphatic hydrocarbon group with a valence of (a+1) which may 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, ethylidene, trimethylene, and propane. -1,2-diyl, tetramethylene, butane-1,3-diyl, butane-1,2-diyl, 2-methylpropane-1,3-diyl, pentamethylene , Hexamethylene, Heptamethylene, Octamethylene, Nonamethylene, Decamethylene, etc. In particular, considering the improvement of heat resistance and high-temperature and high-humidity resistance, among these, those with alkylene groups having 1 to 5 carbon atoms are preferred, those with alkylene groups having 1 to 3 carbon atoms are more preferred, and more preferably An alkylene group having 1 or 2 carbon atoms.

Specific examples of the aforementioned (meth)acryloxyalkyl groups include (meth)acryloxymethyl, 2-(meth)acryloxyethyl, 3-(methyl) 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, more preferably a methylene group, an ethylene group, or a propylidene group. Examples of the alkylene group having 1 to 10 carbon atoms include the same ones as the alkylene group contained in the above-mentioned (meth)acryloxyalkyl group.

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

(式中，＊與上述相同。) 較佳為碳數1~5之伸烷基，更佳為碳數1~3之伸烷基，又更佳為亞甲基及伸乙基。作為A ³之伸烷基，於A ¹所例示之伸烷基中，可舉出碳數1~5之伸烷基。 ^A3 is an (a+1)-valent aliphatic hydrocarbon group that can be substituted by a hydroxyl group. As its specific example, for example, an alkylene group with 1 to 5 carbon atoms and the following formula (k-1)~(k- 3) The base shown,

(wherein, * is the same as above.) Preferably, it is an alkylene group having 1 to 5 carbon atoms, more preferably, it is an alkylene group having 1 to 3 carbon atoms, and still more preferably, it is a methylene group or an ethylene group. Examples of the alkylene group of ^A3 include those having 1 to 5 carbon atoms among the alkylene groups exemplified in ^A1 .

a represents 1 or 2, preferably 1.

As a preferable aspect of the group represented by formula (i), what is represented by following formula (i-1) is mentioned.

(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.)

As a more preferable aspect of the group represented by formula (i), what is represented by following formula (i-2)-(i-5) is mentioned.

(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.

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

Examples of oxetane-containing groups include oxetan-3-yl, (oxetan-3-yl)methyl, 2-(oxetan-3-yl) Ethyl, 3-(oxetan-3-yl)propyl, 4-(oxetan-3-yl)butyl and the like.

As a carboxyl group-containing group, a carboxyl group, a carboxyalkyl group with 2-10 carbon atoms, etc. are mentioned. As a carboxyalkyl group with 2 to 10 carbons, it is preferred that the carbon atom to which the carboxyl group is bonded is a primary carbon atom. As specific examples, carboxymethyl, 2-carboxyethyl, 3-carboxypropyl and 4-carboxybutyl etc.

Examples of the sulfo group-containing group include a sulfo group and a sulfoalkyl group having 1 to 10 carbon atoms. As a sulfoalkyl group having 1 to 10 carbon atoms, it is preferred that the carbon atom to which the sulfo group is bonded is a primary carbon atom. Specific examples include sulfomethyl, 2-sulfoethyl, 3- Sulfopropyl and 4-sulfobutyl, etc.

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

Amine groups having (meth)acryloxyalkyl groups can be introduced into triazine ring-containing polymers with amine groups having hydroxyalkyl groups by using the corresponding (meth)acryloxyalkylamine compounds. (meth)acrylic acid halide (meth)acrylic acid halide (meth)acrylic acid halide (meth)acrylic acid halide, and (meth)acrylic acid glycidyl ester act on the hydroxyl group contained in the above-mentioned hydroxyalkyl group.

The amino group having a group represented by formula (i) can be obtained by introducing an amino group having a hydroxyalkyl group into a triazine ring-containing polymer by using an amino compound having a cross-linking group as a purpose, and then It introduces by making the (meth)acrylate compound which has an isocyanate group represented by following formula (i') act on the hydroxyl group contained in the said hydroxyalkyl group.

(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.)

Specific examples of (meth)acryloxyalkylamine compounds include those in which (meth)acryl halide or glycidyl (meth)acrylate acts on the above-mentioned hydroxyalkylamine compound. An ester compound obtained from a hydroxyl group. As said (meth)acryl halide, (meth)acryl chloride, (meth)acryl bromide, and (meth)acryl iodide are mentioned. Specific examples of the (meth)acrylate compound having an isocyanate group represented by the above formula (i') include 2-isocyanatoethyl acrylate, 2-isocyanatoethyl methyl acrylate and 1,1-(bisacryloxymethyl)ethyl isocyanate. In the present invention, 2-isocyanatoethylacrylate is preferable from the viewpoint of a simple synthesis method.

The weight average molecular weight of the triazine ring-containing polymer in the present invention is not particularly limited, but is preferably 500-500,000, and more preferably 500-100,000, from the viewpoint of improving heat resistance and reducing shrinkage. It is 2,000 or more, and it is preferably 50,000 or less, more preferably 30,000 or less, still more preferably 15,000 or less, and still more preferably 10,000 or less from the viewpoint of improving solubility and reducing the viscosity of the obtained composition. In addition, the weight average molecular weight in this invention is the average molecular weight obtained by the standard polystyrene conversion of the colloid permeation chromatography (henceforth referred to as GPC) analysis.

＜Method for producing triazine ring-containing polymer＞ The triazine ring-containing polymer (hyperbranched polymer) of the present invention can be produced following the method disclosed in the aforementioned International Publication No. 2010/128661.

For example, as shown in the following scheme 1, the triazine ring-containing polymer (24) can be reacted with a triazine compound (21) and a diamine compound (22) in an appropriate organic solvent, and has It is obtained by reacting an amino compound (23) having a crosslinking group (Z).

(式中，X相互獨立地表示鹵素原子，A表示具有酚性羥基之2價基，Z表示具有交聯基之基。)

(In the formula, X independently represents a halogen atom, A represents a divalent group having a phenolic hydroxyl group, and Z represents a group having a crosslinking group.)

In the above scheme 1, the feeding ratio of the diamine-based compound (22) can be arbitrary as long as the target polymer can be obtained, and the ratio of the diamine-based compound (22) to 1 equivalent of the triazine compound (21) is preferably 0.01 ~10 equivalents, more preferably 0.7~5 equivalents. The diamine-based compound (22) can be added as a solvent-free (neat) solution or as a solution dissolved in an organic solvent. Considering the ease of operation and the ease of reaction control, etc., the latter is preferred. s method. The reaction temperature can be appropriately set within the range from the melting point of the solvent used to the boiling point of the solvent, preferably about -30 to 150°C, more preferably -10 to 100°C.

As another aspect, the means shown in the following flow 2 can be mentioned. In this method, after reacting the triazine compound (31) and the diamine compound (32) in an appropriate organic solvent, and an aromatic amino compound having a hydroxyalkyl group (A ¹ ') as a terminal blocking agent (33) react to obtain a triazine ring-containing polymer (34) (stage 1), and then further react the (meth)acrylate compound (35) having an isocyanate group to the triazine ring-containing polymer (34 ) acts on the hydroxyl group of the hydroxyalkyl group contained in (second stage) to obtain a triazine ring-containing polymer (36).

(式中，X相互獨立地表示鹵素原子，Ar表示具有酚性羥基之2價基，A ¹’表示碳數1~10之羥烷基，A ³表示可被羥基取代之(a+1)價之脂肪族烴基，A ⁴表示氫原子或甲基，A ¹表示碳數1~10之伸烷基。)

(In the formula, X independently represents a halogen atom, Ar represents a divalent group having a phenolic hydroxyl group, A ¹ ' represents a hydroxyalkyl group with 1 to 10 carbon atoms, and A ³ represents (a+1) which may be substituted by a hydroxyl group A valent aliphatic hydrocarbon group, A ⁴ represents a hydrogen atom or a methyl group, A ¹ represents an alkylene group with 1 to 10 carbons.)

In the above scheme 2, the feeding ratio and addition method of the diamine compound (32) in the first stage, and the reaction temperature in the reaction until the triazine ring-containing polymer (34) is obtained, can be set as described in scheme 1 or the same. Also, in the second stage, the feeding ratio of the (meth)acrylate compound (35) having an isocyanate group to the triazine ring-containing polymer (34) can be adjusted according to the ratio of the hydroxyalkyl group (A1') to the isocyanate group. Rather, it is set arbitrarily, preferably 0.1 to 10 equivalents, more preferably 0.5 to 5 equivalents, and more preferably 0.7 to 3 Equivalent, and more preferably 0.9~1.5 equivalent. For example, when all the hydroxyalkyl groups (A1') contained in the triazine ring-containing polymer (34) are represented by the formula (i), the feeding ratio is based on the ratio of the hydroxyalkyl groups used. 1 equivalent of the arylamino compound (33) of the alkyl group, the above-mentioned (meth)acrylate compound (35) is preferably 1.0-10 equivalents, more preferably 1.0-5 equivalents, and more preferably 1.0-3 equivalents, More preferably, it is 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 (34). Considering that the (meth)acryl group does not cause polymerization during the reaction, it is preferably 30~80°C , more preferably 40~70°C, more preferably 50~60°C.

