Transparent conductive film protective film composition

Abstract

For example, a composition containing a triazine ring-containing hyperbranched polymer terminated with a fluorine atom-containing arylamino group, a crosslinking agent A having a molecular weight of 1,000 or more, and an ultraviolet absorber, as represented by the following formula [4], provides a film that is excellent in light resistance and can improve the visibility of transparent conductive films, and is suitable as a protective film-forming composition for transparent conductive films.

Description

[Technical Field]

[0001] The present invention relates to a protective film-forming composition for a transparent conductive film. [Background technology]

[0002] In recent years, there has been a growing demand for high-performance polymer materials in the development of electronic devices such as liquid crystal displays, organic electroluminescence (EL) displays, touch panels, optical semiconductor (LED) elements, solid-state imaging elements, organic thin-film solar cells, dye-sensitized solar cells, and organic thin-film transistors (TFTs). Specific properties that are required include 1) heat resistance, 2) transparency, 3) high refractive index, 4) high solubility, 5) low volume shrinkage, 6) high temperature and humidity resistance, and 7) high film hardness. In view of this, the present inventors have already discovered 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, a high refractive index, high solubility, and low volume shrinkage by itself, and is suitable as a film-forming composition for producing electronic devices (Patent Document 1).

[0003] Conventionally, transparent conductive film materials mainly used are indium tin oxide (ITO) and indium zinc oxide (IZO), which are standard materials that exhibit good optical transparency and conductivity. However, obtaining these inorganic oxide films requires complex processes such as sputtering, high-vacuum, and high-temperature annealing. This requires specialized equipment and is costly. In recent years, electronic devices have become more flexible and lightweight through the use of plastic substrates, etc., and they are required to be durable against physical stress such as bending. Although technology for forming ITO and IZO films on flexible substrates is being investigated, the brittleness and susceptibility to damage of inorganic oxides has not been improved.

[0004] Along with the progress in flexibility mentioned above, transparent conductive films with conductive nanostructures (percolation structures of metal nanoparticles or metal nanowires, metal mesh structures, etc.) have been developed as materials with excellent resistance to physical stress. In addition to being flexible, these transparent conductive films have the advantage that they can be produced by a wet process using a dispersion of metal nanoparticles or metal nanowires (Patent Documents 1 to 3), and also that their electrical resistance can be reduced simply by increasing the amount of metal they contain. On the other hand, if the amount of metal in the film is increased to reduce the resistance, not only does the film become cloudy due to diffuse reflection of light, causing it to lose its optical transparency, but there are also problems such as reduced conductivity due to surface deterioration and structural destruction caused by the metal. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication No. 2010 / 128661 [Patent Document 2] Japanese Patent Application Laid-Open No. 2009-505358 [Patent Document 3] Japanese Patent Application Laid-Open No. 2013-77234 [Patent Document 4] Japanese Patent Application Laid-Open No. 2010-108877 [Patent Document 5] International Publication No. 2015 / 093510 Summary of the Invention [Problem to be solved by the invention]

[0006] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a protective film-forming composition for a transparent conductive film that provides a film that is excellent in light resistance and can improve the visibility of the transparent conductive film. [Means for solving the problem]

[0007] The present inventors have already reported a composition containing a triazine ring-containing hyperbranched polymer that provides a film capable of improving the visibility of transparent conductive films (Patent Document 5). Based on this knowledge, the inventors have conducted extensive research from the perspective of improving light resistance, and as a result have found that a composition containing a specific triazine ring-containing hyperbranched polymer that is terminated with a fluorine atom-containing arylamino group, a crosslinking agent with a molecular weight of 1,000 or more, and an ultraviolet absorber provides a film that is excellent in light resistance and can improve the visibility of transparent conductive films, thereby completing the present invention.

