Triazine ring-containing polymer and pattern-forming composition

Abstract

The present invention provides a pattern-forming composition from which it is possible to obtain a film having a high refractive index, excellent weather resistance, and good pattern formability. The present invention pertains to a triazine ring-containing polymer that includes a repeating unit structure represented by formula (1), that has one or more triazine ring terminals, and in which a group having an arylamino group is bonded to at least a portion of the triazine ring terminals.

Description

Triazine Ring-Containing Polymer and Composition for Pattern Formation

[0001] The present invention relates to a novel triazine ring-containing polymer and a composition for pattern formation. More specifically, it relates to a triazine ring-containing polymer having a specific chemical structure and a composition for pattern formation containing the triazine ring-containing polymer.

[0002] In recent years, when developing electronic devices such as liquid crystal displays, organic electroluminescence (EL) displays, touch panels, optical semiconductor (light-emitting diodes (LED), etc.) elements, solid-state imaging devices, organic thin-film solar cells, dye-sensitized solar cells, and organic thin-film transistors (TFTs), high-functional polymer materials have been increasingly required. Specific properties required for polymer materials include 1) heat resistance, 2) transparency, 3) high refractive index, 4) high solubility, 5) low volume shrinkage rate, 6) high temperature and high humidity resistance, 7) high film hardness, etc. In view of this, the present applicant has already found that a polymer containing a repeating unit having a triazine ring and an aromatic ring has a high refractive index, and can achieve high heat resistance, high transparency, high refractive index, high solubility, and low volume shrinkage by itself, and is suitable as a composition for film formation when manufacturing electronic devices (Patent Document 1).

[0003] By the way, organic electroluminescence displays generally have a problem that the light extraction efficiency, that is, the efficiency of the generated light coming out of the device to the outside is low. As a light extraction method for solving this problem, various conventional technologies have been developed. As one of them, in order to eliminate the refractive index difference between layers, which is one of the causes of light loss before it comes out to the outside, a technique using a high refractive index layer or a high refractive index pattern is known. Many negative-type photosensitive compositions have been proposed for this high refractive index pattern, and the present applicant has also reported various materials capable of forming a negative-type high refractive index pattern (see Patent Documents 2 to 5).

[0004] International Publication No. 2010 / 128661 International Publication No. 2016 / 024613 International Publication No. 2016 / 114337 International Publication No. 2019 / 093203 International Publication No. 2022 / 225014

[0005] In the pattern of the prior art proposed above, a good pattern-forming property with a high refractive index has been reported. However, further improvement in weather resistance has been demanded for the existing technology patterns.

[0006] That is, an object of the present invention is to provide a triazine-ring-containing polymer and a pattern-forming composition containing the triazine-ring-containing polymer, which can obtain a pattern having a high refractive index, excellent weather resistance, and good pattern-forming properties.

[0007] As a result of intensive studies to solve the above problems, the inventors of the present invention have found that by using a pattern-forming composition containing a triazine-ring-containing polymer having a specific chemical structure, the obtained film has a high refractive index and excellent weather resistance, and the pattern-forming property is good, thus completing the present invention.

[0008] That is, the present invention and its various aspects are as follows [1] to [8]. However, the present invention is not limited thereto. [1] A triazine-ring-containing polymer containing a repeating unit structure represented by the following formula (1), having at least one triazine-ring terminal, and a group having an arylamino group bonded to at least a part of the triazine-ring terminal. (In formula (1), R １ ~R ８ independently represent a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and R and R' independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group, and * represents a bond.) [2] The triazine-ring-containing polymer according to [1] above, wherein the group having an arylamino group is represented by the following formula (2). (In formula (2), R ９ represents a substituent or a crosslinking group, n is an integer of 1 to 5, and * represents a bond.) [3] The R ９ is a hydroxyalkyl group, a (meth)acryloyloxyalkyl group, -OC(A ６ ) ３ (A ６It represents F, Cl, Br or I.) and a group selected from groups represented by the following formula (3), the triazine ring-containing polymer according to the above [2]. (In the formula, A １ represents an alkylene group having 1 to 10 carbon atoms, and A ２ represents a single bond or the following formula (4) represents a group represented by, and A ３ represents a single bond, -C ｂ H ２ｂ -O-C ｃ H ２ｃ -(b and c are each independently an integer from 0 to 5), or represents a polyvalent aliphatic hydrocarbon group which may be substituted with a hydroxy group, and A ４ represents a single bond or an alkylene group having 1 to 5 carbon atoms, and A ５ represents a hydrogen atom or a methyl group, a represents 1 or 2, and * represents a bond. ) [4] wherein n is 1 or 2, and the R ９ is a hydroxymethyl group, 2-hydroxyethyl group, (meth)acryloyloxymethyl group, (meth)acryloyloxyethyl group, -OCF ３ and a group selected from groups represented by the following formula (3-1) to formula (3-8), the triazine ring-containing polymer according to the above [3]. (In the formula, * represents a bond.) [5] A pattern-forming composition containing the triazine ring-containing polymer according to any one of the above [1] to [4], a crosslinking agent, a photo radical polymerization initiator, a silane coupling agent, and a solvent. [6] The pattern-forming composition according to the above [5], wherein the content of the triazine ring-containing polymer in the pattern-forming composition is 10 to 30% by weight. [7] The pattern-forming composition according to the above [5], wherein the crosslinking agent is a polyfunctional (meth)acrylate-based compound. [8] The pattern-forming composition according to the above [5], wherein the silane coupling agent is an amino-based silane coupling agent, an epoxy-based silane coupling agent, a vinyl-based silane coupling agent, a methacryl-based silane coupling agent, or an acid anhydride-based silane coupling agent.

[0009] According to the present invention, it is possible to provide a pattern-forming composition in which the resulting film has a high refractive index and excellent weather resistance, as well as good pattern-forming properties.

[0010] Compound P-1 １ This is the 1H-NMR spectrum of compound P-2. １ This is the 1H-NMR spectrum diagram. This is an optical microscope image of the patterned film (L / S = 5 μm) obtained in Example 2-1. This is an optical microscope image of the patterned film (L / S = 5 μm) obtained in Example 2-2. This is an optical microscope image of the patterned film (L / S = 5 μm) obtained in Example 2-3. This is an optical microscope image of the patterned film (L / S = 5 μm) obtained in Example 2-4. This is an optical microscope image of the patterned film (L / S = 5 μm) obtained in Example 2-5. This is an optical microscope image of the patterned film (L / S = 5 μm) obtained in Example 2-6. This is an optical microscope image of the patterned film (L / S = 5 μm) obtained in Example 2-7. This is an optical microscope image of the patterned film (L / S = 5 μm) obtained in Example 2-8. This is an optical microscope image of the patterned film (L / S = 5 μm) obtained in Example 2-9. This is an optical microscope image of the patterned film (L / S = 5 μm) obtained in Example 2-10. This is an optical microscope image of the patterned film (L / S = 5 μm) obtained in Example 2-11. This is an optical microscope image of the patterned film (L / S = 5 μm) obtained in Example 2-12. This is an optical microscope image of the patterned film (L / S = 5 μm) obtained in Example 2-13. This is an optical microscope image of the patterned film (L / S = 5 μm) obtained in Example 2-14. This is an optical microscope image of the patterned film (L / S = 5 μm) obtained in Example 2-15. This is an optical microscope image of the patterned film (L / S = 5 μm) obtained in Example 2-16. This is an optical microscope image of the patterned film (L / S = 5 μm) obtained in Example 2-17. This is an optical microscope image of the patterned film (L / S = 5 μm) obtained in Example 2-18.

[0011] <Triadine Ring-Containing Polymer> The triazine ring-containing polymer of the present invention contains a repeating unit structure represented by the following formula (1), and has at least one triazine ring terminus, with at least a portion of this triazine ring terminus having a group having an arylamino group attached. (In formula (1), R １ ~R ８ R and R' independently represent a hydrogen atom, halogen atom, carboxyl group, sulfo group, C1-C10 alkyl group, C1-C10 halogenated alkyl group, or C1-C10 alkoxy group; R and R' independently represent a hydrogen atom, alkyl group, alkoxy group, aryl group, or aralkyl group; and * represents a bond. By using the triazine ring-containing polymer of the present invention, it is possible to provide a pattern-forming composition in which the resulting film has a high refractive index and excellent weather resistance, as well as good pattern-forming properties. The refractive index measured according to the method of this embodiment can be evaluated as high refractive index if it is 1.60 or higher. In addition, the degree of yellowing ΔYI calculated according to the method of this embodiment can be evaluated as high weather resistance if it is 2.0 or lower.

[0012] The triazine ring-containing polymer may be linear or branched. The triazine ring-containing polymer may contain one type of repeating unit structure represented by formula (1) or two or more types. Furthermore, in parts of the triazine ring-containing polymer other than the terminals, the bonds on the triazine ring of one repeating unit structure of formula (1) may be linked to the bonds on the triazine ring of the other repeating unit structure of formula (1) via a group obtained by a crosslinking reaction of a crosslinking group. In this case, examples of crosslinking groups include the groups represented by formulas (3), (3-1) to (3-8) above, and groups obtained by a crosslinking reaction of the following crosslinking agents.

[0013] Triazine ring-containing polymers are, for example, so-called hyperbranched polymers. Hyperbranched polymers are highly branched polymers having an irregular branching structure. Irregularity here means that the branching structure is more irregular than that of dendrimers, which are highly branched polymers having an irregular branching structure. For example, a triazine ring-containing polymer that is a hyperbranched polymer contains a structure (structure X) that is larger than the repeating unit structure represented by formula (1), in which each of the three bonds of the repeating unit structure represented by formula (1) is bonded to the repeating unit structure represented by formula (1). In a triazine ring-containing polymer that is a hyperbranched polymer, structure X is distributed throughout the entire triazine ring-containing polymer except for the ends. In a triazine ring-containing polymer that is a hyperbranched polymer, the repeating unit structure may consist essentially only of the repeating unit structure represented by formula (1), or other repeating unit structures may be present in part.

[0014] The following describes each substituent that constitutes the triazine ring-containing polymer of formula (1).