In the second stage of Scheme 2, in order not to cause polymerization of (meth)acryl-based reaction, the reaction can 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, phenothiazines, and the like. Among these, N-nitrosophenyl hydroxylamine or its salts are preferable from the viewpoint of being excellent in the 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-butylcatechol, 2-t-butylhydroquinone, 2,6-di-t-butyl -4-Methylphenol etc. The amount of polymerization inhibitor used is not particularly limited. For example, with respect to the (meth)acrylate compound with isocyanate group represented by formula (i'), it can be 1~200ppm in terms of mass ratio, or it can be 10~100ppm. By using a polymerization inhibitor, even if the reaction temperature rises to about 60-80°C, the polymerization of (meth)acryloyl groups can be suppressed and the second-stage reaction can be carried out.

As the organic solvent, various solvents commonly used in this reaction can be used, for example, tetrahydrofuran, dioxane, dimethylsulfoxide; N,N-dimethylformamide, N-methyl-2- Pyrrolidone, Tetramethylurea, Hexamethylphosphamide, N,N-Dimethylacetamide, 3-Methoxy-N,N-Dimethylpropionamide, 3-Butoxy- N,N-dimethylacrylamide, N-methyl-2-piperidone, N,N'-dimethylethylene urea, N,N,N',N'-tetramethylmalonyl Amine, N-methylcaprolactam, N-acetylpyrrolidine, N,N-diethylacetamide, N-ethyl-2-pyrrolidone, N,N-dimethylpropionic acid Amide-based solvents such as amide, N,N-dimethylisobutylamide, N-methylformamide, N,N'-dimethylpropylene urea, and their mixed solvents. Among them, N,N-dimethylformamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, 3-methoxy-N ,N-dimethylacrylamide, 3-butoxy-N,N-dimethylacrylamide and their mixtures, especially N,N-dimethylacetamide, N-formyl Base-2-pyrrolidone, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide.

In addition, in the reaction of Scheme 1 above, various bases that are generally used during or after polymerization can be added. Specific examples of the base include potassium carbonate, potassium hydroxide, sodium carbonate, sodium hydroxide, sodium bicarbonate, sodium ethoxide, sodium acetate, lithium carbonate, lithium hydroxide, lithium oxide, potassium acetate, magnesium oxide , calcium oxide, barium hydroxide, trilithium phosphate, trisodium phosphate, tripotassium phosphate, cesium fluoride, aluminum oxide, ammonia, n-propylamine, trimethylamine, triethylamine, diisopropylamine, Diisopropylethylamine, N-methylpiperidine, 2,2,6,6-tetramethyl-N-methylpiperidine, pyridine, 4-dimethylaminopyridine, N-methyl phylloline, 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 (18). In addition, these bases can also be used in the form of an aqueous solution. In the obtained polymer, the raw material components are preferably not left, but a part of the raw materials may remain as long as the effect of the present invention is not impaired. After completion of the reaction, the product can be easily purified by reprecipitation or the like.

A known method can be used as a terminal blocking method using an amino compound having a crosslinking group. At this time, the usage amount of the terminal blocking agent is preferably about 0.05-10 equivalents, more preferably 0.1-5 equivalents, and more The best is 0.5~2 equivalents. As the reaction solvent and reaction temperature, the same conditions as described in the reaction of the above-mentioned scheme 1 or the reaction of the first stage of the scheme 2 can be mentioned, and the terminal blocking agent can be used simultaneously with the diamine compound (22) or (32). feed in. In addition, an unsubstituted amino compound having no crosslinking group may be used to end-block with two or more types of groups.

Also, in addition to terminal blocking using an amine compound having a crosslinking group, an arylamino compound having a specific heteroatom-containing substituent may also be used for terminal blocking. The refractive index of the obtained film can be further increased by end-capping with an arylamine group having a specific heteroatom-containing substituent. Specific heteroatom-containing substituents include cyano, alkylamino, arylamino, nitro, alkylmercapto, arylmercapto, alkoxycarbonyl, and alkoxycarbonyloxy. Examples of the arylamino group having a specific heteroatom-containing substituent include those represented by the following formula (41).

式中，Y為「特定含雜原子之取代基」，表示氰基、烷基胺基、芳胺基、硝基、烷基巰基、芳基巰基、烷氧基羰基或烷氧基羰氧基。m表示1~5之整數。m為2以上時，Y可為相同，亦可為相異。＊表示鍵結鍵。

In the formula, Y is a "specific heteroatom-containing substituent", representing cyano, alkylamino, arylamino, nitro, alkylmercapto, arylmercapto, alkoxycarbonyl 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 bonding key.

Among these, Y is preferably a cyano group or a nitro group. m is preferably 1. When m is 1, Y is preferably substituted at the para or meta position.

Also, in the case of 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 resistance. From the viewpoint of solvent property and high refractive index, relative to 1 mole of amino compound having a crosslinking group, 0.1 to 1.0 mole of the aromatic amino compound having a specific heteroatom-containing substituent is preferred, and more preferably 0.1-0.5 mol, more preferably 0.1-0.3 mol.

(pattern forming composition) The pattern-forming composition of the present invention contains at least the triazine ring-containing polymer of the present invention, and further contains a cross-linking agent, inorganic fine particles, etc. if necessary.

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

＜Crosslinking agent＞ The cross-linking agent used in the present invention is not particularly limited as long as it is a compound that can cause a cross-linking reaction alone or together with the triazine ring-containing polymer to form a cross-linking structure. Examples of such compounds include melamine-based compounds (for example, phenoplast compounds, aminoplast compounds, etc.) having cross-linking substituents such as methylol and methoxymethyl groups, substituted urea compounds, etc. Compounds, compounds containing cross-linked substituents such as epoxy groups or oxetane groups (for example, polyfunctional epoxy compounds, polyfunctional oxetane compounds, etc.), compounds containing blocked isocyanate groups, Compounds having acid anhydride groups, compounds having (meth)acryl groups, etc., preferably contain epoxy groups, blocked isocyanate groups, and (meth)acryl groups from the viewpoint of heat resistance and storage stability. The compound is particularly preferably a compound having a blocked isocyanate group, a polyfunctional epoxy compound and/or a polyfunctional (meth)acrylic compound that can obtain a photocurable composition without using an initiator.

The polyfunctional epoxy compound is not particularly limited as long as it has two or more epoxy groups in one molecule. Specific examples thereof include ginseng (2,3-epoxypropyl) isocyanurate, 1,4-butanediol diglycidyl ether, 1,2-epoxy-4 -(Epoxyethyl)cyclohexane, Glycerin Triglycidyl Ether, Diethylene Glycol Diglycidyl Ether, 2,6-Diglycidylphenyl Glycidyl Ether, 1, 1,3-para[p-(2,3-epoxypropoxy)phenyl]propane, Diglycidyl 1,2-cyclohexanedicarboxylate, 4,4'-Methylenebis (N,N-diepoxypropylaniline), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, trimethylolethane triglycidyl ether, bisphenol-A-diglycidyl ether, pentaerythritol polyglycidyl ether, etc.

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

There are no particular limitations on the polyfunctional (meth)acrylic compound as long as it has two or more (meth)acryl groups in one molecule. Specific examples thereof include ethylene glycol diacrylate, ethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, ethoxylated bisphenol A Acrylates, Ethoxylated Bisphenol A Dimethacrylate, Ethoxylated Trimethylolpropane Triacrylate, Ethoxylated Trimethylolpropane Trimethacrylate, Ethoxylated Triglycerol Acrylates, Ethoxylated Glycerin Trimethacrylate, Ethoxylated Pentaerythritol Tetraacrylate, Ethoxylated Pentaerythritol Tetramethacrylate, Ethoxylated Dipentaerythritol Hexaacrylate, Polyglycerol Monooxiride Alkane Polyacrylate, Polyglycerol Polyethylene Glycol Polyacrylate, Dipentaerythritol Hexaacrylate, Dipentaerythritol Hexamethacrylate, Neopentyl Glycol Diacrylate, Neopentyl Glycol Dimethacrylate, Pentaerythritol Triacrylate Ester, Pentaerythritol Trimethacrylate, Trimethylolpropane Triacrylate, Trimethylolpropane Trimethacrylate, Tricyclodecane Dimethanol Diacrylate, Tricyclodecane Dimethanol Dimethacrylate , 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, polyacid modified acrylic oligomer, etc.