[0008] That is, the present invention is 1. A protective film-forming composition for a transparent conductive film, comprising a triazine ring-containing hyperbranched polymer that contains a repeating unit structure represented by the following formula (1), has at least one triazine ring terminal, and at least a portion of the triazine ring terminal is blocked with a fluorine atom-containing arylamino group; a crosslinking agent A having a molecular weight of 1,000 or more; and an ultraviolet absorber: [ka] In the formula, R and R' each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group, and Ar represents at least one group selected from the group consisting of groups represented by formulas (2) to (13). [ka] [In the formula, R 1 ~R 92 each independently represents a hydrogen atom, a halogen atom, a carboxyl group, a sulfonic acid group, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms; R 93 and R 94 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, W 1 and W 2 are each independently a single bond, -C(R 95 )(R 96 )-(R 95 and R 96 each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R 95and R 96 When both are alkyl groups, they may be bonded to each other to form a ring together with the carbon atoms to which they are attached. 97 )-(R 97 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; 1 and X 2 each independently represents a single bond, an alkylene group having 1 to 10 carbon atoms, or a group represented by formula (14). [ka] (In the formula, R 98 ~R 101 each independently represents a hydrogen atom, a halogen atom, a carboxyl group, a sulfonic acid group, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms; Y 1 and Y 2 each independently represents a single bond or an alkylene group having 1 to 10 carbon atoms.)} 2. A protective film-forming composition for a transparent conductive film, wherein the fluorine atom-containing arylamino group is represented by formula (15). [ka] (In the formula, R 102 represents a fluorine atom or a fluoroalkyl group having 1 to 10 carbon atoms. 3. A protective film-forming composition for a transparent conductive film according to 2, wherein the fluorine atom-containing arylamino group is represented by formula (16). [ka] (In the formula, R 102 represents the same meaning as above.) 4. The above R 102 a perfluoroalkyl group having 1 to 10 carbon atoms; 5. A protective film-forming composition for a transparent conductive film, wherein Ar is any one of 1 to 4 represented by formula (17): [ka] 6. The protective film-forming composition for a transparent conductive film according to any one of 1 to 5, wherein the ultraviolet absorber is a triazine-based or benzotriazole-based ultraviolet absorber. 7. The protective film-forming composition for a transparent conductive film according to any one of 1 to 6, wherein the crosslinking agent A contains a polyfunctional (meth)acrylic compound. 8. A protective film-forming composition for a transparent conductive film according to any one of 1 to 7, which contains a crosslinking agent B having a molecular weight of less than 1,000. 9. The protective film-forming composition for a transparent conductive film according to 8, wherein the crosslinking agent B contains a polyfunctional (meth)acrylic compound. 10. A protective film-forming composition for a transparent conductive film according to any one of 1 to 9, which contains a solvent. 11. A protective film for a transparent conductive film obtained from the protective film-forming composition for a transparent conductive film according to any one of 1 to 10. 12. 11. Protective film for transparent conductive film, which is for transparent conductive film having conductive nanostructure; 13. The protective film for a transparent conductive film of 12, wherein the conductive nanostructure is a silver nanowire. 14. A transparent electrode comprising a transparent conductive film and a protective film for the transparent conductive film 11 formed on the transparent conductive film. 15. An electronic device comprising a transparent conductive film and a protective film for the transparent conductive film 11 formed on the transparent conductive film. 16. 15 Electronic Devices that are Organic Electroluminescent Displays to provide. [Effects of the Invention]

[0009] The protective film formed using the protective film-forming composition for transparent conductive film of the present invention has excellent light resistance, as well as high transparency and refractive index. Therefore, when used as a protective film for transparent conductive films such as ITO and silver nanowires, it is possible to improve visibility and suppress deterioration thereof. [Brief explanation of the drawings]

[0010] [Figure 1] FIG. 1 is a 1H-NMR spectrum of the polymer compound [4] obtained in Synthesis Example 1. DETAILED DESCRIPTION OF THE INVENTION

[0011] [Triazine ring-containing hyperbranched polymer] The protective film-forming composition for a transparent conductive film according to the present invention contains a triazine ring-containing hyperbranched polymer containing a repeating unit represented by the following formula (1).

[0012] [ka]

[0013] In the above formula, R and R' each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group, but from the viewpoint of further increasing the refractive index, it is preferable that both are hydrogen atoms. In the present invention, the number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 20. In consideration of further improving the heat resistance of the polymer, the number of carbon atoms is more preferably 1 to 10, and even more preferably 1 to 3. In addition, the structure may be any of linear, branched, and cyclic.

[0014] Specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, s-butyl, t-butyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-Methyl-cyclobutyl, 1,2-dimethyl-cyclopropyl, 2,3-dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl- n-Butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl-cyclobutyl, 2,4-dimethyl Examples thereof include 1-n-ethyl-cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-isopropyl-cyclopropyl, 2-isopropyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl, and 2-ethyl-3-methyl-cyclopropyl groups.

[0015] The number of carbon atoms in the alkoxy group is not particularly limited, but is preferably 1 to 20. In consideration of further improving the heat resistance of the polymer, the number of carbon atoms is more preferably 1 to 10, and even more preferably 1 to 3. The structure of the alkyl moiety may be linear, branched, or cyclic.