[0015] <<R, and R'>> In the above formula (1), R and R' independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group. However, from the viewpoint of increasing the refractive index, it is preferable that both R and R' are hydrogen atoms. In the present invention, the number of carbon atoms in the alkyl group is not particularly limited, but 1 to 20 is preferred, and considering the further improvement of the heat resistance of the polymer, the number of carbon atoms in the alkyl group is more preferably 1 to 10, and even more preferably 1 to 3. Furthermore, the structure of the alkyl group is not particularly limited and may be linear, branched, cyclic, or any combination of two or more of these.

[0016] Specific examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, s-butyl, t-butyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclobutyl, 1,2-dimethyl-cyclopropyl, 2,3-dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl- n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl-cyclobutyl, 2,4-dimethyl-cyclobutyl Examples include ethyl-cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-isopropyl-cyclopropyl, 2-isopropyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl, and 2-ethyl-3-methyl-cyclopropyl groups.

[0017] The number of carbon atoms in the alkoxy group is not particularly limited, but 1 to 20 is preferred, and considering the need to further improve the heat resistance of the polymer, 1 to 10 carbon atoms are more preferred, and 1 to 3 carbon atoms are even more preferred. Furthermore, the structure of the alkyl portion in the alkoxy group is not particularly limited and may be linear, branched, cyclic, or a combination of two or more of these.

[0018] Specific examples of alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, s-butoxy, t-butoxy, n-pentoxy, 1-methyl-n-butoxy, 2-methyl-n-butoxy, 3-methyl-n-butoxy, 1,1-dimethyl-n-propoxy, 1,2-dimethyl-n-propoxy, 2,2-dimethyl-n-propoxy, 1-ethyl-n-propoxy, n-hexyloxy, 1-methyl-n-pentyloxy, 2-methyl-n-pentyloxy, 3-methyl-n-pentyloxy Examples include pentyloxy, 4-methyl-n-pentyloxy, 1,1-dimethyl-n-butoxy, 1,2-dimethyl-n-butoxy, 1,3-dimethyl-n-butoxy, 2,2-dimethyl-n-butoxy, 2,3-dimethyl-n-butoxy, 3,3-dimethyl-n-butoxy, 1-ethyl-n-butoxy, 2-ethyl-n-butoxy, 1,1,2-trimethyl-n-propoxy, 1,2,2-trimethyl-n-propoxy, 1-ethyl-1-methyl-n-propoxy, and 1-ethyl-2-methyl-n-propoxy groups.

[0019] The number of carbon atoms in the aryl group is not particularly limited, but 6 to 40 is preferred, and considering the need to further improve the heat resistance of the polymer, the number of carbon atoms in the aryl group is more preferably 6 to 16, and even more preferably 6 to 13. In the present invention, the aryl group includes aryl groups having substituents. Examples of substituents include halogen atoms, alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, nitro groups, cyano groups, and the like. Specific examples of aryl groups include phenyl, o-chlorophenyl, m-chlorophenyl, p-chlorophenyl, o-fluorophenyl, p-fluorophenyl, o-methoxyphenyl, p-methoxyphenyl, p-nitrophenyl, p-cyanophenyl, α-naphthyl, β-naphthyl, o-biphenylyl, m-biphenylyl, p-biphenylyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, and 9-phenanthryl groups.

[0020] The number of carbon atoms in the aralkyl group is not particularly limited, but is preferably 7 to 20. The structure of the alkyl portion in the aralkyl group is not particularly limited and may be linear, branched, cyclic, or a combination of two or more of these. In the present invention, the aralkyl group includes aralkyl groups having substituents. Examples of substituents include halogen atoms, alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, nitro groups, and cyano groups. Specific examples include benzyl, p-methylphenylmethyl, m-methylphenylmethyl, o-ethylphenylmethyl, m-ethylphenylmethyl, p-ethylphenylmethyl, 2-propylphenylmethyl, 4-isopropylphenylmethyl, 4-isobutylphenylmethyl, and α-naphthylmethyl groups.

[0021] <<R １ ~R ８ >> In the above formula (1), R １ ~R ８ These are, independently of each other, hydrogen atoms, halogen atoms (F, Cl, Br, I), carboxyl groups (COOH), and sulfo groups (SO). ３H) represents an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.

[0022] The alkyl group has 1 to 10 carbon atoms, but is preferably 1 to 7, more preferably 1 to 5, and even more preferably 1 to 3.Specific examples of alkyl groups include, for example, 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 Tyl, 3-methyl-cyclobutyl, 1,2-dimethyl-cyclopropyl, 2,3-dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl Lu-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl-cyclobutyl, 2,4-di- Examples include methyl-cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-isopropyl-cyclopropyl, 2-isopropyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl, and 2-ethyl-3-methyl-cyclopropyl groups.

[0023] A halogenated alkyl group is one in which at least one hydrogen atom in an alkyl group having 1 to 10 carbon atoms is replaced with a halogen atom. The halogenated alkyl group has 1 to 10 carbon atoms, but preferably 1 to 7, more preferably 1 to 5, and even more preferably 1 to 3. Specific examples of halogenated alkyl groups include, for example, trifluoromethyl, 2,2,2-trifluoroethyl, perfluoroethyl, 3,3,3-trifluoropropyl, 2,2,3,3,3-pentafluoropropyl, 2,2,3,3-tetrafluoropropyl, 2,2,2-trifluoro-1-(trifluoromethyl)ethyl, perfluoropropyl, 4,4,4-trifluorobutyl, 3,3,4,4,4-pentafluorobutyl, and 2,2,3,3,4,4 Examples include 4-heptafluorobutyl, perfluorobutyl, 2,2,3,3,4,4,5,5,5-nonafluoropentyl, 2,2,3,3,4,4,5,5-octafluoropentyl, perfluoropentyl, 2,2,3,3,4,4,5,5,6,6,6-undecafluorohexyl, 2,2,3,3,4,4,5,5,6,6-decafluorohexyl, 3,3,4,4,5,5,6,6,6-nonafluorohexyl, and perfluorohexyl groups. In the present invention, considering the need to improve the solubility of the triazine ring-containing polymer in low-polarity solvents, perfluoroalkyl groups having 1 to 10 carbon atoms are preferred, perfluoroalkyl groups having 1 to 5 carbon atoms are more preferred, and trifluoromethyl groups are even more preferred.

[0024] The alkoxy group has 1 to 10 carbon atoms, but preferably 1 to 7, more preferably 1 to 5, and even more preferably 1 to 3. Specific examples of alkoxy groups include, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, s-butoxy, t-butoxy, n-pentoxy, 1-methyl-n-butoxy, 2-methyl-n-butoxy, 3-methyl-n-butoxy, 1,1-dimethyl-n-propoxy, 1,2-dimethyl-n-propoxy, 2,2-dimethyl-n-propoxy, 1-ethyl-n-propoxy, n-hexyloxy, 1-methyl-n-pentyloxy, 2-methyl-n-pentyloxy, and 3-methyl-n Examples include pentyloxy, 4-methyl-n-pentyloxy, 1,1-dimethyl-n-butoxy, 1,2-dimethyl-n-butoxy, 1,3-dimethyl-n-butoxy, 2,2-dimethyl-n-butoxy, 2,3-dimethyl-n-butoxy, 3,3-dimethyl-n-butoxy, 1-ethyl-n-butoxy, 2-ethyl-n-butoxy, 1,1,2-trimethyl-n-propoxy, 1,2,2-trimethyl-n-propoxy, 1-ethyl-1-methyl-n-propoxy, and 1-ethyl-2-methyl-n-propoxy groups.

[0025] In the triazine ring-containing polymer of the present invention, at least a portion of the triazine ring terminus is bonded to a group having an arylamino group. Here, "triazine ring terminus" refers to the bond of the triazine ring represented by (i) and (ii) in the repeating unit structure that constitutes the terminal portion of the triazine ring-containing polymer, as shown in the following formula (1').

[0026] The triazine ring-containing polymer preferably has a group represented by the following formula (2) as the group having an arylamino group. (In formula (2), R ９represents a substituent or crosslinking group, n is an integer from 1 to 5, and * represents a bond. Typically, triazine ring-containing polymers are encapsulated by groups having arylamino groups. When triazine ring-containing polymers are encapsulated by groups having arylamino groups, the solubility of thin films and cured films obtained using triazine ring-containing polymers in alkaline developers can be improved. Group R when triazine ring-containing polymers are encapsulated by groups having arylamino groups ９ For example, -OC(A ６ ) ３ (A ６ ) represents F, Cl, Br, or I. ), -OH, -CH ２ CH ２ Examples include OH. ９ When the crosslinking group is the triazine ring-containing polymer, the triazine ring-containing polymer may form crosslinks via the group having the arylamino group. When the triazine ring-containing polymer forms crosslinks via the group having the arylamino group, the weather resistance of the film obtained using the triazine ring-containing polymer can be improved. Examples of crosslinking groups include groups selected from hydroxyl-containing groups, vinyl-containing groups, epoxy-containing groups, oxetane-containing groups, carboxyl-containing groups, sulfo-containing groups, thiol-containing groups, and (meth)acryloyl-containing groups.

[0027] Examples of hydroxyl-containing groups include hydroxyl groups and hydroxyalkyl groups, but hydroxyalkyl groups having 1 to 10 carbon atoms are preferred, hydroxyalkyl groups having 1 to 5 carbon atoms are more preferred, and hydroxyalkyl groups having 1 to 3 carbon atoms are even more preferred. Examples of hydroxyalkyl groups having 1 to 10 carbon atoms include hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 5-hydroxypentyl, 6-hydroxyhexyl, 7-hydroxyheptyl, 8-hydroxyoctyl, 9-hydroxynonyl, 10-hydroxydecyl, 2-hydroxy-1-methylethyl, 2-hydroxy-1,1-dimethylethyl, 3-hydroxy-1-methylpropyl, 3-hydroxy-2-methylpropyl, 3-hydroxy-1,1-dimethylpropyl, 3-hydroxy-1,2-dimethylpropyl, 3-hydroxy-2,2-dimethylpropyl, and 4-hydroxy Examples include groups such as -1-methylbutyl, 4-hydroxy-2-methylbutyl, and 4-hydroxy-3-methylbutyl, where the carbon atom to which the hydroxyl group is bonded is a primary carbon atom; and groups such as 1-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 1-hydroxybutyl, 2-hydroxybutyl, 1-hydroxyhexyl, 2-hydroxyhexyl, 1-hydroxyoctyl, 2-hydroxyoctyl, 1-hydroxydecyl, 2-hydroxydecyl, 1-hydroxy-1-methylethyl, and 2-hydroxy-2-methylpropyl, where the carbon atom to which the hydroxyl group is bonded is a secondary or tertiary carbon atom.