In addition, the polyfunctional (meth)acrylic compound can be obtained as a commercial item, and specific examples thereof include NK ESTER A-200, TO A-400, TO A-600, TO A-1000, TO A -9300 (isocyanuric acid ginseng (2-acryloxyethyl) ester), same as A-9300-1CL, same as A-TMPT, same as UA-53H, same as 1G, same as 2G, same as 3G, same as 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 as 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, A-DPH, Same as A-TMPT, Same as A-DCP, Same as A-HD-N , same TMPT, same DCP, same NPG, same HD-N, same A-DPH-12E, same A-DPH-48E, same A-DPH-96E, NK oligo U-15HA, NK polymer Vanaresin GH-1203 (above , New Nakamura Chemical Industry Co., Ltd.), KAYARAD (registered trademark) DPHA, same NPGDA, same PET30, same DPEA-12, same PEG400DA, same THE-330, same RP-1040, DN-0075 (above, Japanized Pharmaceutical Co., Ltd.), aronix M-210, same M-303, same M-305, same M-306, same M-309, same M-306, same M-310, same M-313, same M- 315, same M-321, same M-350, same M-360, same M-400, same M-402, same M-403, same M-404, same M-405, same M-406, same M- 408, same as M-450, same as M-452, same as M-460 (above, manufactured by Toa Gosei Co., Ltd.), DPGDA, HDDA, TPGDA, HPNDA, PETIA, PETRA, TMPTA, TMPEOTA, EBECRYL11, same 40, same 135 , Same 140, Same 145, Same 150, Same 180, Same 1142, Same 204, Same 205, Same 210, Same 215, Same 220, Same 230, Same 244, Same 245, Same 265, Same 270, Same 280/15IB , Same 284, Same 294/25HD, Same 303, Same 436, Same 438, Same 446, Same 450, Same 524, Same 525, Same 600, Same 605, Same 645, Same 648, Same 767, Same 770, Same 800 , Same 810, Same 811, Same 812, Same 846, Same 851, Same 852, Same 853, Same 860, Same 884, Same 885, Same 1259, Same 1290, Same 1606, Same 1830, Same 1870, Same 3500, Same 3603, same 3608, same 3700, same 3701, same 3702, same 3703, same 3708, same 4820, same 4858, same 5129, same 6040, same 8210, same 8454, same 8301R, same 8307, same 8311, same 8402, Same as 8405, same 8411, same 8465, same 8701, same 8800, same 8804, same 8807, same 9270, same 9227EA, same 936, KRM8200, same 8200AE, same 7735, same 8296, same 08452, same 8904, same 8528, Same as 8912, OTA480, IRR214-K, same 616, same 679, same 742, same 793, PEG400DA-D (ACA) Z200M, same Z230AA, same Z250, same Z251, same Z300, same Z320, same Z254F (above, DAICEL -ALLNEX Co., Ltd.), etc. The said polybasic-acid modified acrylic oligomer can also be acquired as a commercial item, and aronix M-510, 520 (above, manufactured by Toagosei Co., Ltd.) etc. are mentioned as a specific example.

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. Specific examples thereof include phthalic anhydride, tetrahydrophthalic anhydride, Hexahydrophthalic Anhydride, Methyltetrahydrophthalic Anhydride, Methylhexahydrophthalic Anhydride, Nadic Anhydride, Methyl Nadic Anhydride, Maleic Anhydride, Succinic Anhydride, Octylsuccinic Anhydride, Dodecenyl succinic anhydride and other molecules have an acid anhydride group; 1,2,3,4-cyclobutanetetracarboxylic dianhydride, pyromellitic anhydride, 3,4-dicarboxy-1,2, 3,4-tetrahydro-1-naphthalene succinic dianhydride, bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic dianhydride, 5-(2,5-dioxotetrahydro -3-furyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 1,2,3,4-butanetetracarboxylic dianhydride, 3,3',4,4 '-Diphenyl ketone tetracarboxylic dianhydride, 3,3',4,4'-biphenyl tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane di Anhydrides, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, etc. have two acid anhydride groups in the molecule.

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, it is a blocked isocyanate group that is exposed to high temperature during thermal curing When the protecting group (capping part) is thermally dissociated and detached, there is no particular limitation on the one that causes a urethane bonding reaction between the generated isocyanate group and the phenolic hydroxyl group of the triazine ring-containing polymer of the present invention. For example, a compound having two or more groups represented by the following formula in one molecule (in addition, these groups may be the same or different) may be mentioned.

(式中，R _b表示封端部之有機基。)

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

Such a compound can be obtained, for example, by reacting an appropriate blocking agent with a compound having two or more isocyanate groups in one molecule. Examples of compounds having two or more isocyanate groups in one molecule include isophorone diisocyanate, 1,6-hexamethylene diisocyanate, methylene bis(4-cyclohexyl isocyanate), trimethyl Polyisocyanates of hexamethylene diisocyanate, their 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, cyclic Alcohols such as hexanol; phenols such as phenol, o-nitrophenol, p-chlorophenol, o-, m-, or p-cresol; lactams such as ε-caprolactam, acetone oxime, methyl ethyl ketone oxime, methyl isobutyl Ketoxime, cyclohexanone oxime, acetophenone oxime, diphenyl ketone oxime and other oximes; pyrazoles, 3,5-dimethylpyrazole, 3-methylpyrazole and other pyrazoles; dodecylsulfur Alcohols, thiols such as benzenethiol, etc.

Compounds containing blocked isocyanate groups can be obtained as commercially available products. Specific examples thereof include TAKENATE (registered trademark) B-830, B-815N, B-842N, B-870N, B-874N, B-882N, B-7005, B-7030, B-7075, B-5010 (above, 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 (above, manufactured by Asahi Kasei Co., Ltd.), Karenz MOI-BM (registered trademark) (above, manufactured by Showa Denko Co., Ltd.), TRIXENE (registered trademark) BI7950, same as 7951, same as 7960, Same as 7961, same as 7982, same as 7990, same as 7991, same as 7992 (above, manufactured by Baxenden Chemical Co., Ltd.), etc.

The aminoplast compound is not particularly limited as long as it has two or more methoxymethylene groups in one molecule. For example, hexamethoxymethylmelamine CYMEL (registered trademark) 303, Tetra Butoxymethyl glycoluril is the same as 1170, tetramethoxymethylbenzoguanamine is the same as 1123 (above, manufactured by Japan Cytec Industrial Co., Ltd.), etc. CYMEL series, Nikalac (registered trademark) MW- of methylated melamine resin 30HM, same MW-390, same MW-100LM, same MX-750LM, same MX-270, same MX-280, same MX-290 of methylated urea resin Series and other melamine compounds. The oxetane compound is not particularly limited as long as it has two or more oxetanyl groups in one molecule, and examples include OXT-221 and OX-SQ-H containing oxetanyl groups. , OX-SC (above, manufactured by Toagosei Co., Ltd.), etc.

The phenolic plastic compound has two or more hydroxymethylene groups in one molecule, and when exposed to high temperature during thermosetting, it interacts with the phenolic hydroxyl group of the triazine ring-containing polymer of the present invention through a dehydration condensation reaction. joint responders. Examples of phenoplast compounds include 2,6-dihydroxymethyl-4-methylphenol, 2,4-dihydroxymethyl-6-methylphenol, bis(2-hydroxy-3-hydroxymethylphenol) -5-methylphenyl)methane, bis(4-hydroxy-3-hydroxymethyl-5-methylphenyl)methane, 2,2-bis(4-hydroxy-3,5-dihydroxymethylbenzene yl) 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. Bakelite compounds can be obtained as commercially available products, and specific examples thereof include 26DMPC, 46DMOC, DM-BIPC-F, DM-BIOC-F, TM-BIP-A, BISA-F, BI25X-DF, BI25X -TPA (above, manufactured by Asahi Organic Materials Co., Ltd.), etc.

Among these, polyfunctional (meth)acrylic compounds are preferable from the viewpoint of suppressing the decrease in the refractive index caused by the blending of the crosslinking agent and rapidly advancing the curing reaction. From the viewpoint of dipentaerythritol hexaacrylate and its EO adduct are preferred. As such a polyfunctional (meth)acrylic compound, NK ESTER A-DPH, Tong A-DPH-12E (all are Shin-Nakamura Chemical Co., Ltd. make), etc. are mentioned, for example.

These crosslinking agents may be used alone or in combination of two or more. The content of the cross-linking agent in the pattern-forming composition is preferably 1 to 200 parts by mass relative to 100 parts by mass of the triazine ring-containing polymer, and the lower limit is preferably 2 parts by mass if solvent resistance is considered, and more preferably It is preferably 5 parts by mass, and further, considering the control of the refractive index and the residue of the unexposed part, the upper limit is preferably 150 parts by mass, more preferably 100 parts by mass, and still more preferably 90 parts by mass.

＜Inorganic fine particles＞ The pattern-forming composition of the present invention preferably contains inorganic fine particles. By making the pattern-forming composition contain inorganic fine particles, a pattern with a higher refractive index can be obtained.

The inorganic fine particles preferably have an alkali-reactive group on the surface. Inorganic microparticles have an alkali-reactive group on the surface, so that when the unexposed part of the patterned film obtained from the pattern-forming composition is developed with an alkali developing solution, the inorganic microparticles in the unexposed part become easily compatible with three Other components such as oxazine ring polymer and cross-linking agent are removed by alkaline developer. As a result, even if inorganic fine particles are contained, the patterning properties are good.

Inorganic microparticles having alkali-reactive groups on the surface (hereinafter also referred to as "surface-modified inorganic microparticles") are obtained by, for example, using unmodified inorganic microparticles as core particles and modifying the core with an organosilicon compound having alkali-reactive groups. obtained from the surface of the particle. The organosilicon compound has a hydrolyzable group that generates a Si—OH group by hydrolysis. As a hydrolyzable group, the alkoxy group bonded to a silicon atom, the acetyloxy group bonded to a silicon atom, etc. are mentioned, for example. The number of hydrolyzable groups in the organosilicon compound is not particularly limited, and examples include 1 to 3 groups.