[0016] Specific examples of the alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, s-butoxy, t-butoxy, n-pentoxy, 1-methyl-n-butoxy, 2-methyl-n-butoxy, 3-methyl-n-butoxy, 1,1-dimethyl-n-propoxy, 1,2-dimethyl-n-propoxy, 2,2-dimethyl-n-propoxy, 1-ethyl-n-propoxy, n-hexyloxy, 1-methyl-n-pentyloxy, 2-methyl-n-pentyloxy, and 3-methyl-n-pentyloxy. Examples thereof 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.

[0017] The number of carbon atoms in the aryl group is not particularly limited, but is preferably 6 to 40, and in consideration of further improving the heat resistance of the polymer, the number of carbon atoms is more preferably 6 to 16, and even more preferably 6 to 13. Specific examples of the aryl group include phenyl, o-chlorophenyl, m-chlorophenyl, p-chlorophenyl, o-fluorophenyl, p-fluorophenyl, o-methoxyphenyl, p-methoxyphenyl, p-nitrophenyl, p-cyanophenyl, α-naphthyl, β-naphthyl, o-biphenylyl, m-biphenylyl, p-biphenylyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, and 9-phenanthryl groups.

[0018] The number of carbon atoms in the aralkyl group is not particularly limited, but preferably 7 to 20 carbon atoms, and the alkyl portion thereof may be linear, branched, or cyclic. Specific examples thereof include benzyl, p-methylphenylmethyl, m-methylphenylmethyl, o-ethylphenylmethyl, m-ethylphenylmethyl, p-ethylphenylmethyl, 2-propylphenylmethyl, 4-isopropylphenylmethyl, 4-isobutylphenylmethyl, and α-naphthylmethyl groups.

[0019] The above Ar represents at least one selected from the group represented by formulas (2) to (13).

[0020] [ka]

[0021] Above R 1 ~R 92 each independently represents a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group having 1 to 10 carbon atoms which may have a branched structure, or an alkoxy group having 1 to 10 carbon atoms which may have a branched structure; R 93 and R 94 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a branched structure, W 1 and W 2 are each independently a single bond, CR 95 R 96 (R 95 and R96 each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a branched structure (however, these may be joined together to form a ring), C=O, O, S, SO, SO2, or NR 97 (R 97 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a branched structure. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The alkyl group and alkoxy group include the same as those mentioned above. Also, X 1 and X 2 each independently represents a single bond, an alkylene group having 1 to 10 carbon atoms which may have a branched structure, or a group represented by formula (14).

[0022] [ka]

[0023] Above R 98 ~R 101 each independently represents a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group having 1 to 10 carbon atoms which may have a branched structure, or an alkoxy group having 1 to 10 carbon atoms which may have a branched structure; Y 1 and Y 2 each independently represents a single bond or an alkylene group having 1 to 10 carbon atoms and which may have a branched structure. Examples of these halogen atoms, alkyl groups and alkoxy groups are the same as those mentioned above. Examples of the alkylene group having 1 to 10 carbon atoms and which may have a branched structure include methylene, ethylene, propylene, trimethylene, tetramethylene, and pentamethylene groups.

[0024] Among these, R 1 ~R 92 and R 98 ~R 101is preferably a hydrogen atom, a halogen atom, a sulfo group, an alkyl group having 1 to 5 carbon atoms which may have a branched structure, or an alkoxy group having 1 to 5 carbon atoms which may have a branched structure, and more preferably a hydrogen atom.

[0025] In particular, Ar is preferably at least one of the aryl groups represented by formulas (2), (5) to (13), and more preferably at least one of the aryl groups represented by formulas (2), (5), (7), (8), and (11) to (13). Specific examples of the aryl groups represented by formulas (2) to (13) include, but are not limited to, those represented by the following formulas:

[0026] [ka]

[0027] Among these, aryl groups represented by the following formula are more preferred because they can give polymers with higher refractive indexes.

[0028] [ka]

[0029] In particular, in consideration of further increasing the solubility of the polymer in organic solvents such as low-polarity solvents, Ar is preferably a m-phenylene group represented by formula (17).