[0028] In particular, considering the improvement of heat resistance and resistance to high temperature and high humidity, it is preferable that the carbon atom to which the hydroxyl group is bonded is a primary carbon atom, and among these, a hydroxyalkyl group having 1 to 5 carbon atoms is more preferable, a hydroxyalkyl group having 1 to 3 carbon atoms is even more preferable, a hydroxymethyl group and a 2-hydroxyethyl group are even more preferable, and a 2-hydroxyethyl group is most preferable.

[0029] Examples of vinyl-containing groups include alkenyl groups having 2 to 10 carbon atoms and having a vinyl group at one end. Specific examples include ethenyl, 1-propenyl, allyl, isopropenyl, 1-butenyl, 2-butenyl, and 2-pentenyl groups.

[0030] Examples of epoxy-containing groups include epoxy, glycidyl, and glycidyloxy groups. Specific examples include glycidylmethyl, 2-glycidylethyl, 3-glycidylpropyl, and 4-glycidylbutyl groups.

[0031] Examples of oxetane-containing groups include oxetane-3-yl, (oxetane-3-yl)methyl, 2-(oxetane-3-yl)ethyl, 3-(oxetane-3-yl)propyl, and 4-(oxetane-3-yl)butyl groups.

[0032] Examples of carboxyl-containing groups include carboxyl groups and carboxyalkyl groups having 2 to 10 carbon atoms. Among carboxyalkyl groups having 2 to 10 carbon atoms, those to which the carboxyl group is bonded are preferably primary carbon atoms. Specific examples include carboxymethyl, 2-carboxyethyl, 3-carboxypropyl, and 4-carboxybutyl groups.

[0033] Examples of sulfo-containing groups include sulfo groups and sulfoalkyl groups having 1 to 10 carbon atoms. Among sulfoalkyl groups having 1 to 10 carbon atoms, those to which the sulfo group is bonded are preferably primary carbon atoms. Specific examples include sulfomethyl, 2-sulfoethyl, 3-sulfopropyl, and 4-sulfobutyl groups.

[0034] Examples of thiol-containing groups include thiol groups and mercaptoalkyl groups having 1 to 10 carbon atoms. Preferably, the mercaptoalkyl groups to which the thiol group is bonded are secondary carbon atoms. Specific examples include mercaptomethyl, 2-mercaptoethyl, 3-mercaptopropyl, and 4-mercaptobutyl groups.

[0035] Examples of (meth)acryloyl-containing groups include (meth)acryloyl groups, (meth)acryloyloxyalkyl groups, and groups selected from those represented by the following formula (3). (In the formula, A １ represents an alkylene group with 1 to 10 carbon atoms, A ２ is a single bond or the following formula (4) It represents a base represented by A ３ This is a single bond, -C ｂ H ２ｂ -O-C ｃ H ２ｃ - (where b and c are each independently integers from 0 to 5), or represents an aliphatic hydrocarbon group with an (a+1) valency that may be substituted with a hydroxyl group, A ４ represents a single bond or an alkylene group having 1 to 5 carbon atoms, A ５ (where represents a hydrogen atom or a methyl group, 'a' represents 1 or 2, and * represents a bonding bond.)

[0036] As the (meth)acryloyloxyalkyl group, a (meth)acryloyloxyalkyl group having an alkylene group with 1 to 10 carbon atoms is preferred. Examples of alkylene groups included in the (meth)acryloyloxyalkyl group having an alkylene group (alkanediyl group) with 1 to 10 carbon atoms include methylene, ethylene, trimethylene, propane-1,2-diyl, tetramethylene, butane-1,3-diyl, butane-1,2-diyl, 2-methylpropane-1,3-diyl, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, etc. Considering the improvement of heat resistance and resistance to high temperature and high humidity, among these, those having an alkylene group with 1 to 5 carbon atoms are preferred, those having an alkylene group with 1 to 3 carbon atoms are more preferred, and those having an alkylene group with 1 or 2 carbon atoms are even more preferred.

[0037] Specific examples of the above (meth)acryloyloxyalkyl groups include, for example, (meth)acryloyloxymethyl group, 2-(meth)acryloyloxyethyl group, 3-(meth)acryloyloxypropyl group, and 4-(meth)acryloyloxybutyl group.

[0038] In equation (3), A１ The alkylene group has 1 to 10 carbon atoms, but an alkylene group with 1 to 5 carbon atoms is preferred, and a methylene group, an ethylene group, or a propylene group is more preferred. Examples of alkylene groups with 1 to 10 carbon atoms include those similar to the alkylene groups included in the (meth)acryloyloxyalkyl groups described above.

[0039] In equation (3), A ３ Specific examples of (a+1) valent aliphatic hydrocarbon groups that may be substituted with a hydroxyl group include, for example, alkylene groups having 1 to 5 carbon atoms and the following formulas (k-1) to (k-3) (In the formula, * represents a bond.) Examples of groups represented by are, preferably alkylene groups having 1 to 5 carbon atoms, more preferably alkylene groups having 1 to 3 carbon atoms, and even more preferably methylene groups and ethylene groups. A ３ The alkylene group is the above R ９ Among the alkylene groups exemplified above, examples include alkylene groups having 1 to 5 carbon atoms.

[0040] 'a' represents either 1 or 2, but 1 is preferred.

[0041] In equation (3), A ４ Specific examples of alkylene groups having 1 to 5 carbon atoms include, for example, methylene groups and ethylene groups. ４ The alkylene group is the above R ９ Among the alkylene groups exemplified above, examples include alkylene groups having 1 to 5 carbon atoms.

[0042] R ９ This includes hydroxyalkyl groups, (meth)acryloyloxyalkyl groups, and -OC(A ６ ) ３ (A ６ ) represents F, Cl, Br, or I. ) and preferably a group selected from the group represented by the above formula (3). R ９ These groups can be used to impart solubility and crosslinking effects.

[0043] The triazine ring-containing polymer has n = 1 or 2, and R ９However, hydroxymethyl group, 2-hydroxyethyl group, (meth)acryloyloxymethyl group, (meth)acryloyloxyethyl group, -OCF ３ And it is more preferable that the group is selected from the groups represented by the following formulas (3-1) to (3-8). In a triazine ring-containing polymer, n is 1 or 2, and R ９ Because the above-mentioned group is present, the triazine ring-containing polymer can achieve excellent crosslinking strength. As a result, films obtained using the triazine ring-containing polymer can have excellent weather resistance. (In the formula, * represents a bond.)

[0044] The weight-average molecular weight of the triazine ring-containing polymer in the present invention is not particularly limited, but is preferably 500 to 500,000, more preferably 500 to 100,000, preferably 2,000 or more from the viewpoint of further improving heat resistance and lowering shrinkage rate, preferably 50,000 or less, more preferably 30,000 or less, even more preferably 25,000 or less, and still preferably 10,000 or less from the viewpoint of reducing the viscosity of the obtained composition. The weight-average molecular weight in the present invention is the average molecular weight obtained on a standard polystyrene basis by gel permeation chromatography (hereinafter referred to as GPC) analysis.

[0045] <<Method for Producing Triazine Ring-Containing Polymers>> The triazine ring-containing polymer (hyperbranched polymer) of the present invention can be produced, for example, in accordance with the method disclosed in International Publication No. 2010 / 128661.

[0046] For example, as shown in Scheme 1 below, the triazine ring-containing polymer (8) is produced by reacting a triazine compound (5) and a diamino compound (6) in a suitable organic solvent (represented by A), and then the group R ９ It can be obtained by reacting it with an arylamino compound (7) having (represented by B). (In the above formula, X represents a halogen atom independently of each other, n, R, R', and R １ ~R ９(This represents the meanings described in formulas (1) and (2) above.) In the reaction represented by A above, the charging ratio of aryldiamino compound (6) is arbitrary as long as the desired triazine ring-containing polymer is obtained, but 0.01 to 10 equivalents of aryldiamino compound (6) per 1 equivalent of triazine compound (5) is preferred, and 0.7 to 5 equivalents is more preferred. The aryldiamino compound (6) may be added neat or as a solution dissolved in an organic solvent, but the latter method is preferred considering the ease of operation and ease of controlling the reaction. The reaction temperature of the reaction represented by A above can be appropriately set within the range from the melting point of the organic solvent used to the boiling point of the solvent, but 30 to 150°C is preferred, and -10 to 100°C is more preferred.

[0047] In the reaction represented by B above, the charging ratio of the arylamino compound (7) is arbitrary as long as the desired triazine ring-containing polymer is obtained, but it is preferably 0.01 to 10 equivalents of the arylamino compound (7) per 1 equivalent of the triazine compound (5), and more preferably 1 to 3 equivalents. The reaction temperature of the reaction represented by B above can be appropriately set within the range from the melting point of the organic solvent used to the boiling point of the solvent, but it is preferably around -10 to 150°C, and more preferably 50 to 100°C.

[0048] As organic solvents used in the reactions represented by A and B above, various solvents commonly used in this type of reaction can be used, for example, amide solvents such as tetrahydrofuran, dioxane, dimethyl sulfoxide; N,N-dimethylformamide, N-methyl-2-pyrrolidone, tetramethylurea, hexamethylphosphoramide, N,N-dimethylacetamide, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, N-methyl-2-piperidone, N,N'-dimethylethyleneurea, N,N,N',N'-tetramethylmalonamide, N-methylcaprolactam, N-acetylpyrrolidine, N,N-diethylacetamide, N-ethyl-2-pyrrolidone, N,N-dimethylpropionic acid amide, N,N-dimethylisobutylamide, N-methylformamide, N,N'-dimethylpropyleneurea, and mixed solvents thereof. Among these, N,N-dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, and mixtures thereof are preferred, and in particular, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 3-methoxy-N,N-dimethylpropanamide, and 3-butoxy-N,N-dimethylpropanamide are preferred.