As an alkali reactive group, an acid anhydride group, an epoxy group, a phenol group etc. are mentioned, for example. Examples of organosilicon compounds having acid anhydride groups include 3-trimethoxysilylpropyl succinic anhydride, 3-triethoxysilylpropyl succinic anhydride, 3-dimethylmethoxysilylpropyl Succinic anhydride, succinic anhydride such as 3-dimethylethoxysilylpropyl succinic anhydride, 3-trimethoxysilylpropylcyclohexyl dicarboxylic anhydride, 3-triethoxysilylpropylcyclohexyl Dicarboxylic acid anhydride, 3-dimethylmethoxysilylpropylcyclohexyldicarboxylic anhydride, 3-dimethylethoxysilylpropylcyclohexyldicarboxylic anhydride and other dicarboxylic anhydrides, 3-trimethoxy Silylpropyl phthalic anhydride, 3-triethoxysilylpropyl phthalic anhydride, 3-dimethylmethoxysilylpropyl phthalic anhydride, 3-dimethyl Alkoxysilyl group-containing alkyl carboxylic acid anhydrides such as ethoxysilylpropyl phthalic anhydride and other phthalic anhydrides. Examples of the organosilicon compound having an epoxy group include 3-glycidoxypropyltrimethoxysilane and the like.

There is no particular limitation on the bond amount of the organosilicon compound on the surface of the core particle, but it is preferably 0.1-30% by mass, more preferably 1-15% by mass relative to the core particle.

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

For example, surface-modified inorganic microparticles can be added by adding an organosilicon compound in a predetermined amount to the aqueous dispersion of the core particles or a hydrophilic organic solvent dispersion, and using a catalyst such as dilute hydrochloric acid to hydrolyze the organosilicon compound and bond it to the core particles. obtained from the surface.

The above aqueous dispersion of core particles or dispersion in a hydrophilic organic solvent may be further substituted with a hydrophobic organic solvent. This substitution method can be performed by a common method such as a distillation method or an ultrafiltration method. Examples of the hydrophobic solvent include ketones such as methyl ethyl ketone and methyl isobutyl ketone, cyclic ketones such as cyclopentanone and cyclohexanone, and esters such as ethyl acetate and butyl acetate.

The organic solvent dispersion of the aforementioned core particles may contain optional components. In particular, by containing phosphoric acid, phosphoric acid derivatives, phosphoric acid-based surfactants, oxycarboxylic acid, 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 phosphoric acid-based surfactants include Disperbyk (manufactured by BYK-Chemie), PHOSPHANOL (manufactured by Toho Chemical Industry Co., Ltd.), and NIKKOL (manufactured by Nikko Chemical Co., Ltd.). Examples of the hydroxycarboxylic acid include lactic acid, tartaric acid, citric acid, gluconic acid, malic acid and glycolic acid. The content of these optional components is preferably about 30% by mass or less with respect to the total metal oxides in the above-mentioned core particles.

Considering the dispersion stability, the concentration of the organic solvent dispersion of the core particles is preferably 10-60% by mass, more preferably 30-50% by mass.

The inorganic fine particles that become the core particles of the surface-modified inorganic fine particles include, for example, those selected from Be, Al, Si, Ti, V, Fe, Cu, Zn, Y, Zr, Nb, Mo, In, Sn, Sb, Ta, W, One or more metal oxides, sulfides, or nitrides of the group consisting of Pb, Bi, and Ce, particularly preferably metal oxides containing these. In addition, the inorganic fine particles may be used alone or 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. Moreover, it is also effective to use multiple metal oxides as a composite oxide. The composite oxide means a mixture of two or more inorganic oxides in the production stage of fine particles. For example, the composite oxide of _TiO2 and _ZrO2 , the composite oxide of _TiO2 and _ZrO2 and _SnO2 , the composite oxide of _ZrO2 and _SnO2 etc. are mentioned. Furthermore, compounds of the above-mentioned metals may also be used. For example, _ZnSb2O6 , _BaTiO3 , _SrTiO3 , _SrSnO3 etc. are mentioned _. 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.

Also, the inorganic fine particles that become the core particles of the surface-modified inorganic fine particles may be, for example, third metal oxide 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, treatment with a hydrogen ion exchange resin selected from Ti, Fe, Cu, Zn, Y, Zr, Nb, Mo, In, Sn, Sb, Ta, W, Pb, Bi, and Ce A method of treating an acid salt of at least one metal in the group, 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, it is possible to decompose the gel obtained by neutralizing the acid salts of the above metals with alkalis or the basic salts of the metals with acids, and then decomposing them with acids or alkalis. glue method. Examples of the hydrolysis method include a method of hydrolyzing an alkoxide of the above-mentioned metal, or a method of removing an unnecessary acid after hydrolyzing a basic salt of the above-mentioned metal under heating. As an example of the reaction method, the method of making the powder of the said metal react with an acid is mentioned.

The first metal oxide particle (A) is preferably a metal oxide having an atomic valence of 2 to 6, more preferably selected from Ti, Fe, Cu, Zn, Y, Zr, Nb, Mo, In, Sn, Sb, Ta , W, Pb, Bi, Ba, Al, Sr, Hf and Ce at least one metal oxide group. Examples of the form of the metal oxide include TiO ₂ , Fe ₂ O ₃ , CuO, ZnO, Y ₂ O ₃ , ZrO ₂ , Nb ₂ O ₅ , MoO ₃ , In ₂ O ₃ , SnO ₂ , Sb ₂ O _5. Ta ₂ O ₅ , WO ₃ , PbO, Bi ₂ O ₃ , BaO, Al ₂ O ₃ , SrO, HfO ₂ , CeO ₂ , etc. These metal oxides may be used alone or in combination of two or more. As a method of combining the above-mentioned metal oxides, for example, a method of mixing a plurality of the above-mentioned metal oxides, a method of compositing the above-mentioned metal oxides, or a method of forming the above-mentioned metal oxides into a solid solution at the atomic level may be mentioned.

Examples of combinations of the above-mentioned metal oxides include 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. The composite SnO ₂ -WO ₃ composite particles, SnO ₂ particles and ZrO ₂ particles are chemically bonded at the interface and the composite SnO ₂ -ZrO ₂ composite particles, TiO ₂ and ZrO ₂ and SnO ₂ form solid particles at the atomic level. TiO ₂ -ZrO ₂ -SnO ₂ composite particles obtained from solution.

In addition, the first metal oxide particle (A) can be used as a compound by combining metal components, for example, 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 particle (A) contains TiO ₂ , TiO ₂ contained in the particle may have anatase type, rutile type, anatase-rutile mixed type, brookite Any crystal structure of the mineral type, among these, it is preferable to include the rutile type in consideration of the refractive index and transparency of the obtained thin film.

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

From the viewpoint of dispersion stability, refractive index and transparency of the obtained film, the primary particle size (observed by a transmission electron microscope) of the first metal oxide particle (A) is preferably 2 to 60 nm, More preferably, it is 2-30 nm, and most preferably, it is 2-20 nm. From the viewpoint of dispersion stability, the refractive index of the obtained film, and transparency, the dynamic light scattering method particle size (using the dynamic light scattering method), which is the secondary particle size of the first metal oxide particle (A), Preferably it is 5-100nm, more preferably 5-50nm, particularly preferably 5-30nm.

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

The second metal oxide particles (B) are preferably at least one metal oxide particle selected from the group consisting of Si, Al, Sn, Zr, Mo, Sb, and W. As the form of the second metal oxide particle (B), SiO ₂ , Al ₂ O ₃ , SnO ₂ , ZrO ₂ , MoO ₃ , Sb ₂ O ₅ , WO ₃ and the like can be illustrated, for example. Next, these metal oxides may be used alone or in combination of two or more. As a method of combining the above-mentioned metal oxides, for example, a method of mixing a plurality 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 may be mentioned.

Specific examples of the second metal oxide particles (B) include SnO ₂ -WO ₃ composite particles, SnO ₂ particles and SiO ₂ particles that are chemically bonded at the interface of SnO ₂ particles and WO ₃ particles. SnO ₂ -SiO ₂ composite particles formed by chemical bonding at the interface, SnO ₂ -WO ₃ -SiO 2 composite particles formed by chemical bonding _at the interface of SnO ₂ particles, WO ₃ particles and SiO ₂ particles, SnO ₂ -MoO ₃ -SiO ₂ composite particles chemically bonded at the interface between SnO ₂ particles and MoO ₃ particles and SiO ₂ particles, Sb ₂ O ₅ particles and SiO ₂ particles chemically bonded at the interface and composited Sb ₂ O ₅ -SiO ₂ composite particles, etc.

When using multiple metal oxides as the second metal oxide particles (B), the ratio (mass ratio) of the metal oxides contained is not particularly limited. For example, in SnO ₂ -SiO ₂ composite particles, SiO ₂ /SnO The mass ratio of 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 or an oxidation method. As an example of the ion exchange method, a method of treating acid salts of the above-mentioned metals with a hydrogen form ion exchange resin is mentioned. 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.