[0030] [ka]

[0031] The triazine ring-containing hyperbranched polymer used in the present invention has at least one triazine ring terminal, and at least a portion of this triazine ring terminal is capped with a fluorine atom-containing arylamino group. The aryl group may be the same as those mentioned above, with a phenyl group being particularly preferred. Examples of the fluorine atom-containing group include a fluorine atom and a fluorine atom-containing hydrocarbon group such as a fluoroalkyl group, with a fluorine atom and a fluoroalkyl group having 1 to 10 carbon atoms being preferred. The fluoroalkyl group having 1 to 10 carbon atoms may be linear, branched, or cyclic, and examples thereof include a trifluoromethyl group, a pentafluoroethyl group, a 2,2,2-trifluoroethyl group, a heptafluoropropyl group, a 2,2,3,3,3-pentafluoropropyl group, a 2,2,3,3-tetrafluoropropyl group, a 2,2,2-trifluoro-1-(trifluoromethyl)ethyl group, a nonafluorobutyl group, a 4,4,4-tri ... Examples thereof include a methyl group, an undecafluoropentyl group, a 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, a 2,2,3,3,4,4,5,5-octafluoropentyl group, a tridecafluorohexyl group, a 2,2,3,3,4,4,5,5,6,6,6-undecafluorohexyl group, a 2,2,3,3,4,4,5,5,6,6-decafluorohexyl group, and a 3,3,4,4,5,5,6,6,6-nonafluorohexyl group.

[0032] In particular, in consideration of increasing the solubility of the triazine ring-containing hyperbranched polymer in low-polarity solvents while maintaining the refractive index, a perfluoroalkyl group having 1 to 10 carbon atoms is preferred, and a perfluoroalkyl group having 1 to 5 carbon atoms is more preferred, with a trifluoromethyl group being the most suitable.

[0033] The number of fluorine atom-containing groups is not particularly limited and can be any number that can be substituted on the aryl group. However, taking into consideration the balance between maintaining the refractive index and solubility in the solvent, the number is preferably 1 to 4, more preferably 1 or 2, and even more preferably 1.

[0034] Suitable fluorine atom-containing arylamino groups include those represented by formula (15), and particularly preferred are those represented by formula (16) having a fluorine atom-containing group at the para position relative to the amino group.

[0035] [ka] (In the formula, R 102 represents a fluorine atom or a fluoroalkyl group having 1 to 10 carbon atoms.

[0036] [ka] (In the formula, R 102 has the same meaning as above.)

[0037] Specific examples of fluorine atom-containing arylamino groups include, but are not limited to, those represented by the following formulas:

[0038] [ka]

[0039] The fluorine atom-containing arylamino group can be introduced by using a corresponding fluorine atom-containing arylamino compound in the production method described below. Specific examples of fluorine atom-containing arylamino compounds include 4-fluoroaniline, 4-trifluoromethylaniline, and 4-pentafluoroethylaniline.

[0040] In the present invention, particularly suitable triazine ring-containing hyperbranched polymers include those represented by formulas (18) to (21).

[0041] [ka] (In the formula, R, R′, R 1 ~R 4 , and R 102 has the same meaning as above.)

[0042] [ka] (In the formula, R 1 ~R 4 and R 102has the same meaning as above.)

[0043] [ka] (In the formula, R 102 has the same meaning as above.)

[0044] [ka] (In the formula, R 102 has the same meaning as above.)

[0045] The weight average molecular weight of the triazine ring-containing hyperbranched polymer is not particularly limited, but is preferably 500 to 500,000, more preferably 500 to 100,000, and is preferably 2,000 or more in order to further improve heat resistance and reduce shrinkage, and is preferably 50,000 or less, more preferably 30,000 or less, and even more preferably 10,000 or less in order to further increase solubility and reduce the viscosity of the resulting solution. The weight average molecular weight in the present invention is an average molecular weight obtained by gel permeation chromatography (hereinafter referred to as GPC) analysis in terms of standard polystyrene.

[0046] The triazine ring-containing hyperbranched polymer of the present invention can be produced in accordance with the method disclosed in Patent Document 1 mentioned above. For example, as shown in Scheme 1 below, a triazine ring-containing hyperbranched polymer (20) can be obtained by reacting a triazine compound (22) with an aryldiamino compound (23) in an appropriate organic solvent, followed by reaction with a fluorine atom-containing aniline compound (24) as an end-capping agent.

[0047] [ka] (In the formula, each X independently represents a halogen atom, and R 102 has the same meaning as above.)

[0048] In the above reaction, the charging ratio of the aryldiamino compound (23) is arbitrary as long as the target polymer is obtained, but the ratio is preferably 0.01 to 10 equivalents, more preferably 1 to 5 equivalents, of the aryldiamino compound (23) relative to 1 equivalent of the triazine compound (22). The aryldiamino compound (23) may be added neat or in the form of a solution dissolved in an organic solvent. However, the latter method is preferred in view of ease of operation and reaction control. The reaction temperature may be appropriately set within the range from the melting point to the boiling point of the solvent used, and is preferably about -30 to 150°C, more preferably -10 to 100°C.