[0049] Furthermore, in the reaction of Scheme 1 described above, various bases commonly used during or after polymerization may be added. Specific examples of these bases include potassium carbonate, potassium hydroxide, sodium carbonate, sodium hydroxide, sodium bicarbonate, sodium ethoxide, sodium acetate, lithium carbonate, lithium hydroxide, lithium oxide, potassium acetate, magnesium oxide, calcium oxide, barium hydroxide, trilithium phosphate, trisodium phosphate, tripotassium phosphate, cesium fluoride, aluminum oxide, ammonia, n-propylamine, trimethylamine, triethylamine, diisopropylamine, diisopropylethylamine, N-methylpiperidine, 2,2,6,6-tetramethyl-N-methylpiperidine, pyridine, 4-dimethylaminopyridine, N-methylmorpholine, 2-aminoethanol, ethyldiethanolamine, and diethylaminoethanol. The amount of base added is preferably 1 to 100 equivalents, and more preferably 1 to 10 equivalents, per equivalent of the triazine compound (5). These bases may also be used in aqueous solution. Preferably, the resulting triazine ring-containing polymer (8) does not contain any residual raw material components, but some raw materials may remain as long as the effects of the present invention are not impaired. After the reaction is complete, the product can be easily purified by reprecipitation or the like.

[0050] Another embodiment is the method shown in Scheme 2 below. In this method, the triazine ring-containing polymer (12) is formed by reacting a triazine compound (5) and a diamino compound (6) in a suitable organic solvent (represented by C), and then a hydroxyalkyl group A having 1 to 10 carbon atoms. １ It can be obtained by reacting an arylamino compound (9) having ' (represented by D) with a triazine ring-containing polymer (10) (first step), and then reacting the hydroxyl group of the hydroxyalkyl group contained in the triazine ring-containing polymer (10) with an isocyanate group (meth)acrylic acid ester compound (11) (second step; represented by E). (In the formula, X represents a halogen atom independently of A) １ ' represents a hydroxyalkyl group having 1 to 10 carbon atoms, A １This represents an alkylene group with 1 to 10 carbon atoms, A ４ A represents a single bond or an alkylene group having 1 to 5 carbon atoms. ５ represents a hydrogen atom or a methyl group, and a, R, R', and R １ ~R ８ This represents the meanings described in formulas (1) and (2) above.

[0051] In Scheme 2 described above, the charging ratio, reaction temperature, addition method, organic solvent and base for the reaction represented by C between the triazine compound (5) and the diamino compound (6) in the first step, the charging ratio, reaction temperature, organic solvent and base for the reaction represented by D, and the organic solvent for the reaction represented by E can be the same as those described in Scheme 1. Furthermore, in the reaction represented by E in the second step, the charging ratio of the (meth)acrylic acid ester compound (11) having an isocyanate group to the triazine ring-containing polymer (10) is such that the hydroxyalkyl group (A １ The ratio of the (meth)acryloyl group to the isocyanate group can be arbitrarily set, and is preferably 0.1 to 10 equivalents, more preferably 0.5 to 5 equivalents, even more preferably 0.7 to 3 equivalents, and still more preferably 0.9 to 1.5 equivalents per equivalent of the arylamino compound (9) having a hydroxyalkyl group used. The reaction temperature in the reaction represented by E is the same as the reaction temperature in the reaction to obtain the triazine ring-containing polymer (8), but considering that the (meth)acryloyl group does not undergo polymerization during the reaction, it is preferably 30°C to 80°C, more preferably 40°C to 70°C, and even more preferably 50°C to 60°C.

[0052] In the second step of Scheme 2, the reaction may be carried out in the presence of a polymerization inhibitor to prevent polymerization of the (meth)acryloyl group during the reaction. Examples of polymerization inhibitors include N-methyl-N-nitrosoaniline, N-nitrosophenylhydroxyamine or its salts, benzoquinones, phenolic polymerization inhibitors, and phenothiazines. Among these, N-nitrosophenylhydroxyamine or its salts are preferred for their excellent polymerization inhibitory effect. Examples of N-nitrosophenylhydroxyamine salts include N-nitrosophenylhydroxyamine ammonium salt and N-nitrosophenylhydroxyamine aluminum salt. Examples of benzoquinones include p-benzoquinone and 2-methyl-1,4-benzoquinone. Examples of phenolic polymerization inhibitors include hydroquinone, p-methoxyphenol, 4-t-butylcatechol, 2-t-butylhydroquinone, and 2,6-di-t-butyl-4-methylphenol. There are no particular restrictions on the amount of polymerization inhibitor used, but for example, it may be 1 ppm to 200 ppm or 10 ppm to 100 ppm by mass ratio with respect to the (meth)acrylic acid ester compound having an isocyanate group represented by formula (11). By using a polymerization inhibitor, the polymerization of the (meth)acryloyl group can be suppressed even when the reaction temperature is raised to about 60°C to 80°C, and the reaction represented by the second step E can be carried out.

[0053] Preferably, the resulting polymer contains no residual raw material components, but some raw materials may remain as long as the effects of the present invention are not impaired. After the reaction is complete, the product can be easily purified by methods such as reprecipitation.

[0054] <Pattern-forming composition> The pattern-forming composition of the present invention comprises the above-mentioned triazine ring-containing polymer, a crosslinking agent, a photoradical polymerization initiator, a silane coupling agent, and a solvent. The following describes each component included in the pattern-forming composition of the present invention.

[0055] <<Triazine Ring-Containing Polymer>> As the triazine ring-containing polymer, the triazine ring-containing polymer described above is used. The content of the triazine ring-containing polymer in the pattern-forming composition is preferably 10 to 30% by weight, more preferably 10 to 20% by weight, and even more preferably 15 to 20% by weight. By having the content of the triazine ring-containing polymer in the pattern-forming composition within the above range, a film can be formed with good pattern-forming properties.

[0056] <<Crosslinking Agent>> The crosslinking agent that can be used in the present invention is not particularly limited as long as it is a compound that can undergo a crosslinking reaction on its own or in combination with the above-mentioned triazine ring-containing polymer to form a crosslinked structure. Examples of such compounds include polyfunctional (meth)acrylate compounds, melamine compounds having crosslinking substituents such as methylol groups and methoxymethyl groups (e.g., phenoplast compounds, aminoplast compounds, etc.), substituted urea compounds, compounds containing crosslinking substituents such as epoxy groups or oxetane groups (e.g., polyfunctional epoxy compounds, polyfunctional oxetane compounds, etc.), compounds containing blocked isocyanate groups, compounds having acid anhydride groups, and compounds having (meth)acrylic groups. From the viewpoint of heat resistance and storage stability, compounds containing epoxy groups, blocked isocyanate groups, and (meth)acrylic groups are preferred, and polyfunctional (meth)acrylate compounds are particularly preferred because the curing reaction can proceed rapidly. In this specification, "polyfunctional (meth)acrylate compound" refers to a polyfunctional acrylate compound, a polyfunctional methacrylate compound, or a mixture of a polyfunctional acrylate compound and a polyfunctional methacrylate compound.

[0057] The polyfunctional (meth)acrylate compounds are not particularly limited as long as they have two or more (meth)acrylic groups in one molecule. Specific examples include ethoxylated trimethylolpropane triacrylate, ethoxylated trimethylolpropane trimethacrylate, ethoxylated glycerin triacrylate, ethoxylated glycerin trimethacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetramethacrylate, ethoxylated dipentaerythritol hexaacrylate, polyglycerin monoethylene oxide polyacrylate, polyglycerin polyethylene glycol polyacrylate, and dipentaerythritol hexaacrylate. Examples include dipentaerythritol hexamethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tricyclodecanedimethanol diacrylate, tricyclodecanedimethanol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, and polybasic acid-modified acrylic oligomers.

[0058] Furthermore, polyfunctional (meth)acrylate compounds are available commercially, and specific examples include NK ester A-200, A-400, A-600, A-1000, A-9300 (tris(2-acryloyloxyethyl) isocyanurate), A-9300-1CL, A-TMPT, UA-53H, 1G, 2G, 3G, 4G, 9G, 14G, 23G, ABE-300, A-BPE-4, A-BPE-6, A-BPE-10, A-BPE-20, and A-BPE- 30, BPE-80N, BPE-100N, BPE-200, BPE-500, BPE-900, BPE-1300N, A-GLY-3E, A-GLY-9E, A-GLY-20E, A-TMPT-3EO, A-TMPT-9EO, AT-20E, ATM-4E, ATM-35E, A-DPH, A-TMPT, A-DCP, A-HD-N, TMPT, DCP, NPG, HD-N, A-DPH-12E, A-DPH-48E, A-DPH-96E, NK Oligo U-15HA, NK Polymer Banaresin GH-1203, APG-100, APG-200 (all manufactured by Shin Nakamura Chemical Industry Co., Ltd.), KAYARAD® DPHA, NPGDA, PET30, DPEA-12, PEG400DA, THE-330, RP-1040, DN-0075 (all manufactured by Nippon Kayaku Co., Ltd.), Aronix M-210, M-303, M-305, M-306, M-309, M-306, M-310, M-313, M-315, M-321, M-350, M-360, M-400, M-402, M-403, M-404, and M-405, M-406, M-408, M-450, M-452, M-460 (manufactured by Toagosei Co., Ltd.), DPGDA, HDDA, T PGDA, HPNDA, PETIA, PETRA, TMPTA, TMPEOTA, EBECRYL11, 40, 135, 140, 145, 145 150, 180, 1142, 204, 205, 210, 215, 220, 230, 244, 245, 265, 270, 280 / 15IB, 284, 294 / 25HD, 303, 436, 438, 446, 450, 524, 525, 600, 605,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 8405, same 8411 Examples include the 8465, 8701, 8800, 8804, 8807, 9270, 9227EA, 936, KRM8200, 8200AE, 7735, 8296, 08452, 8904, 8528, 8912, OTA480, IRR214-K, 616, 679, 742, 793, PEG400DA-D(ACA)Z200M, Z230AA, Z250, Z251, Z300, Z320, and Z254F (all manufactured by Daicel Ornex Co., Ltd.). The above-mentioned polybasic acid-modified acrylic oligomers are also available commercially, with specific examples including Aronics M-510 and M-520 (both manufactured by Toagosei Co., Ltd.).

[0059] The polyfunctional epoxy compound is not particularly limited as long as it has two or more epoxy groups in one molecule. Specific examples include tris(2,3-epoxypropyl) isocyanurate, 1,4-butanediol diglycidyl ether, 1,2-epoxy-4-(epoxyethyl)cyclohexane, glycerol triglycidyl ether, diethylene glycol diglycidyl ether, 2,6-diglycidylphenyl glycidyl ether, 1,1,3-tris[p-(2,3-epoxypropoxy)phenyl]propane, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, 4,4'-methylenebis(N,N-diglycidylaniline), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, trimethylolethane triglycidyl ether, bisphenol-A-diglycidyl ether, pentaerythritol polyglycidyl ether, and the like.