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

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 manufacturing method, the following 1st method and 2nd method are mentioned, for example.

The first method is to mix the aqueous dispersion containing the first metal oxide particles (A) and the aqueous dispersion containing the second metal oxide particles (B) at a mass ratio shown in (B)/(A) ( A method of heating the aqueous dispersion after mixing so that the metal oxide conversion value) becomes 0.05 to 0.5. For example, an aqueous dispersion containing the first metal oxide particles (A), and composite particles containing Sb ₂ O ₅ -SiO ₂ (Sb ₂ O ₅ /SiO ₂ =0.1 The aqueous dispersion of ~5) is mixed so that the above-mentioned mass ratio becomes 0.05 to 0.5, and the aqueous dispersion obtained by mixing is heated at 70 to 350°C to obtain the first metal oxide particle (A) An aqueous dispersion of third metal oxide particles (C) whose surfaces are coated with Sb ₂ O ₅ -SiO ₂ composite particles.

The second method is to mix the aqueous dispersion containing the first metal oxide particle (A) with the water-soluble alkali salt of tin oxide and alkali salt of silicon oxide as the second metal oxide particle (B) in the form of SnO ₂ /SiO The water dispersion of SnO ₂ -SiO ₂ composite particles obtained by performing cation exchange and removing alkali metal ions after mixing so that the mass ratio (metal oxide conversion value) shown in ₂ becomes 0.1~5, is expressed as (B)/ (A) A method of heating the aqueous dispersion obtained by mixing so that the mass ratio (metal oxide conversion value) shown in (A) becomes 0.05 to 0.5. As the aqueous solution of water-soluble alkali salt used in the second method, an aqueous solution of sodium salt can be preferably used. For example, SnO ₂ obtained by cation-exchanging an aqueous dispersion containing the first metal oxide particles (A) and an aqueous solution of sodium stannate and sodium silicate as the second metal oxide particles (B). - The aqueous dispersion of SiO ₂ composite particles is mixed so that the above-mentioned mass ratio becomes 0.05 to 0.5, and the aqueous dispersion is heated at 70 to 350° C., thereby obtaining the first metal oxide particle (A) as the nucleus and An aqueous dispersion of third metal oxide particles (C) whose surface is coated with second metal oxide particles (B) composed of SnO ₂ -SiO ₂ composite particles.

The temperature at the time of 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. In addition, the heating temperature after mixing is preferably 70-350°C, more preferably 70-150°C. Also, 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 particle (C) may contain optional components. In particular, by containing hydroxycarboxylic acids, performances such as dispersibility of the third metal oxide particles (C) can be further improved. As said hydroxycarboxylic acid, lactic acid, tartaric acid, citric acid, gluconic acid, malic acid, and glycolic acid are mentioned, for example. It is preferable that content of the said hydroxycarboxylic acid is about 30 mass % or less with respect to the whole metal oxide of a 3rd metal oxide particle (C).

Moreover, the dispersion liquid of the 3rd metal oxide particle (C) may contain an alkali component. Examples of the alkali component include alkali metal hydroxides such as Li, Na, K, Rb, and Cs; ammonia; ethylamine, isopropylamine, n-propylamine, n-butylamine, and diethylamine. , di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, triethylamine, tripropylamine, tributylamine, triisobutylamine, tripentylamine (Tri-n-pentylamine), tri-n-hexylamine, tri-n-octylamine, dimethylpropylamine, dimethylbutylamine, dimethylhexylamine and other primary, secondary and tertiary alkylamines; Aralkylamines such as benzylamine and dimethylbenzylamine; alicyclic amines such as piperidine; alkanolamines such as monoethanolamine and triethanolamine; tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrahydroxide Quaternary ammonium salts such as propyl ammonium. These may be used alone or in combination of two or more. It is preferable that content of the said alkali component is about 30 mass % or less with respect to the whole metal oxide of a 3rd metal oxide particle (C). Moreover, these alkali components can be used together with the said hydroxycarboxylic 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 this method, an evaporation method and an ultrafiltration method are mentioned, for example. Also, when the pH of the aqueous dispersion is to be adjusted, the above-mentioned alkali metal hydroxides, amines, quaternary ammonium salts, hydroxycarboxylic acids and the like may be added. The concentration of all metal oxides in the solvent dispersion of the third metal oxide particles (C) is preferably from 10 to 60% by mass, more preferably from 20 to 50% by mass.

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

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

The refractive index of the surface-modified 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 inorganic fine particles can be measured, for example, by the method of dispersing a liquid of surface-modified inorganic fine particles in a solvent or resin whose refractive index is known, measuring the refractive index with an Abbe refractometer, and extrapolating from the value , or the method of measuring the refractive index of the film or cured product containing surface-modified inorganic fine particles with an Abbe refractometer or spectroscopic ellipsometer, and extrapolating from the value.

As the content of the surface-modified inorganic fine particles in the composition, as long as it is in the range that does not impair its dispersibility in the final composition obtained, the refractive index and transmittance that are the purpose of the film to be produced can be controlled together , heat resistance, etc. For example, with respect to 100 parts by mass of the triazine ring-containing polymer, it can be added in the range of 0.1 to 1,000 parts by mass, preferably 1 to 500 parts by mass, from the viewpoint of maintaining film quality, obtaining stable refractive index and solvent resistance , more preferably 10 to 300 parts by mass.

＜Organic solvent＞ The pattern-forming composition of the present invention may contain an organic solvent. Examples of organic solvents include toluene, p-xylene, o-xylene, m-xylene, ethylbenzene, styrene, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, and ethylene glycol monomethyl ether. , propylene glycol, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol mono Ethyl ether acetate, diethylene glycol dimethyl ether, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, diethylene glycol diethyl ether, dipropylene glycol monomethyl ether, diethylene glycol Monomethyl ether, dipropylene glycol monoethyl ether, diethylene glycol monoethyl ether, triethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol, 1-octyl Alcohol, Ethylene Glycol, Hexylene Glycol, Trimethylene Glycol, 1-Methoxy-2-Butanol, Cyclohexanol, Diacetone Alcohol, Furfuryl Alcohol, Tetrahydrofurfuryl Alcohol, Propylene Glycol, Benzyl Alcohol, 1,3- Butanediol, 1,4-butanediol, 2,3-butanediol, γ-butyrolactone, acetone, methyl ethyl ketone, methyl isopropyl ketone, diethyl ketone, methyl isobutyl ketone, methyl n-butyl ketone, 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-dimethylformamide Acetamide (DMAc), N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethylsulfoxide, N-cyclohexyl-2-pyrrolidone, etc. , these may be used alone or in combination of two or more.

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 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 from 0.1 to 50% by mass, more preferably from 0.1 to 40% by mass.

＜Initiator＞ In the pattern forming composition of the present invention, an initiator corresponding to each crosslinking agent can be blended. In addition, as mentioned above, in the case of using a polyfunctional epoxy compound and/or a polyfunctional (meth)acrylic compound as a crosslinking agent, it is possible to provide a cured film by photocuring without using an initiator, but in this case use The starters are also fine.

When using a polyfunctional epoxy compound as a crosslinking agent, a photoacid generator and a photobase generator can be used. As a photoacid generator, what is necessary is just to select suitably from well-known persons and use, For example, onium salt derivatives, such as a diazonium salt, a permeicium salt, and an iodonium salt, can be used. Specific examples thereof include aryl groups such as phenyldiazonium hexafluorophosphate, 4-methoxyphenyldiazonium hexafluoroantimonate, and 4-methylphenyldiazonium hexafluorophosphate. Diazonium salts; diaryl groups such as diphenyliodonium hexafluoroantimonate, bis(4-methylphenyl)iodonium hexafluorophosphate, bis(4-tert-butylphenyl)iodonium hexafluorophosphate, etc. Odonium salt; triphenylpercited hexafluoroantimonate, ginseng (4-methoxyphenyl) percited hexafluorophosphate, diphenyl-4-thiophenoxyphenyl percited hexafluoroantimonate, diphenyl Phenyl-4-thiophenoxyphenyl percolium hexafluorophosphate, 4,4'-bis(diphenyl percolium)phenyl sulfide-bis hexafluoroantimonate, 4,4'-bis( Diphenylpermeyl)phenylsulfide-bishexafluorophosphate, 4,4'-bis[bis(β-hydroxyethoxy)phenylpermeyl]phenylsulfide-bishexafluoroantimonate, 4,4'-Bis[bis(β-hydroxyethoxy)phenylperidyl]phenylsulfide-bis-hexafluorophosphate, 4-[4'-(benzoyl)phenylthio]benzene Base-bis(4-fluorophenyl) percite hexafluoroantimonate, 4-[4'-(benzoyl)phenylthio]phenyl-bis(4-fluorophenyl) percite hexafluorophosphate, etc. Triaryl cobalt salts, etc.

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

On the other hand, as the photobase generator, it may be appropriately selected from those known in the art and used, for example, Co-amine complex type, oxime carboxylate type, urethane type, quaternary ammonium salt type, etc. Department of photobase generators and so on. 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, hexaammine cobalt (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 be used for a photobase generator, and TPS-OH, NBC-101, ANC-101 (all are a product name, the product made by Midori Kagaku Co., Ltd.) etc. are mentioned as a specific example.