[0049] The organic solvent can be any of various solvents commonly used in this type of reaction, and examples thereof include tetrahydrofuran, dioxane, dimethyl sulfoxide; amide solvents such as N,N-dimethylformamide, N-methyl-2-pyrrolidone, tetramethylurea, hexamethylphosphoramide, N,N-dimethylacetamide, 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-dimethylisobutyramide, N-methylformamide, and N,N'-dimethylpropyleneurea; and mixed solvents thereof. Among these, N,N-dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, and mixtures thereof are preferred, and N,N-dimethylacetamide and N-methyl-2-pyrrolidone are particularly preferred.

[0050] In the first step of the reaction in Scheme 1, various bases that are commonly used may be added during or after the polymerization. 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, and N-methylmorpholine. The amount of the base added is preferably 1 to 100 equivalents relative to 1 equivalent of the triazine compound (22), more preferably 1 to 10 equivalents. These bases may be used in the form of an aqueous solution. It is preferred that no raw material components remain in the resulting polymer, but some raw materials may remain as long as the effects of the present invention are not impaired. After the reaction is complete, the product can be easily purified by reprecipitation or the like.

[0051] As a method for terminal blocking using the fluorine atom-containing aniline compound (24), a known method may be used. In this case, the amount of the end-capping agent used is preferably about 0.05 to 10 equivalents, more preferably 0.1 to 5 equivalents, and even more preferably 0.5 to 2 equivalents, per equivalent of halogen atoms derived from the excess triazine compound not used in the polymerization reaction. The reaction solvent and reaction temperature may be the same as those described for the first step reaction in Scheme 1 above, and the end-capping agent may be charged simultaneously with the aryldiamino compound (23). An arylamino compound having no fluorine atom may be used and end-capping may be performed with two or more groups. Examples of the aryl group in this arylamino compound having no substituent include the same as those described above.

[0052] [Crosslinking agent] The composition of the present invention contains a crosslinking agent A having a molecular weight of 1,000 or more, preferably 1,200 or more, and more preferably 1,500 or more, which can increase the film density of the protective film and improve its resistance to high temperatures and high humidity. The composition of the present invention preferably contains crosslinking agent B having a molecular weight of less than 1,000 in addition to crosslinking agent A. Addition of crosslinking agent B can further increase the film density of the protective film and further improve resistance to high temperatures and high humidity. The molecular weight of crosslinking agent B is preferably 900 or less, more preferably 800 or less.

[0053] Examples of crosslinking agents A and B include melamine compounds having a crosslinking group such as a methylol group or a methoxymethyl group as a crosslinking group, substituted urea compounds, compounds containing a crosslinking group such as an epoxy group or an oxetane group, compounds containing a blocked isocyanate, compounds containing an acid anhydride, compounds containing a (meth)acryloyl group, aminoplast compounds, and phenoplast compounds. Among these, compounds containing an epoxy group, a blocked isocyanate group, or a (meth)acrylic group are preferred from the viewpoint of heat resistance and storage stability, and particularly preferred are compounds having a blocked isocyanate group, and polyfunctional epoxy compounds and / or polyfunctional (meth)acrylic compounds that provide a photocurable composition without the use of an initiator. These polyfunctional compounds must have at least two cross-linking groups, but preferably have three or more cross-linking groups.

[0054] The polyfunctional epoxy compound is not particularly limited as long as it has two or more epoxy groups per molecule. Specific examples thereof include tris(2,3-epoxypropyl)isocyanurate, 1,4-butanediol diglycidyl ether, 1,2-epoxy-4-(epoxyethyl)cyclohexane, glycerol triglycidyl ether, diethylene glycol diglycidyl ether, 2,6-diglycidylphenyl glycidyl ether, 1,1,3-tris[p-(2,3-epoxypropoxy)phenyl]propane, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, 4,4'-methylenebis(N,N-diglycidylaniline), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, trimethylolethane triglycidyl ether, bisphenol-A diglycidyl ether, and pentaerythritol polyglycidyl ether.