[0060] Furthermore, commercially available epoxy resins include YH-434 and YH434L (manufactured by Nippon Steel Chemical & Material Co., Ltd.), which have at least two epoxy groups; Epolid GT-401, GT-403, GT-301, GT-302, Celoxide 2021, and GT-3000 (manufactured by Daicel Corporation), which have a cyclohexene oxide structure; JER1001, 1002, 1003, 1004, 1007, 1009, 1010, and 828 (all manufactured by Mitsubishi Chemical Corporation), which are bisphenol A type epoxy resins; and bisphenol F type epoxy resins. jER807 (manufactured by Mitsubishi Chemical Corporation), phenol novolac type epoxy resins jER152, jER154 (both manufactured by Mitsubishi Chemical Corporation), EPPN201, EPPN202 (both manufactured by Nippon Kayaku Co., Ltd.), cresol novolac type epoxy resins EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, EOCN-1027 (all manufactured by Nippon Kayaku Co., Ltd.), jER180S75 (manufactured by Mitsubishi Chemical Corporation), alicyclic epoxy resins Denacol EX-252 (manufactured by Nagase ChemteX Corporation), CY175, CY177, CY179 (all manufactured by CIBA-GEIGY You can also use aliphatic polyglycidyl ethers such as Araldite CY-182, CY-192, CY-184 (all manufactured by CIBA-GEIGY A.G.), Epiclon 200, 400 (both manufactured by DIC Corporation), JER871, 872 (both manufactured by Mitsubishi Chemical Corporation), ED-5661, ED-5662 (both manufactured by Celanese Coatings Co., Ltd.), and Denacol EX-611, EX-612, EX-614, EX-622, EX-411, EX-512, EX-522, EX-421, EX-313, EX-314, EX-321 (manufactured by Nagase ChemteX Corporation).

[0061] Compounds containing an acid anhydride group are not particularly limited as long as they are carboxylic acid anhydrides obtained by dehydrating and condensing two molecules of carboxylic acid. Specific examples include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, maleic anhydride, succinic anhydride, octyl succinic anhydride, dodecenyl succinic anhydride, etc., which have one acid anhydride group in their molecule; 1,2,3,4-cyclobutanetetracarboxylic dianhydride, pyromellitic anhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene Examples include succinic acid dianhydride, bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic acid dianhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, 1,2,3,4-butanetetracarboxylic acid dianhydride, 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, and 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, which have two acid anhydride groups in their molecule.

[0062] Compounds containing blocked isocyanate groups are not particularly limited as long as they have two or more blocked isocyanate groups in one molecule, in which the isocyanate group (-NCO) is blocked by an appropriate protecting group, and when exposed to high temperatures during thermal curing, the protecting group (blocking portion) thermally dissociates and detaches, and the resulting isocyanate group undergoes a crosslinking reaction with the crosslinking group (e.g., hydroxyl group) of the triazine ring-containing polymer included in the present invention. For example, compounds having two or more groups represented by the following formula in one molecule (these groups may be the same or different) are included. (In the formula, R ｂ (This represents the organic group in the block.)

[0063] Such compounds can be obtained, for example, by reacting a compound having two or more isocyanate groups in one molecule with a suitable blocking agent. Examples of compounds having two or more isocyanate groups in one molecule include polyisocyanates of isophorone diisocyanate, 1,6-hexamethylene diisocyanate, methylenebis(4-cyclohexyl isocyanate), and trimethylhexamethylene diisocyanate, as well as their dimers and trimers, and reaction products of these with diols, triols, diamines, or triamines. Examples of blocking agents include alcohols such as methanol, ethanol, isopropanol, n-butanol, 2-ethoxyhexanol, 2-N,N-dimethylaminoethanol, 2-ethoxyethanol, and cyclohexanol; phenols such as phenol, o-nitrophenol, p-chlorophenol, and o-, m-, or p-cresol; lactams such as ε-caprolactam; oximes such as acetone oxime, methyl ethyl ketone oxime, methyl isobutyl ketone oxime, cyclohexanone oxime, acetophenone oxime, and benzophenone oxime; pyrazoles such as pyrazole, 3,5-dimethylpyrazole, and 3-methylpyrazole; and thiols such as dodecanethiol and benzenethiol.

[0064] Compounds containing blocked isocyanate groups are available commercially. Specific examples include Takenate® B-830, B-815N, B-842N, B-870N, B-874N, B-882N, B-7005, B-7030, B-7075, B-5010 (all manufactured by Mitsui Chemicals, Inc.), Duranate® 17B-60PX, TPA-B80E, MF-B60X, MF-K60X, E402-B80T (all manufactured by Asahi Kasei Corporation), Karens MOI-BM® (all manufactured by Showa Denko K.K.), and TRIXENE®. Examples include BI7950, BI7951, BI7960, BI7961, BI7963, BI7982, BI7990, BI7991, and BI7992 (all manufactured by Baxenden Chemical).

[0065] The aminoplast compound is not particularly limited as long as it has two or more methoxymethylene groups in one molecule. Examples include the Cymel series such as hexamethoxymethylmelamine CYMEL® 303, tetrabutoxymethylglycoluryl® 1170, and tetramethoxymethylbenzoguanamine® 1123 (all manufactured by Japan Cytec Industries Co., Ltd.), the Nikalac series such as methylated melamine resins MW-30HM, MW-390, MW-100LM, and MX-750LM, and methylated urea resins MX-270, MX-280, and MX-290 (all manufactured by Sanwa Chemical Co., Ltd.). The polyfunctional oxetane compound is not particularly limited as long as it has two or more oxetanyl groups in one molecule. Examples include OXT-221, OX-SQ-H, and OX-SC (all manufactured by Toagosei Co., Ltd.), which contain oxetanyl groups.

[0066] The phenoplast compound has two or more hydroxymethylene groups in one molecule, and when exposed to high temperatures during thermosetting, it undergoes a crosslinking reaction via dehydration condensation with the phenolic hydroxyl groups of the triazine ring-containing polymer of the present invention. Examples of phenoplast compounds include 2,6-dihydroxymethyl-4-methylphenol, 2,4-dihydroxymethyl-6-methylphenol, bis(2-hydroxy-3-hydroxymethyl-5-methylphenyl)methane, bis(4-hydroxy-3-hydroxymethyl-5-methylphenyl)methane, 2,2-bis(4-hydroxy-3,5-dihydroxymethylphenyl)propane, bis(3-formyl-4-hydroxyphenyl)methane, bis(4-hydroxy-2,5-dimethylphenyl)formylmethane, and α,α-bis(4-hydroxy-2,5-dimethylphenyl)-4-formyltoluene. Phenoplast compounds are also available commercially, and specific examples include 26DMPC, 46DMOC, DM-BIPC-F, DM-BIOC-F, TM-BIP-A, BISA-F, BI25X-DF, and BI25X-TPA (all manufactured by Asahi Organic Chemicals Co., Ltd.).

[0067] The crosslinking agents described above may be used alone or in combination of two or more. The crosslinking agent content in the pattern-forming composition is preferably 1 to 200 parts by mass per 100 parts by mass of the triazine ring-containing polymer, but considering solvent resistance, the lower limit is preferably 2 parts by mass, more preferably 5 parts by mass, and further considering control of refractive index and residue in unexposed areas, the upper limit is preferably 150 parts by mass, more preferably 120 parts by mass, and even more preferably 110 parts by mass.

[0068] <<Photoradical polymerization initiator>> The pattern-forming composition of the present invention contains a photoradical polymerization initiator. The photoradical polymerization initiator may be appropriately selected from known ones, for example, acetophenones, benzophenones, Michler's benzoylbenzoate, amyloxime esters, oxime esters, tetramethylthiuram monosulfide, and thioxanthones. Photocleavage-type photoradical polymerization initiators are particularly preferred. Photocleavage-type photoradical polymerization initiators are described in "Latest UV Curing Technology" (page 159, publisher: Kazuhiro Takasuki, publisher: Technical Information Association Co., Ltd., published in 1991). Examples of commercially available photoradical polymerization initiators include, for example, BASF products: Irgacure 127, 184, 369, 379, 379EG, 651, 500, 754, 819, 903, 907, 784, 2959, CGI1700, CGI1750, CGI1850, CG24-61, OXE01, OXE02, OXE03, OXE04, Darocure 1116, 1173, MBF, BASF product name: Lucilin TPO, UCSB product name: Ebecryl P36, and Fratezuri-Lamberti product name: Ezacure Examples include KIP150, KIP65LT, KIP100F, KT37, KT55, KTO46, and KIP75 / B. When using a photoradical polymerization initiator, it is preferable to use it in the range of 0.1 to 200 parts by mass, and more preferably in the range of 1 to 150 parts by mass, per 100 parts by mass of the crosslinking agent.

[0069] <<Silane Coupling Agent>> The silane coupling agent that can be used in the pattern-forming composition of the present invention is not particularly limited as long as it contains a silicon atom to which one or more alkoxy groups and predetermined functional groups are bonded in one molecule, and is capable of undergoing a crosslinking reaction alone or together with the above-mentioned triazine ring-containing polymer to form a crosslinked structure. Examples of silane coupling agents include epoxy silane coupling agents, styrene silane coupling agents, amino silane coupling agents, isocyanate silane coupling agents, isocyanurate silane coupling agents, mercapto silane coupling agents, vinyl silane coupling agents, acrylic silane coupling agents, methacrylic silane coupling agents, ureido silane coupling agents, phenyl silane coupling agents, fluorinated alkyl silane coupling agents, and acid anhydride silane coupling agents. Among these silane coupling agents, amino-based silane coupling agents, epoxy-based silane coupling agents, vinyl-based silane coupling agents, methacrylic-based silane coupling agents, or acid anhydride-based silane coupling agents are preferred because they yield patterning films with excellent patternability. Amino-based silane coupling agents are compounds containing a silicon atom bonded to one or more alkoxy groups and amino groups in a single molecule, wherein the amino group is -NH ２ , -NHR'', or -N(R'') ２Any of the following may be used (where "R" represents an organic group). Examples of amino silane coupling agents include N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, and N-phenyl-3-aminopropyltrimethoxysilane. Epoxy silane coupling agents contain one or more alcohols per molecule. These are compounds containing silicon atoms bonded to a group having a xyl group and one or more epoxy groups. Vinyl-based silane coupling agents are compounds containing silicon atoms bonded to a group having one or more alkoxy groups and one or more vinyl groups in one molecule. Methacrylic-based silane coupling agents are compounds containing silicon atoms bonded to a group having one or more alkoxy groups and one or more methacrylic groups in one molecule. Acid anhydride-based silane coupling agents are compounds containing silicon atoms bonded to a group having one or more alkoxy groups and one or more acid anhydride groups in one molecule. More specifically, silane coupling agents having the following structures can be listed.