When using a photoacid or base generator, it is preferable to use the range of 0.1-15 mass parts with respect to 100 mass parts of polyfunctional epoxy compounds, and the range of 1-10 mass parts is more preferable. In addition, an optional epoxy resin curing agent can be blended in an amount of 1 to 100 parts by mass with respect to 100 parts by mass of the polyfunctional epoxy compound.

On the other hand, when using a polyfunctional (meth)acryl 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, acetophenones, benzophenones, Michler's benzoyl benzoic acid can be mentioned Esters, amyl oxime esters, oxime esters, tetramethylthiuram monosulfide and thioxanthones, etc. Particularly preferred is a photocleavage type photoradical polymerization initiator. The photocleavage-type photoradical polymerization initiator is described in Latest UV Curing Technology (159 pages, publisher: Kazuhiro Takahasa, publisher: Technical Information Association Co., Ltd., 1991 issue). 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, OXE03, OXE04, 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 preferable to use the range of 0.1-200 mass parts with respect to 100 mass parts of polyfunctional (meth)acrylate compounds, and it is more preferable to use the range of 1-150 mass parts.

＜Other additives＞ In the pattern forming composition of the present invention, as long as the effect of the present invention is not impaired, other components other than the triazine ring-containing polymer, crosslinking agent and solvent may be included, such as leveling agent, surfactant, silane coupling agent, etc. Compounding agent, polymerization inhibitor, antioxidant, rust inhibitor, release agent, plasticizer, defoamer, tackifier, dispersant, antistatic agent, anti-sedimentation agent, pigment, dye, ultraviolet absorber, light stabilizer additives such as agents. Examples of surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; Polyoxyethylene alkyl allyl ethers such as octylphenol ether and polyoxyethylene nonylphenol ether; polyoxyethylene-polyoxypropylene block copolymers; sorbitan monolaurate, sorbitan monopalm Sorbitan fatty acid esters such as esters, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate; polyoxyethylene sorbitan Monolaurate, Polyoxyethylene sorbitan monopalmitate, Polyoxyethylene sorbitan monostearate, Polyoxyethylene sorbitan trioleate, Polyoxyethylene sorbitan tristearate Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters, trade names EFTOP EF301, EF303, EF352 (manufactured by Mitsubishi Materials Corporation (formerly JEMCO Co., Ltd.)), trade name MEGAFAC F171 , F173, R-08, R-30, R-40, R-41, F-114, F-410, F-430, F-444, F-477, F-552, F-553, F-554 , F-555, F-556, F-557, F-558, F-559, F-561, F-562, F-563, RS-75, RS-72-K, RS-76-E, RS -76NS, RS-77 (manufactured by DIC Co., Ltd.), Fluorad FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), trade name AsahiGuard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (AGC Co., Ltd.) and other fluorine-based surfactants, organosiloxane polymer KP341 (Shin-Etsu Chemical Co., Ltd.), BYK-302, BYK-307, BYK-322, BYK-323, BYK-330, BYK -333, BYK-370, BYK-375, BYK-378 (manufactured by BYK-Chemie JAPAN Co., Ltd.), etc.

These surfactants may be used alone or in combination of two or more. The usage-amount of the surfactant 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.

(How to make graphics and hardened products) In the pattern making method using the composition of the present invention, it can be applied to the substrate, and then heated to evaporate the solvent if necessary, and then heated or irradiated with light to form a desired cured film. When making a cured film with light irradiation, By irradiating light through a mask with a desired pattern and developing it with a developer, a fine pattern can be formed. Also, a cured product can be obtained by using the pattern-forming composition of the present invention. At this time, the coating method of the composition is optional, for example, spin coating method, dipping method, flow coating method, inkjet method, jet dispenser method, spray method, rod coating method, gravure coating method can be used , Slit coating method, roll coating method, transfer printing method, brush coating, doctor blade coating method, air knife coating method and other methods.

Furthermore, examples of substrates include silicon, glass on which indium tin oxide (ITO) is deposited, glass on which indium zinc oxide (IZO) is deposited, polyethylene terephthalate (PET), Substrates made of plastic, glass, quartz, ceramics, etc., can also use flexible substrates with flexibility. The firing temperature is not particularly limited for the purpose of evaporating the solvent, but it can be performed at, for example, 70 to 400°C. The firing time may be any time required to evaporate the solvent, for example, 1 to 600 seconds. 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. The firing temperature and firing time may be selected according to the process steps of the intended electronic device, and the firing conditions can be selected so that the physical properties of the obtained film are suitable for the characteristics required for 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 image development after exposure can be performed by immersing the exposure resin in an organic solvent developing solution or an aqueous developing solution, for example. Specific examples of organic solvent developers include PGME (propylene glycol monomethyl ether), PGMEA (propylene glycol monomethyl ether acetate), mixed solvents of PGME and PGMEA, NMP (N-methyl-2-pyrrole Pyridone), γ-butyrolactone, DMSO (dimethylsulfoxide), etc. On the other hand, as specific examples of aqueous developer solutions, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, hydrogen An aqueous alkali solution such as tetramethylammonium oxide.

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

As a photocurable catalyst, a photocation generator is mentioned. Specific examples of photocation generators include triaryl permeates such as triphenyl perme hexafluorophosphate and triphenyl perme hexafluoro antimonate; triaryl selenium salts; diphenyl perme hexafluoro phosphate, Diaryliodonium salts such as diphenyliodonium hexafluoroantimonate, etc. These may be used alone or in combination of two or more. The blending amount of the photocurable catalyst is not particularly limited, but may be about 0.1 to 100 parts by mass relative to 100 parts by mass of the triazine ring-containing polymer.

These oxirane ring-containing compounds and photocurable catalysts can be blended in any order with the components constituting the composition of the present invention. In addition, the above-mentioned organic solvents can be used at this time. After coating the composition containing these by the above-mentioned method, it can be hardened by irradiating ultraviolet light at 1 to 4000 mj/cm ² , for example. Irradiation with light may be performed by various known techniques such as high-pressure mercury lamp, metal halide lamp, xenon lamp, LED, and laser light. Moreover, it may heat at about 110-180 degreeC before and after exposure as needed. The image development after exposure can be performed by immersing the exposed resin in the above-mentioned organic solvent developing solution or aqueous developing solution.

The cured product obtained by the above method can achieve high heat resistance, high refractive index and low volume shrinkage, so it can be suitably used in liquid crystal displays, organic electroluminescent (EL) displays, touch panels, and optical semiconductor (LED) elements , solid-state imaging elements, organic thin-film solar cells, dye-sensitized solar cells, organic thin-film transistors (TFTs), lenses, thin-film cameras, binoculars, microscopes, semiconductor exposure devices, etc. material field. [Example]

Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples. In addition, each measuring device used in the examples is as follows.

[ ¹ H-NMR] Device: Bruker NMR System AVANCE III HD 500 (500 MHz) Determination solvent: deuterated dimethylsulfide (DMSO-d ₆ ) Reference substance: tetramethylsilane (TMS) (δ0.0ppm) [GPC] Apparatus: HLC-8200 GPC manufactured by TOSOH Co., Ltd. Column: TOSOH TSKgel α-3000 + TOSOH TSKgel α-4000 Column temperature: 40°C Solvent: Dimethylformamide (DMF) Detector: UV ( 271nm) Calibration line: standard polystyrene [ellipsometer] Apparatus: Multi-incident Angle Spectroscopic Ellipsometer VASE [spectrocolorimeter] manufactured by JA Woollam Japan Apparatus: CM-3700A [turbidity meter] manufactured by KONICA MINOLTA Apparatus: HAZE METER NDH 5000 [Optical Microscope] made by Nippon Denshoku Kogyo Co., Ltd. Device: OLYMPUS BX51 made by Olympus Optical Industry Co., Ltd. [Electron Microscope] Device: JSM-7400F made by JEOL Ltd. [Exposure] Device: Mask pair made by SUSS Co., Ltd. Calibrator MA6 [Developing] Device: Small developing device ADE-3000S manufactured by Actes Kyosan Co., Ltd.

[1] Synthesis of triazine ring-containing polymer [Example 1-1] Synthesis of polymer compound [4]

In a 3,000mL four-neck flask, add 2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane [2] (76.0g, 0.207mol, manufactured by Central Glass Co., Ltd.), and N- 764.5 g of methyl-2-pyrrolidone (NMP, manufactured by Kanto Chemical Co., Ltd.), after nitrogen substitution, stirred to make 2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane [ 2] Dissolve in NMP. Thereafter, it was cooled to -5°C with an ethanol-dry ice bath, and 2,4,6-trichloro-1,3,5-triazine[1] (45.0 g, 0.244 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), washed with NMP96.8g. After stirring for 30 minutes, the entire reaction vessel was moved to an oil bath set at 110 to 150°C, and the temperature of the reaction solution was raised until the internal temperature became 85°C±5°C. After stirring for 1 hour, 2-(4-aminophenyl)ethanol [3] (50.2 g, 0.366 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 106.5 g of NMP (manufactured by Kanto Chemical Co., Ltd.) was added dropwise , stirring for 3 hours. Thereafter, 2-aminoethanol (44.7 g, manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise, stirred for 30 minutes, and then the stirring was stopped. Tetrahydrofuran (THF, 591.8 g), ammonium acetate (532.6 g) and ion-exchanged water (532.6 g) were added to the reaction solution, and stirred for 30 minutes. After the stirring was stopped, the solution was transferred to a separatory funnel, the organic layer and the aqueous layer were separated and the organic layer was recovered. The recovered organic layer was dropped into a mixed liquid of methanol (1,184 g) and ion-exchanged water (2,959 g), and reprecipitated. The obtained precipitate was filtered, and it dried at 150 degreeC for 8 hours with the decompression drier, and obtained 125.9 g of the target polymer compound [4] (henceforth referred to as P-1). Compound P-1 had a weight average molecular weight Mw of 6,732 measured in terms of polystyrene by GPC, and a polydispersity Mw/Mn of 3.8. The measurement results of the ¹ H-NMR spectrum of Compound P-1 are shown in FIG. 1 .