[0055] Commercially available products include epoxy resins having at least two epoxy groups, such as YH-434 and YH434L (manufactured by Tohto Kasei Co., Ltd.); epoxy resins having a cyclohexene oxide structure, such as Epolead GT-401, GT-403, GT-301, GT-302, Celloxide 2021, and 3000 (manufactured by Daicel Chemical Industries, Ltd.); bisphenol A type epoxy resins, such as Epicoat (now jER) 1001, 1002, 1003, 1004, 1007, 1009, 1010, and 828 (all manufactured by Japan Epoxy Resins Co., Ltd.); and bisphenol F type epoxy resin, such as Epicoat (now jER) 807. (manufactured by Japan Epoxy Resins Co., Ltd.), phenol novolac epoxy resins Epicoat (now jER) 152 and 154 (both manufactured by Japan Epoxy Resins Co., Ltd.), EPPN201 and 202 (both manufactured by Nippon Kayaku Co., Ltd.), cresol novolac epoxy resins EOCN-102, 103S, 104S, 1020, 1025 and 1027 (all manufactured by Nippon Kayaku Co., Ltd.), Epicoat (now jER) 180S75 (manufactured by Japan Epoxy Resins Co., Ltd.), alicyclic epoxy resins Denacol EX-252 (manufactured by Nagase ChemteX Corporation), CY175, CY177 and CY179 (all manufactured by CIBA-GEIGY Other examples that can be used include resins such as Araldite CY-182, CY-192, and CY-184 (manufactured by CIBA-GEIGY AG), Epiclon 200 and 400 (manufactured by DIC Corporation), Epicoat (now jER) 871 and 872 (manufactured by Japan Epoxy Resins Co., Ltd.), ED-5661 and ED-5662 (manufactured by Celanese Coatings Co., Ltd.), and aliphatic polyglycidyl ethers such as Denacol EX-611, EX-612, EX-614, EX-622, EX-411, EX-512, EX-522, EX-421, EX-313, EX-314, and EX-321 (manufactured by Nagase ChemteX Corporation).

[0056] The polyfunctional (meth)acrylic compound is not particularly limited as long as it has two or more (meth)acrylic groups in one molecule. Specific examples thereof include ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, ethoxylated glycerin tri(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, ethoxylated dipentaerythritol hexa(meth)acrylate, ethoxylated isocyanuric acid tri(meth)acrylate, tris(2-(meth)acryloyloxyethyl)isocyanurate, ε-caproic acid tri(meth)acrylate, ... ethylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, ethylene glycol di( Examples of suitable acrylate copolymers include lactone-modified tris-(2-(meth)acryloxyethyl)isocyanurate, polyglycerin monoethylene oxide poly(meth)acrylate, polyglycerin polyethylene glycol poly(meth)acrylate, dipentaerythritol hexa(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, and 1,6-hexanediol di(meth)acrylate.

[0057] Polyfunctional (meth)acrylic compounds are commercially available, and specific examples thereof include NK Ester A-200, A-400, A-600, A-1000, A-9300, A-9300-1CL, A-TMPT, A-TMM-3, A-TMM-3L, A-TMP, A-TMMT, A-DPH, UA-53H, 1G, 2G, 3G, and 4G. , 9G, 14G, 23G, ABE-300, A-BPE-4, A-BPE-6, A-BPE-10, A-BPE-20, 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-3E O, A-TMPT-9EO, ATM-4E, ATM-35E, AT-20E (manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD (registered trademark) DPEA-12, PEG400DA , THE-330, RP-1040 (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, M-405, M-406, M-408, KAYARAD (registered trademark) DPHA, NPGDA, PET30 (manufactured by Nippon Kayaku Co., Ltd.), NK ester Examples of such copolymers include A-DPH, A-TMPT, A-DCP, A-HD-N, TMPT, DCP, NPG, and HD-N (all manufactured by Shin-Nakamura Chemical Co., Ltd.), NK Oligo U-15HA (manufactured by Shin-Nakamura Chemical Co., Ltd.), NK Polymer Vanaresin GH-1203 (manufactured by Shin-Nakamura Chemical Co., Ltd.), EBECRYL 11, 40, 135, 140, 145, 150, 180, 1142, OTA480, IRR214-K, and PEG400DA-D (all manufactured by Daicel-Allnex Co., Ltd.).

[0058] In addition, as polyfunctional (meth)acrylic compounds, polyfunctional urethane acrylates such as EBECRYL 204, 205, 210, 215, 220, 230, 244, 245, 270, 284, 285, 264, 265, 294 / 25HD, 1259, 1290, 4820, 4858, 5120, 8210, 8254, 8301R, 8405, and 84 65, 8296, 8307, 8402, 8311, 8411, 8701, 8800, 8804, 8807, 9260, 9270, 9277EA, KRM7735, 8200, 8452, 8528, 8667, 8904 (all manufactured by Daicel-Allnex Co., Ltd.), UV-1700B, UV-6300B, UV-7510B, UV-7550V, UV-7550 B, UV-7600B, UV-7605B, UV-7610B, UV-7620EA, UV-7630B, UV-7640B, UV-7650B (all manufactured by Nippon Synthetic Chemical Industry Co., Ltd.); multifunctional polyester acrylates EBECRYL 436, 438, 446, 450, 524, 525, 800, 810, 811, 812, 1830, 846, 851, and 85 2, 853, 1870, 884, and 885 (all manufactured by Daicel-Allnex Co., Ltd.); epoxy acrylates EBECRYL 600, 605, 645, 648, 860, 1606, 3500, 3603, 3608, 3700, 3701, 3702, 3703, 3708, and 6040 (all manufactured by Daicel-Allnex Co., Ltd.) can also be used.