[0070] <<Solvent>> The solvents that can be used in the pattern-forming composition of the present invention are not particularly limited, but specific examples of the solvents include toluene, p-xylene, o-xylene, m-xylene, ethylbenzene, styrene, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, diethylene glycol diethyl ether, dipropylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether, triethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate Diethylene glycol, 1-octanol, ethylene glycol, hexylene glycol, trimethylene glycol, 1-methoxy-2-butanol, cyclohexanol, diacetone alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, propylene glycol, benzyl alcohol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, γ-butyrolactone, acetone, methyl ethyl ketone, methyl isopropyl ketone, 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,Examples include N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, and N-cyclohexyl-2-pyrrolidinone, which may be used individually or in combination of two or more.

[0071] <<Other Additives>> The pattern-forming composition of the present invention may contain additives other than the triazine ring-containing polymer, crosslinking agent, photoradical polymerization initiator, silane coupling agent, and solvent described above, insofar as they do not impair the effects of the present invention. For example, additives such as leveling agents, surfactants, polymerization inhibitors, antioxidants, rust inhibitors, mold release agents, plasticizers, defoaming agents, thickeners, dispersants, antistatic agents, anti-settling agents, pigments, dyes, ultraviolet absorbers, and light stabilizers may be included.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 polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether; polyoxyethylene-polyoxypropylene block copolymers; sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, and sorbitan monolaurate. Nonionic surfactants such as sorbitan fatty acid esters including sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate; polyoxyethylene sorbitan fatty acid esters including polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; trade names EFS-131, EFS-321, EFS-521, EFS-801 (manufactured by DIC Corporation (formerly DIC Corporation) (Manufactured by Dainippon Ink and Chemicals, Inc.), Product names: F-Top EF301, EF303, EF352 (Manufactured by Mitsubishi Materials Electronic Chemicals, Inc. (formerly GEMCO Corporation)), Product names: Megafac F171, F173, R-08, R-30, R-40, R-41, F-114, F-410, F-430, F-444, F-477, F-552, F-553, F-554, F-555, F-556, F-557, F-558, F-559, F-561, F-562, F-563, RS-75, RS-72-K, RS-76-E, RS-76NS, RS-77 (DIC Corporation) Examples include fluorine-based surfactants such as (manufactured by Sumitomo 3M Co., Ltd.), Florard FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), product names Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Inc.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), BYK-302, BYK-307, BYK-322, BYK-323, BYK-330, BYK-333, BYK-370, BYK-375, BYK-378 (manufactured by BIC Chemie Japan Co., Ltd.), etc.

[0072] These surfactants may be used individually or in combination of two or more. The amount of surfactant used is preferably 0.0001 to 5 parts by mass, more preferably 0.001 to 1 part by mass, and even more preferably 0.01 to 0.5 parts by mass, per 100 parts by mass of the triazine ring-containing polymer.

[0073] (Method for forming patterns) In the method for forming patterns using the pattern-forming composition of the present invention, the pattern-forming composition is applied to a substrate, and then, if necessary, the solvent is evaporated by heating. After that, the applied portion of the pattern-forming composition is irradiated with light (exposed), developed, and then fired to obtain a desired cured film. By using the pattern-forming composition of the present invention, a patterning film can be obtained that has a high refractive index and excellent weather resistance, as well as being a cured product with regular and excellent patternability. The pattern-forming composition of the present invention can be used as a pattern-forming composition for forming a patterning film of a predetermined width.

[0074] In this case, the method of applying the pattern-forming composition is arbitrary, and methods such as spin coating, dip coating, flow coating, inkjet coating, jet dispenser coating, spray coating, bar coating, gravure coating, slit coating, roll coating, transfer printing, brush coating, blade coating, and air knife coating can be employed.

[0075] Furthermore, suitable substrates for the cured product (pattern) include silicon, glass coated with indium tin oxide (ITO), glass coated with indium zinc oxide (IZO), substrates coated with silicon nitride (for example, glass coated with silicon nitride), polyethylene terephthalate (PET), plastics, glass, quartz, ceramics, etc. Flexible substrates with flexibility can also be used. The pattern-forming composition of the present invention exhibits good pattern-forming properties even on substrates coated with silicon nitride, which was difficult to achieve good pattern formation with conventional pattern-forming compositions. Therefore, substrates coated with silicon nitride are preferred as the substrate. In other words, the pattern-forming composition of the present invention can be suitably used as a composition for forming patterns on a substrate coated with silicon nitride.

[0076] The firing temperature during pattern formation is not particularly limited for the purpose of evaporating the solvent, and can be set to, for example, 70 to 400°C. Since the pattern-forming composition of the present invention exhibits good pattern-forming properties even at low firing temperatures, the firing temperature may be 70 to 90°C. The firing time may be any time required for the solvent to evaporate, for example, 1 to 600 seconds. The firing time is preferably 30 seconds or more, and more preferably 60 seconds or more. Since the pattern-forming composition of the present invention exhibits good pattern-forming properties even at short firing times, the firing time may be 1 to 200 seconds, 30 to 200 seconds, or 60 to 200 seconds. The firing method is not particularly limited, and for example, evaporation may be performed using a hot plate or oven under a suitable atmosphere such as air, an inert gas such as nitrogen, or a vacuum. The firing temperature and firing time should be selected to suit the process steps of the target electronic device, and firing conditions should be selected such that the physical properties of the resulting film are suitable for the required characteristics of the electronic device. The conditions for light irradiation are not particularly limited, and appropriate irradiation energy and time can be adopted depending on the triazine ring-containing polymer and crosslinking agent used. The irradiation energy is not particularly limited, for example, 10 to 500 mJ / cm². ２This can be done. The pattern-forming composition of the present invention exhibits good pattern-forming properties even at low irradiation energy, therefore the irradiation energy is 10 to 100 mJ / cm². ２ That's fine.

[0077] Development after exposure can be carried out, for example, by immersing the exposure resin in an organic solvent developer or an aqueous developer. Specific examples of organic solvent developers include PGME (propylene glycol monomethyl ether), PGMEA (propylene glycol monomethyl ether acetate), a mixed solvent of PGME and PGMEA, NMP (N-methyl-2-pyrrolidone), γ-butyrolactone, and DMSO (dimethyl sulfoxide). Specific examples of aqueous developers include sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, and tetramethylammonium.

[0078] The cured pattern obtained as described above achieves a high refractive index, excellent weather resistance, and pattern formation properties, making it suitable for use in the fields of electronic devices and optical materials, such as liquid crystal displays, organic electroluminescent (EL) displays, touch panels, photoluminescent (LED) elements, solid-state image sensors, organic thin-film solar cells, dye-sensitized solar cells, organic thin-film transistors (TFTs), lenses, prism cameras, binoculars, microscopes, and semiconductor exposure equipment. For example, the pattern can be used as a lens of a desired convex shape, and this lens can have a high refractive index and excellent transparency. The size of the lens is not particularly limited, but the width of the lens is preferably 0.1 to 1,000 μm, more preferably 0.5 to 500 μm, and even more preferably 1 to 100 μm, and the height of the lens is preferably 0.1 to 100 μm, more preferably 0.5 to 50 μm, and even more preferably 1 to 25 μm.

[0079] The present invention will be described in more detail below with reference to synthesis examples and embodiments, but the present invention is not limited to the embodiments described below. The measuring devices used in the embodiments are as follows.

[0080] [ １[H-NMR] Instrument: Bruker NMR System AVANCE III HD 500 (500MHz) Measurement solvent: Deuterated dimethyl sulfoxide (DMSO-d ６ ) Reference material: Tetramethylsilane (TMS) (δ 0.0 ppm) [GPC] Instrument: Tosoh Corporation HLC-8200 GPC Column: Tosoh TSKgel α-3000 + Tosoh TSKgel α-4000 Column temperature: 40℃ Solvent: Dimethylformamide (DMF) Detector: UV (271 nm) Detection line: Standard polystyrene [Optical microscope] Instrument: Evident Co., Ltd. Erecting microscope system BX53M [Exposure] Instrument: SUSS Corporation Mask aligner MA6GEN4 [Development] Instrument: Actes Kyosan Co., Ltd. Compact developer ADE-3000S

[0081] [1] Synthesis of triazine ring-containing polymers [Synthesis Example 1-1] Synthesis of polymer compound [5] The reaction for synthesizing polymer compound [5] is shown below.

[0082] In a 3,000 mL four-necked flask, 9,9-bis(3-amino-4-hydroxyphenyl)fluorene [2] (BAHF, 33.0 g, 0.087 mol, manufactured by JFE Chemical Corporation) and 3-methoxy-N,N-dimethylpropanamide (KJCMPA-100, 320.0 g, manufactured by KJ Chemicals Corporation) were added, the flask was purged with nitrogen, and the mixture was stirred to dissolve BAHF [2] in KJCMPA-100. The mixture was then cooled to -5°C using an ethanol-dry ice bath, and 2,4,6-trichloro-1,3,5-triazine [1] (20.0 g, 0.108 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) was added while ensuring that the internal temperature did not exceed 5°C. Finally, the mixture was washed with 20.0 g of KJCMPA-100. After stirring for 30 minutes, the reaction solution was heated until the internal temperature reached 85°C ± 5°C and stirred for 1 hour. Then, 4-aminophenethyl alcohol [3] (17.9 g, 0.130 mol, Oakwood) and 4-aminobenzotrifluoride [4] (4TFMA, 7.7 g, 0.043 mol, Tokyo Chemical Industry Co., Ltd.) were added, washed with 80.0 g of KJCMPA-100, and stirred for 3 hours. Then, N,N-diethylethanolamine (43.3 g, 0.325 mol, Kanto Chemical Co., Ltd.) was added dropwise, stirred for 30 minutes, and then the stirring was stopped. Tetrahydrofuran (THF, 180 g, Junsei Chemical Co., Ltd.), ammonium acetate (250 g), and deionized water (250 g) were added to the reaction solution and stirred for 30 minutes. After stopping the stirring, the solution was transferred to a separatory funnel and separated into an organic layer and an aqueous layer, and the organic layer was recovered. Ammonium acetate (250 g) and deionized water (250 g) were added again to the recovered organic layer and stirred for 30 minutes. After stopping the stirring, the solution was transferred to a separatory funnel and separated into an organic layer and an aqueous layer, and the organic layer was recovered again. The recovered organic layer was added dropwise to methanol (440 g) and deionized water (660 g) and reprecipitation was performed. The obtained precipitate was filtered off and dried in a vacuum dryer at 80°C for 8 hours to obtain 68.7 g of the target polymer compound [5] (hereinafter referred to as "compound P-1"). The weight-average molecular weight Mw of compound P-1, measured in polystyrene equivalent by GPC, was 1,953, and the polydispersity Mw / Mn was 2.5. １ The measurement results of the H-NMR spectrum are shown in Figure 1.