[Example 1-2] Synthesis of polymer compound [5]

In a 300mL four-neck flask, add P-1[4] (24.60g) obtained in Example 1-1 and 92.45g of cyclopentanone (CPN, manufactured by Japan Zeon Co., Ltd.), and stir after nitrogen substitution and let it dissolve. Thereafter, the solution was heated until the inner temperature became 70° C., and 0.0025 g of N-nitrosophenylhydroxylamine aluminum salt (Q-1301, manufactured by Fujifilm Wako Pure Chemicals Co., Ltd.) and 2-isocyanatoethylamine were added dropwise. 15.02 g of acrylate-based acrylate (AOI-VM, manufactured by Showa Denko Co., Ltd.), set the internal temperature to 70°C±5°C and stirred for 1 hour to prepare a CPN solution containing 30% by mass of the polymer compound [5] (hereinafter referred to as For P-2 solution).

[2] Preparation of surface-treated inorganic fine particles The methods and measuring devices for measuring physical properties to be carried out in Production Examples 1 to 4 below are shown below. (1) Moisture content: determined by Karl Fisher titration. (2) Primary particle diameter: The dispersion liquid was dried on a copper grid, observed with a transmission electron microscope, and 100 particle diameters were measured, and the average value thereof was determined as the primary particle diameter. (3) Specific gravity: Calculated by the hydrometer method (20°C). (4) Viscosity: Calculated with an Oswald viscometer (20°C). (5) Particle diameter by dynamic light scattering method: obtained by measuring with a Zetasizer Nano manufactured by Malvern. (6) Solid content concentration: Calculated from the residual solid content when fired at 500°C. (7) Bonding amount of organosilane compound: The amount of organosilane compound bonded to the modified 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 particles (A1) Add 126.2 g of pure water to a 1-liter container, and add 17.8 g of metastannic acid (15 g in terms of SnO ₂ , manufactured by Showa Chemical Industry Co., Ltd.) under stirring. ), 284 g of titanium tetraisopropoxide (contains 80 g in terms of TiO ₂ , manufactured by Nippon Soda Co., Ltd. A-1), oxalic acid dihydrate 98 (contains 70 g in terms of oxalic acid, manufactured by Ube Industries, Ltd.), 35 mass % tetraethylammonium hydroxide aqueous solution 438g (manufactured by Sachem Japan). The molar ratio of oxalic acid/titanium atom in the obtained mixed solution 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 the pressure was further 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. Put 950 g of the above-mentioned titanium mixed solution and 950 g of pure water to 3 liters into a glass-lined autoclave container, and perform hydrothermal treatment at 140° C. for 5 hours. After cooling at room temperature, the taken out hydrothermally treated solution is a milky white water dispersion of colloidal particles containing titanium oxide. The obtained dispersion liquid had a pH of 3.9, a conductivity of 19.7 mS/cm, _a TiO concentration of 4.2% by mass, a concentration of tetraethylammonium hydroxide of 8.0% by mass, a concentration of oxalic acid of 3.7% by mass, and a dynamic light scattering particle size of 16 nm. In the transmission electron microscope observation, elliptical particles with a primary particle size of 4~10nm were observed. X-ray diffraction analysis of the powder obtained by drying the obtained dispersion liquid at 110° C. confirmed that it was a rutile crystal. The obtained titanium oxide-containing colloidal particles were used as core particles (A). Next, 70.8 g of zirconium oxychloride (containing 21.19% by mass in terms of ZrO ₂ , manufactured by Daiichi Razor Chemical Industry Co., Ltd.) was diluted with 429.2 g of pure water, and 500 g of an aqueous zirconium oxychloride solution (containing 3.0% in terms of ZrO ₂ ) was prepared separately. % by mass), 1,000 g of the dispersion liquid (water dispersion sol) of the core particle (A) was added therein under stirring. Then, hydrolysis was performed by heating at 95° C. to obtain a water dispersion 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 of the obtained water-dispersed sol was 1.2, and the concentration of all metal oxides was 20% by mass. Colloidal particles with a primary particle size of 4 to 10 nm were observed in a transmission electron microscope.

Production Example 2: Production of Second Metal Oxide Particles (B1) Dissolve 77.2 g of JIS No. 3 sodium silicate (29.8% by mass in terms of SiO ₂ , manufactured by Fuji Chemical Co., Ltd.) in 1,282 g of pure water, and then dissolve tin NaSnO ₃ ·H ₂ O (contains 55.1% by mass in terms of SnO ₂ , manufactured by Showa Chemical Industry Co., Ltd.) 20.9 g. Pass the obtained aqueous solution through a column filled with a hydrogen-type cation exchange resin (Amberlite (registered trademark) IR-120B), thereby obtaining an aqueous dispersion of acidic silica-tin(IV) oxide composite colloidal particles (B1) Sol (pH 2.4, 0.44% by mass in terms of SnO ₂ , 0.87% by mass in terms of SiO ₂ , SiO ₂ /SnO ₂ mass ratio: 2.0) 2,634 g. Next, 6.9 g of diisopropylamine was added to the obtained water dispersion sol. The obtained sol was a water-dispersed sol of alkaline silica-tin(IV) oxide composite colloidal particles (B1) (hereinafter referred to as second metal oxide particles (B1)), and had a pH of 8.0. In the water-dispersed sol, colloidal particles with a primary particle size of 4 nm or less were observed 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 while stirring. Next, the liquid was passed through a column packed with 500 ml of anion exchange resin (Amberlite (registered trademark) IRA-410, manufactured by Organo Co., Ltd.). Next, after heating the water-dispersed sol at 95° C. for 3 hours, pass the liquid to a column filled with a hydrogen-type cation exchange resin (Amberlite (registered trademark) IR-120B), and use tri-n-pentylamine to It is stabilized and concentrated by ultrafiltration membrane method to obtain silica- Water-dispersed sol of tin (IV) oxide composite oxide-coated colloidal particles (C1) containing titanium oxide (hereinafter referred to as third metal oxide particles (C1)). 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 methanol dispersion sol has a total metal oxide concentration of 30.0% by mass, a viscosity of 1.5mPa·s, a particle diameter of 18nm obtained by the dynamic light scattering method, and a water content of 1.0% by mass.

Production Example 4: Production of Surface Modified Inorganic Microparticles (D1) 3-Glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM- 403) 12.6 g, heated under reflux at 70° C. for 5 hours. A methanol dispersion of surface-modified inorganic fine particles (D1) (hereinafter, surface-modified inorganic fine particles (D1)) in which 3-glycidoxypropyltrimethoxysilane was bonded to the surface was obtained. Next, methanol was distilled off while adding propylene glycol monomethyl ether at 80 Torr using an evaporator to replace methanol with propylene glycol monomethyl ether to obtain 530 g of a propylene glycol monomethyl ether dispersion of surface-modified inorganic fine particles (D1). The obtained dispersion (hereinafter referred to as D-1 solution) had a specific gravity of 1.210, a viscosity of 3.8 mPa·s, a concentration of all metal oxides of 30.3% by mass, and a primary particle size of 4 ~10nm, the particle size of dynamic light scattering method is 15nm. In the obtained surface-modified inorganic fine particles (D1), the 3-glycidyl oxide bonded to the surface of the third metal oxide particle (C1) relative to the entire metal oxide of the third metal oxide particle (C1) 4.7% by mass of propyltrimethoxysilane.

[2] Preparation of composition for pattern formation and fabrication of patterns [Example 2-1] 10.031 A-DPH-12E (manufactured by Shin-Nakamura Chemical Co., Ltd.) blended with the P-2 solution (6.799 g) obtained in Example 1-2, and an 80% by mass propylene glycol monomethyl ether (PGME) solution as a crosslinking agent g. 10.031 g of 30.3 mass % D-1 solution as inorganic microparticles, 0.612 g of OXE-04 (manufactured by BASF Corporation) as 10 mass % CPN solution as photoradical generator, and 10 mass % CPN as surfactant 0.041 g of MEGAFAC R-40 (manufactured by DIC Co., Ltd.) and PGME (0.041 g) of the solution were visually confirmed to be dissolved, and a paint having a solid content of 35% by mass was prepared (hereinafter referred to as SP-1 solution).