[0059] The acid anhydride compound is not particularly limited as long as it is a carboxylic acid anhydride obtained by dehydration condensation of two molecules of carboxylic acid. Specific examples thereof 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, and the like, which have one acid anhydride group in the molecule; 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, Examples of the dianhydride include those having two acid anhydride groups in the molecule, such as 8-tetracarboxylic acid dianhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid dianhydride, 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.

[0060] The compound containing a blocked isocyanate is not particularly limited as long as it has two or more blocked isocyanate groups per molecule, in which the isocyanate group (-NCO) is blocked with an appropriate protecting group, and when exposed to high temperatures during thermal curing, the protecting group (blocking moiety) is thermally dissociated and removed, and the resulting isocyanate group undergoes a crosslinking reaction with the resin. For example, a compound having two or more groups represented by the following formula per molecule (note that these groups may be the same or different from each other) may be mentioned.

[0061] [ka] (In the formula, R b represents an organic group in the block portion.)

[0062] Such a compound can be obtained, for example, by reacting a compound having two or more isocyanate groups in one molecule with an appropriate blocking agent.

[0063] Examples of compounds having two or more isocyanate groups in one molecule include polyisocyanates such as isophorone diisocyanate, 1,6-hexamethylene diisocyanate, methylenebis(4-cyclohexylisocyanate), and trimethylhexamethylene diisocyanate, as well as dimers and trimers thereof, and reaction products of these with diols, triols, diamines, or triamines.

[0064] 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.

[0065] Compounds containing blocked isocyanates are also commercially available, and specific examples thereof include B-830, B-815N, B-842N, B-870N, B-874N, B-882N, B-7005, B-7030, B-7075, and B-5010 (all manufactured by Mitsui Chemicals Polyurethanes, Inc.), Duranate (registered trademark) 17B-60PX, TPA-B80E, MF-B60X, MF-K60X, and E402-B80T (all manufactured by Asahi Kasei Chemicals Corporation), and Karenz MOI-BM (registered trademark) (all manufactured by Showa Denko K.K.).

[0066] The aminoplast compound is not particularly limited as long as it has two or more methoxymethylene groups per molecule. Examples include melamine compounds such as the Cymel series, including hexamethoxymethylmelamine CYMEL (registered trademark) 303, tetrabutoxymethylglycoluril 1170, and tetramethoxymethylbenzoguanamine 1123 (all manufactured by Nippon Cytec Industries Co., Ltd.), and the Nikalac series, including methylated melamine resins Nikalac (registered trademark) MW-30HM, MW-390, MW-100LM, and MX-750LM, and methylated urea resins MX-270, MX-280, and MX-290 (all manufactured by Sanwa Chemical Co., Ltd.).

[0067] The oxetane compound is not particularly limited as long as it has two or more oxetanyl groups in one molecule, and examples thereof include OXT-221, OX-SQ-H, and OX-SC (all manufactured by Toagosei Co., Ltd.), which contain oxetane groups.

[0068] Phenoplast compounds have two or more hydroxymethylene groups per molecule, and when exposed to high temperatures during thermal curing, they undergo a crosslinking reaction via a dehydration condensation reaction with the hyperbranched polymer used in 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.

[0069] Phenoplast compounds are also available as commercially available products, 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.).