[0083] [Synthesis Example 1-2] Synthesis of polymer compound [6] The reaction for synthesizing polymer compound [6] is shown below. 20.00 g of P-1[5] obtained in Synthesis Example 1-1 and 56.97 g of PGMEA were added to a 100 mL four-necked flask, and after purging with nitrogen, the mixture was stirred to dissolve. The solution was then heated to an internal temperature of 70°C, and 0.0050 g of 2,2'-ethylidenebis(4,6-di-tert-amylphenol) monoacrylate (SUMILIZER GS, Sumitomo Chemical Co., Ltd.) and 4.42 g of 2-isocyanatoethyl acrylate (AOI-VM, Showa Denko K.K.) were added dropwise. The mixture was stirred at an internal temperature of 70°C for 3 hours to obtain a 30 wt% PGMEA solution (hereinafter referred to as "P-1-1 solution").

[0084] [Synthesis Example 2-1] Synthesis of polymer compound [7] The reaction for synthesizing polymer compound [7] is shown below.

[0085] In a 3,000 mL four-necked flask, 9,9-bis(3-amino-4-hydroxyphenyl)fluorene [2] (BAHF, 66.0 g, 0.174 mol, manufactured by JFE Chemical Corporation) and 3-methoxy-N,N-dimethylpropanamide (KJCMPA-100, 640.0 g, manufactured by KJ Chemicals Corporation) were added, the flask was purged with nitrogen, and the mixture was stirred to dissolve BAHF [2] in KJCMPA-100. The mixture was then cooled to -5°C using an ethanol-dry ice bath, and 2,4,6-trichloro-1,3,5-triazine [1] (40.0 g, 0.217 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) was added while ensuring that the internal temperature did not exceed 5°C. Finally, the mixture was washed with 40.0 g of KJCMPA-100. After stirring for 30 minutes, the reaction solution was heated until the internal temperature reached 85°C ± 5°C and stirred for 1 hour. Then, 4-aminophenethyl alcohol [3] (47.6 g, 0.347 mol, Oakwood) was added, washed with 180.0 g of KJCMPA-100, and stirred for 3 hours. Then, N,N-diethylethanolamine (86.7 g, 0.651 mol, Kanto Chemical Co., Ltd.) was added dropwise, stirred for 30 minutes, and then the stirring was stopped. Tetrahydrofuran (THF, 360 g, Junsei Chemical Co., Ltd.), ammonium acetate (500 g), and deionized water (500 g) were added to the reaction solution and stirred for 30 minutes. After stopping the stirring, the solution was transferred to a separatory funnel, separated into an organic layer and an aqueous layer, and the organic layer was recovered. 500 g of ammonium acetate and 500 g of deionized water were added again to the recovered organic layer, and the mixture was stirred for 30 minutes. After stopping the stirring, the solution was transferred to a separatory funnel and separated into an organic layer and an aqueous layer, and the organic layer was recovered again. The recovered organic layer was added dropwise to 880 g of methanol and 1320 g of deionized water and reprecipitated. The obtained precipitate was filtered off and dried in a vacuum dryer at 80°C for 8 hours to obtain 224.4 g of the target polymer compound [7] (hereinafter referred to as "compound P-2"). The weight-average molecular weight Mw of compound P-2, measured in polystyrene equivalent by GPC, was 1,784, and the polydispersity Mw / Mn was 2.2. １ The measurement results of the H-NMR spectrum are shown in Figure 2.

[0086] [Synthesis Example 2-2] Synthesis of polymer compound [8] The reaction for synthesizing polymer compound [8] is shown below.

[0087] 19.90 g of compound P-2[7] obtained in Synthesis Example 2-1 and 1.60 g of PGMEA were added to a 100 mL four-necked flask. After purging with nitrogen, the mixture was stirred to dissolve. The solution was then heated to an internal temperature of 70°C, and 0.0050 g of 2,2'-ethylidenebis(4,6-di-tert-amylphenol) monoacrylate (SUMILIZER GS, Sumitomo Chemical Co., Ltd.) and 6.50 g of 2-isocyanatoethyl acrylate (AOI-VM, Showa Denko K.K.) were added dropwise. The mixture was stirred at an internal temperature of 70°C for 3 hours to obtain a 30 wt% PGMEA solution (hereinafter referred to as "P-2-1 solution").

[0088] [Synthesis Example 3-1] Synthesis of polymer compound

[11] The reaction for synthesizing polymer compound

[11] is shown below.

[0089] The target polymer compound

[11] (hereinafter referred to as "compound P-3") was obtained in the same manner as in Example 1 of International Publication No. 2021 / 117692.

[0090] [Example 1-1] To the P-1-1 solution (5.337 g) obtained in Synthesis Example 1-2, 0.015 g of Megafac R-40 (manufactured by DIC Corporation), a 10% by mass PGMEA solution, was added as a surfactant, and 4.65 g of PGMEA was added as an additional solvent. Visual confirmation of dissolution was made to prepare the solution (hereinafter referred to as "P-1-2 solution"). This P-1-2 solution was spin-coated onto an alkali-free glass substrate measuring 50 mm × 50 mm × 0.7 t (thickness) using a spin coater at 200 rpm for 5 seconds and then at 500 rpm for 30 seconds. The film was then dried on a hot plate at 100°C for 3 minutes to obtain a cured film (hereinafter referred to as "P-1-2 film").

[0091] [Example 1-2] A solution was prepared in the same manner as in Example 1-1, except that the P-2-1 solution obtained in Synthesis Example 2-2 was used (hereinafter referred to as "P-2-2 solution"). This P-2-2 solution was spin-coated onto an alkali-free glass substrate measuring 50 mm × 50 mm × 0.7 t (thickness) using a spin coater at 200 rpm for 5 seconds and then at 700 rpm for 30 seconds, and dried on a hot plate at 100°C for 3 minutes to obtain a cured film (hereinafter referred to as "P-2-2 film").

[0092] [Comparative Example 1-1] Compound P-3 (1.499 g) obtained in Synthesis Example 3-1 was mixed with R-40 (0.015 g) of a 10% by mass PGME solution as a surfactant, and PGME (8.487 g) as an additional solvent. Visual confirmation of dissolution was made to prepare the solution (hereinafter referred to as "P-3 solution"). This P-3 solution was spin-coated onto a 50 mm × 50 mm × 0.7 t (thickness) alkali-free glass substrate using a spin coater at 200 rpm for 5 seconds and then at 2000 rpm for 30 seconds. A cured film (hereinafter referred to as "P-3 film") was obtained by drying on a hot plate at 100°C for 3 minutes.

[0093] The refractive index and film thickness of the cured film obtained above were measured. Furthermore, 418 W / m ２ A weather resistance test was conducted at 55°C, and the yellowness YI was measured at the start of the weather resistance test (0 hours) and 4 hours after the start of the weather resistance test. Next, the degree of yellowing ΔYI (= yellowness YI at 4 hours - yellowness YI at 0 hours), which is the difference between the yellowness YI at 0 hours and 4 hours later, was calculated. The results of these yellowness measurement results and yellowing degree calculation results are shown in Table 1 below. Note that a refractive index of 1.60 or higher can be evaluated as high refractive index. Also, a degree of yellowing ΔYI of 2.0 or less can be evaluated as high weather resistance.

[0094] As shown in Table 1, the polymer film obtained from solution P-3 had a high refractive index but exhibited low weather resistance. In contrast, the polymer film obtained from solutions P-1-2 and P-2-2 achieved both a high refractive index and high weather resistance.

[0095] [2] Preparation of pattern-forming composition and production of pattern (1) Preparation of pattern-forming composition [Example 2-1] To the P-1-1 solution (6.679 g) synthesized in Synthesis Example 1-2, ethoxylated dipentaerythritol hexaacrylate (1.098 g, NK ester A-DPH-12E, manufactured by Shin Nakamura Chemical Industry Co., Ltd.) was added as a crosslinking agent, Irgacure Oxe04 (0.055 g, manufactured by BASF) as a UV radical generator, EFS-521 (0.091 g, manufactured by DIC Corporation) of 20% by mass PGMEA solution as a surfactant, Silquest A-187T (0.054 g, manufactured by Dow Toray Industries, Ltd.) as a silane coupling agent, and PGMEA (2.077 g) as an additional solvent was added and the solution was prepared by visual confirmation that it was dissolved (hereinafter referred to as "SP-1 solution").

[0096] [Example 2-2] A solution was prepared in the same manner as in Example 2-1, except that KBM-573 (0.054 g, manufactured by Shin-Etsu Chemical Co., Ltd.) was used as the silane coupling agent (hereinafter referred to as "SP-2 solution").

[0097] [Example 2-3] A solution was prepared in the same manner as in Example 2-1, except that KBM-602 (0.054 g, manufactured by Shin-Etsu Chemical Co., Ltd.) was used as the silane coupling agent (hereinafter referred to as "SP-3 solution").

[0098] [Example 2-4] A solution was prepared in the same manner as in Example 2-1, except that KBM-903 (0.054 g, manufactured by Shin-Etsu Chemical Co., Ltd.) was used as the silane coupling agent (hereinafter referred to as "SP-4 solution").