(1) Confirmation of the physical properties of the cured film [Example 3-1] Put the SP-1 solution on a 50mm×50mm×0.7mm alkali-free glass substrate, and use a spin coater to perform 200rpm for 5 seconds and 680rpm for 30 seconds. After spin-coating and pre-drying at 100° C. for 1 minute using a hot plate, an exposure dose of 150 mJ/cm ² was irradiated with light having a wavelength of 365 nm using a mask aligner MA6 manufactured by SUSS Corporation. After UV irradiation, develop with 2.38% tetramethylammonium hydroxide (hereinafter referred to as TMAH) solution for 40 seconds, and then rinse with ultrapure water for 30 seconds. After rinsing, it was made to dry at 85 degreeC for 10 minutes using the hotplate, and the cured film was obtained. For 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 1. In addition, regarding the transmittance, the average transmittance of 400 to 800 nm was calculated.

From these results, it is known that the cured film obtained from the SP-1 solution can maintain a high refractive index even after washing with an alkaline aqueous solution, and has the excellent effect of maintaining a high transmittance and a low HAZE value.

[Solvent resistance (crack resistance) test] [Example 4-1] Using the SP-1 solution obtained in Example 2-1, a cured film (hereinafter referred to as NP-1 film) was obtained in the same manner as in Example 3-1. The alkali-free glass substrate with the cured film produced above was set in the spin coater, and 1 mL of propylene glycol monomethyl ether (PGME) was applied. Next, the cured film was exposed to the solvent by rotating at 50 rpm for 60 seconds so as not to scatter the liquid from the substrate. Thereafter, it was spun at 1,000 rpm for 30 seconds to remove the solvent from the substrate. Finally, after drying at 85° C. for 10 seconds using a hot plate, the measurement of the refractive index and the film thickness, the calculation of the residual film rate, and the observation of the film surface with an optical microscope were performed. The remaining film rate is calculated by the following formula. Residual film rate (%)=[(film thickness after solvent exposure)÷(film thickness before solvent exposure)]×100

[Example 4-2] Except that the solvent to be coated was changed to propylene glycol monomethyl ether acetate (PGMEA), the preparation of the cured film and the solvent resistance test were performed in the same manner as in Example 4-1.

[Example 4-3] Except that the solvent to be coated was changed to cyclopentanone (CPN), the preparation of the cured film and the solvent resistance test were performed in the same manner as in Example 4-1.

The film thickness measurement results of Examples 4-1 to 4-3 are shown in Table 2, and the photomicrographs of the surface of the cured film after solvent exposure are shown in Figures 2 to 4.

From these results, it was found that the cured film obtained from the SP-1 solution not only did not suffer from film damage but also did not observe cracking, thus maintaining high solvent resistance.

(2) Fabrication of patterned film [Example 5-1] Put the SP-1 solution prepared in Example 2-1 on an alkali-free glass substrate of 50mm x 50mm x 0.7mm with a spin coater Spin coating at 200rpm for 5 seconds and 300rpm for 30 seconds. After pre-drying on a hot plate at 85°C for 10 minutes, use a mask aligner MA6 made by SUSS to set a circle with a diameter of 10 μm at an interval of 10 μm. A mask corresponding to the space (ultraviolet shielding portion) between the opening and the remainder other than the opening was placed on the coating film, and an exposure amount of 150 mJ/cm ² was irradiated with light of a wavelength of 365 nm. After UV irradiation, develop with 2.38% TMAH solution for 40 seconds, and rinse with ultrapure water for 30 seconds. After rinsing, it was dried at 85° C. for 10 minutes using a hot plate to obtain a patterned film. Optical micrographs and electron micrographs of the obtained patterned film are shown in FIGS. 5 and 6 .

[Example 6-1] Except that the mask used was changed to a mask called a line and a space (Line and Space) with a width of 30 μm of a linear opening portion and a width of 30 μm of a linear gap (ultraviolet shielding portion), in the same manner as in Example 5- 1 In the same manner, a patterned film was obtained. The optical micrographs and electron micrographs of the obtained patterned film are shown in FIGS. 7 and 8 .

From these results, it is known that the cured film obtained from the SP-1 solution has excellent patterning properties.

[ Fig. 1 ] ¹ H-NMR spectrum chart of compound P-1 (polymer compound [4]) obtained in Example 1-1. [ Fig. 2 ] An optical micrograph of the surface after the solvent exposure of the cured film in Example 4-1 was observed. [ Fig. 3 ] An optical micrograph of the surface after the solvent exposure of the cured film in Example 4-2 was observed. [ Fig. 4 ] An optical micrograph of the surface after the solvent exposure of the cured film in Example 4-3 was observed. [ Fig. 5 ] An optical micrograph of the patterned film produced in Example 5-1. [ Fig. 6 ] An electron micrograph of the patterned film produced in Example 5-1. [ Fig. 7 ] An optical micrograph of the patterned film produced in Example 6-1. [ Fig. 8 ] An electron micrograph of the patterned film produced in Example 6-1.

Claims (23)

A triazine ring-containing polymer characterized by comprising a repeating unit structure represented by the following formula (1), and having at least one triazine ring terminal, at least a part of the triazine ring terminal being covered with an amine having a crosslinking group base closed,

(In formula (1), R and R' independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or an aralkyl group, Ar represents a divalent group having a phenolic hydroxyl group, and * represents a bond). The triazine ring-containing polymer as claimed in item 1, wherein Ar in the aforementioned formula (1) represents at least one selected from the group shown in formulas (2) to (13),

[In formulas (2) to (13), R ¹ to R ⁹² independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, a sulfo group, an alkyl group with 1 to 10 carbons, and a halogenated group with 1 to 10 carbons. An alkyl group 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 independently represent a hydrogen atom, an alkyl group with 1 to 10 carbons (but these can 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, an alkyl group with 1 to 10 carbons or a phenyl group), X ¹ and X ² independently represent a single bond, an alkylene group with 1 to 10 carbons or the formula (14 ) as shown in the base,

(In formula (14), R ⁹⁸ to R ¹⁰¹ independently represent a hydrogen atom, a halogen atom, a hydroxyl group, 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 carbon An alkoxy group with a number of 1 to 10, Y1 ^{and Y2} independently represent a single bond or an alkylene group with a carbon number of 1 to 10) However, each of the formulas (2) to (13) has at least one phenolic hydroxyl group, ＊ means a bonding key]. The triazine ring-containing polymer as claimed in claim 1, wherein the aforementioned amino group with a crosslinking group is represented by formula (15),

(In the formula (15), R ¹⁰² represents a crosslinking group, and * represents a bonding bond). The triazine ring-containing polymer as claimed in claim 3, wherein the aforementioned amino group with a crosslinking group is represented by formula (16),

(In the formula (16), R ¹⁰² represents the same meaning as above, and * represents a bonding bond). The triazine ring-containing polymer as claimed in claim 3, wherein the aforementioned R ¹⁰² is a hydroxyl-containing group or a (meth)acryloyl-containing group. As the triazine ring-containing polymer of claim 5, wherein the aforementioned R ¹⁰² is a hydroxyalkyl group, a (meth)acryloxyalkyl group or a group represented by the following formula (i),

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

A ³ represents an aliphatic hydrocarbon group with a valence of (a+1) which may 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). As the triazine ring-containing polymer of claim 6, wherein the aforementioned R ¹⁰² is selected from hydroxymethyl, 2-hydroxyethyl, (meth)acryloxymethyl, (meth)acryloxyethyl , and the base represented by the following formula (i-2) ~ formula (i-5),

(In formula (i-2) to formula (i-5), * represents a bonding bond). The triazine ring-containing polymer according to claim 1, wherein Ar in the aforementioned formula (1) has a halogenated alkyl group. The triazine ring-containing polymer as claimed in item 1, wherein Ar in the aforementioned formula (1) is represented by formula (5A),

(In the formula (5A), * represents a bonding bond). The triazine ring-containing polymer as claimed in item 9, wherein Ar in the aforementioned formula (1) is represented by formula (5B),

(In the formula (5B), * represents a bonding bond). A pattern-forming composition comprising the triazine ring-containing polymer according to any one of claims 1-10. The pattern-forming composition according to claim 11, further comprising an organic solvent. The pattern-forming composition according to claim 12, wherein the organic solvent includes at least one selected from glycol ester solvents, ketone solvents, and ester solvents. The pattern-forming composition according to claim 11, further comprising a crosslinking agent. The pattern-forming composition according to claim 14, wherein the crosslinking agent is a polyfunctional (meth)acrylic compound. The pattern-forming composition according to claim 11, further comprising inorganic fine particles. The pattern-forming composition according to claim 16, wherein the aforementioned inorganic fine particles have alkali-reactive groups on the surface. The pattern-forming composition according to Claim 11, which is used for the light extraction layer of an organic electroluminescent device. A cured product made of the pattern-forming composition according to claim 11. An electronic device comprising a base material and the cured product according to claim 19 formed on the base material. As the electronic device of claim 20, it is an organic electroluminescence. An optical member comprising a base material and the hardened product according to claim 19 formed on the base material. A method for making a pattern, characterized in that the pattern-forming composition according to claim 11 is coated on a substrate, the organic solvent is evaporated, light is irradiated through a mask formed with a pattern, and then developed and further fired.

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