[0099] [Example 2-5] A solution was prepared in the same manner as in Example 2-1, except that KBM-5103 (0.054 g, manufactured by Shin-Etsu Chemical Co., Ltd.) was used as the silane coupling agent (hereinafter referred to as "SP-5 solution").

[0100] [Example 2-6] A solution was prepared in the same manner as in Example 2-1, except that KBM-6803 (0.054 g, manufactured by Shin-Etsu Chemical Co., Ltd.) was used as the silane coupling agent (hereinafter referred to as "SP-6 solution").

[0101] [Example 2-7] A solution was prepared in the same manner as in Example 2-1, except that KBE-585 (0.054 g, manufactured by Shin-Etsu Chemical Co., Ltd.) was used as the silane coupling agent (hereinafter referred to as "SP-7 solution").

[0102] [Example 2-8] A solution was prepared in the same manner as in Example 2-1, except that KBE-903 (0.054 g, manufactured by Shin-Etsu Chemical Co., Ltd.) was used as the silane coupling agent (hereinafter referred to as "SP-8 solution").

[0103] [Example 2-9] A solution was prepared in the same manner as in Example 2-1, except that X-12-967C (0.054 g, manufactured by Shin-Etsu Chemical Co., Ltd.) was used as the silane coupling agent (hereinafter referred to as "SP-9 solution").

[0104] [Example 2-10] A solution was prepared in the same manner as in Example 2-1, except that X-12-1290 (0.054 g, manufactured by Shin-Etsu Chemical Co., Ltd.) was used as the silane coupling agent (hereinafter referred to as "SP-10 solution").

[0105] [Example 2-11] A solution was prepared in the same manner as in Example 2-1, except that X-12-1333A (0.054 g, manufactured by Shin-Etsu Chemical Co., Ltd.) was used as the silane coupling agent (hereinafter referred to as "SP-11 solution").

[0106] [Example 2-12] A solution was prepared in the same manner as in Example 2-1, except that X-12-1360 (0.054 g, manufactured by Shin-Etsu Chemical Co., Ltd.) was used as the silane coupling agent (hereinafter referred to as "SP-12 solution").

[0107] [Example 2-13] A solution was prepared in the same manner as in Example 2-1, except that X-12-1369A (0.054 g, manufactured by Shin-Etsu Chemical Co., Ltd.) was used as the silane coupling agent (hereinafter referred to as "SP-13 solution").

[0108] [Example 2-14] A solution was prepared in the same manner as in Example 2-1, except that X-12-1269B (0.054 g, manufactured by Shin-Etsu Chemical Co., Ltd.) was used as the silane coupling agent (hereinafter referred to as "SP-14 solution").

[0109] [Example 2-15] A solution was prepared in the same manner as in Example 2-1, except that X-12-1369C (0.054 g, manufactured by Shin-Etsu Chemical Co., Ltd.) was used as the silane coupling agent (hereinafter referred to as "SP-15 solution").

[0110] [Example 2-16] A solution was prepared in the same manner as in Example 2-1, except that X-12-1370 (0.054 g, manufactured by Shin-Etsu Chemical Co., Ltd.) was used as the silane coupling agent (hereinafter referred to as "SP-16 solution").

[0111] [Example 2-17] A solution was prepared in the same manner as in Example 2-1, except that X-12-1397A (0.054 g, manufactured by Shin-Etsu Chemical Co., Ltd.) was used as the silane coupling agent (hereinafter referred to as "SP-17 solution").

[0112] [Example 2-18] A solution was prepared in the same manner as in Example 2-8, except that the P-2-1 solution synthesized in Synthesis Example 2-2 was used (hereinafter referred to as "SP-18 solution").

[0113] (2) Fabrication of patterned film [Example 3-1] The SP-1 solution prepared in Example 2-1 was used to make a 50 mm × 50 mm × 0.7 t (thickness) (0.7 mm) SiN ｘ The coated glass substrate was spin-coated using a spin coater at 200 rpm for 5 seconds and then at 1000 rpm for 30 seconds. After pre-drying on a 100°C hot plate for 3 minutes, a mask was placed on the coated film using a SUSS MA6GEN4 mask aligner. The mask had 5 μm wide linear openings spaced 10 μm apart, and the remaining space (UV shielding area) was then exposed to light at a wavelength of 365 nm at a rate of 50 mJ / cm². ２ The following exposure levels were applied. After UV irradiation, the film was developed for 40 seconds using a 2.38% TMAH aqueous solution, and then rinsed with pure water for 30 seconds to obtain a patterned film.

[0114] [Example 3-2] A patterned film was obtained in the same manner as in Example 3-1, except that the SP-2 solution prepared in Example 2-2 was used instead.

[0115] [Example 3-3] A patterned film was obtained in the same manner as in Example 3-1, except that the SP-3 solution prepared in Example 2-3 was used instead.

[0116] [Example 3-4] A patterned film was obtained in the same manner as in Example 3-1, except that the SP-4 solution prepared in Example 2-4 was used instead.

[0117] [Example 3-5] A patterned film was obtained in the same manner as in Example 3-1, except that the SP-5 solution prepared in Example 2-5 was used instead.

[0118] [Example 3-6] A patterned film was obtained in the same manner as in Example 3-1, except that the SP-6 solution prepared in Example 2-6 was used instead.

[0119] [Example 3-7] A patterned film was obtained in the same manner as in Example 3-1, except that the SP-7 solution prepared in Example 2-7 was used instead.

[0120] [Example 3-8] A patterned film was obtained in the same manner as in Example 3-1, except that the SP-8 solution prepared in Example 2-8 was used instead.

[0121] [Example 3-9] A patterned film was obtained in the same manner as in Example 3-1, except that the SP-9 solution prepared in Example 2-9 was used instead.

[0122] [Example 3-10] A patterned film was obtained in the same manner as in Example 3-1, except that the SP-10 solution prepared in Example 2-10 was used instead.

[0123] [Example 3-11] A patterned film was obtained in the same manner as in Example 3-1, except that the SP-11 solution prepared in Example 2-11 was used instead.

[0124] [Example 3-12] A patterned film was obtained in the same manner as in Example 3-1, except that the SP-12 solution prepared in Example 2-12 was used instead.

[0125] [Example 3-13] A patterned film was obtained in the same manner as in Example 3-1, except that the SP-13 solution prepared in Example 2-13 was used instead.

[0126] [Example 3-14] A patterned film was obtained in the same manner as in Example 3-1, except that the SP-14 solution prepared in Example 2-14 was used instead.

[0127] [Example 3-15] A patterned film was obtained in the same manner as in Example 3-1, except that the SP-15 solution prepared in Example 2-15 was used instead.

[0128] [Example 3-16] A patterned film was obtained in the same manner as in Example 3-1, except that the SP-16 solution prepared in Example 2-16 was used instead.

[0129] [Example 3-17] A patterned film was obtained in the same manner as in Example 3-1, except that the SP-17 solution prepared in Example 2-17 was used instead.

[0130] [Example 3-18] A patterned film was obtained in the same manner as in Example 3-1, except that the SP-18 solution prepared in Example 2-18 was used instead.

[0131] The patterned films obtained above were observed on the surface using the Evident Co., Ltd. upright microscope system BX53M. Optical microscope images of the patterned films obtained in Examples 3-1 to 3-18 are shown in Figures 3 to 20, and the results are shown in Table 2. In Table 2, "◎" indicates that good patterning properties were obtained and there was no residual film.

[0132] As shown in Figures 3-20 and Table 2, the patterned films obtained using a solution containing the triazine ring-containing polymer of the present invention exhibit excellent adhesion to the substrate and patterning properties, regardless of the type of silane coupling agent.

Claims

1. A triazine ring-containing polymer comprising a repeating unit structure represented by the following formula (1), having at least one triazine ring terminus, wherein at least a portion of this triazine ring terminus is bonded to a group having an arylamino group. (In formula (1), R １ ~R ８ R and R' independently represent a hydrogen atom, halogen atom, carboxyl group, sulfo group, C1-C10 alkyl group, C1-C10 halogenated alkyl group, or C1-C10 alkoxy group; R and R' independently represent a hydrogen atom, alkyl group, alkoxy group, aryl group, or aralkyl group; and * represents a bond.

2. The triazine ring-containing polymer according to claim 1, wherein the group having the arylamino group is represented by the following formula (2). (In formula (2), R ９ (where * represents a substituent or bridging group, n is an integer from 1 to 5, and * represents a bond.) 3. The R ９ is a group selected from a hydroxyalkyl group, a (meth)acryloyloxyalkyl group, -OC(A ６ ), where A ３ is F, Cl, Br or I; and a group represented by the following formula (3). The triazine ring-containing polymer according to claim 2. (In the formula, A １ represents an alkylene group having 1 to 10 carbon atoms, A ２ represents a single bond or a group represented by the following formula (4) , A ３ represents a single bond, -C ｂ H ２ｂ -O-C ｃ H ２ｃ -(b and c are each independently an integer of 0 to 5), or an optionally hydroxy-substituted (a + 1)-valent aliphatic hydrocarbon group, A ４ represents a single bond or an alkylene group having 1 to 5 carbon atoms, A ５ represents a hydrogen atom or a methyl group, a represents 1 or 2, and * represents a bond.)​​ 4. n is 1 or 2, and R ９ However, hydroxymethyl group, 2-hydroxyethyl group, (meth)acryloyloxymethyl group, (meth)acryloyloxyethyl group, -OCF ３ The triazine ring-containing polymer according to claim 3, wherein the group is selected from the groups represented by the following formulas (3-1) to (3-8). (In the formula, * represents a bond.) 5. A pattern-forming composition comprising a triazine ring-containing polymer according to any one of claims 1 to 4, a crosslinking agent, a photoradical polymerization initiator, a silane coupling agent, and a solvent.

6. The pattern-forming composition according to claim 5, wherein the content of the triazine ring-containing polymer in the pattern-forming composition is 10 to 30% by weight.

7. The pattern-forming composition according to claim 5, wherein the crosslinking agent is a polyfunctional (meth)acrylate compound.

8. The pattern-forming composition according to claim 5, wherein the silane coupling agent is an amino-based silane coupling agent, an epoxy-based silane coupling agent, a vinyl-based silane coupling agent, a methacrylic-based silane coupling agent, or an acid anhydride-based silane coupling agent.

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