[0070] The crosslinking agent A preferably has a molecular weight of 1,000 or more due to a long chain length between crosslink-forming groups, and specifically preferably has a polyether structure, polyester structure, polyurethane structure, or the like, which results in a long chain length between crosslink-forming groups. Among the above-mentioned crosslinking agents, examples of crosslinking agent A include NK Ester A-GLY-20E, ATM-35E, AT-20E, 23G, A-BPE-20, BPE-900, and BPE-1300N (all manufactured by Shin-Nakamura Chemical Co., Ltd.), EBECRYL 204, EBECRYL 205, EBECRYL 210, EBECRYL 215, EBECRYL 230, EBECRYL 244, EBECRYL 245, EBECRYL 270, EBECRYL 284, EBECRYL 285, EBECRYL 264, EBECRYL 265, EBECRYL 294 / 25HD, EBECRYL 1259, EBECRYL 1290, EBECRYL 4820, EBECRYL 8254, EBECRYL 8301R, EBECRYL 8405, EBECRYL 8465, EBECRYL 8296, EBECRYL 8307, EBECRYL 8411, EBECRYL 8701, EBECRYL 8800, EBECRYL 8804, EBECRYL 8805, EBECRYL 8806, EBECRYL 8807 / 25HD, EBECRYL 1259, EBECRYL 1290, EBECRYL 4820, EBECRYL 8254, EBECRYL 8301R, EBECRYL 8405, EBECRYL 8465, EBECRYL 8296, EBECRYL 8307, EBECRYL 8 9260, 9277EA, KRM8200, 8452, 8528, 8667, 8904, 436, 438, 446, 450, 525, 1830, 846, 1870, 884, 885, 860, and 3708 (all manufactured by Daicel-Allnex Co., Ltd.), UV-1700B, UV-6300B, UV-7510B, UV-7550V, UV-7550B, UV-7600B, UV-7605B, UV-7610B, UV-7620EA, UV-7630B, UV-7640B, and UV-7650B (all manufactured by Nippon Synthetic Chemical Industry Co., Ltd.). Of these, NK Ester A-GLY-20E, NK Ester ATM-35E, and the like are preferred.

[0071] Among the above-mentioned crosslinking agents, examples of crosslinking agent B having a molecular weight of less than 1,000 include Aronix M-303, M-305, M-305, M-306, M-400, M-402, M-403, M-404, M-405, M-406, M-450, and M-452 (all manufactured by Toagosei Co., Ltd.), NK Ester A-9300, A-9300-1CL, A-TMM-3, and A-TMM -3L, A-TMPT, A-TMP, A-TMMT, A-DPH, 1G, 2G, 3G, 4G, 9G, 14G, ABE-300, A-BPE-4, A-BPE-6, A -BPE-10, A-BPE-20, A-BPE-30, BPE-80N, BPE-100N, BPE-200, BPE-500 (manufactured by Shin-Nakamura Chemical Co., Ltd.), EBECRYL Examples of suitable amines include 11, 40, 135, 140, 145, 150, 180, 800, 853, 860, 1142, 4858, 5129, 8210, 600, 605, 645, 648, 1606, 3500, 3603, 3608, 3700, 3701, 3702, 3703, and 6040OTA 480 (all manufactured by Daicel-Allnex Co., Ltd.), and KAYARAD DN-0075 (manufactured by Nippon Kayaku Co., Ltd.). Among these, Aronix M-303, M-305, M-305, M-306, M-400, M-402, M-403, M-404, M-405, M-406, M-450, and M-452 (all manufactured by Toagosei Co., Ltd.), NK Ester A-9300 and A-9300-1CL (all manufactured by Shin-Nakamura Chemical Co., Ltd.), and KAYARAD DN-0075 (manufactured by Nippon Kayaku Co., Ltd.) are preferred.

[0072] As the crosslinking agents A and B, a polyfunctional (meth)acrylic compound is preferred, since it can suppress the decrease in refractive index due to the incorporation of the crosslinking agent and the curing reaction proceeds quickly.

[0073] The crosslinking agents A and B may be used either alone or in combination of two or more. The amount of crosslinking agent A used is preferably 0.1 to 30 parts by mass per 100 parts by mass of the triazine ring-containing hyperbranched polymer, but in consideration of solvent resistance, the lower limit is preferably 1 part by mass, more preferably 5 parts by mass, and in consideration of controlling the refractive index, the upper limit is preferably 25 parts by mass, more preferably 20 parts by mass. The amount of crosslinking agent B used is preferably 100 to 3000 parts by mass, more preferably 1000 to 2000 parts by mass, per 100 parts by mass of crosslinking agent A, from the viewpoints of further improving the optical properties of the transparent conductive film and preventing a significant decrease in the refractive index.

[0074] [UV absorber] The composition of the present invention contains an ultraviolet absorber in addition to the above-described triazine ring-containing hyperbranched polymer and crosslinking agent, which can suppress deterioration of the triazine ring-containing hyperbranched polymer in the cured film due to the influence of ultraviolet rays and improve light resistance. Examples of ultraviolet absorbers include organic compounds such as benzotriazole compounds, benzophenone compounds, triazine compounds, cyclic iminoester compounds, cyanoacrylate compounds, malonic acid ester compounds, and salicylic acid phenyl ester compounds, and inorganic particles that absorb ultraviolet light such as titanium oxide particles, zinc oxide particles, and tin oxide particles. Among these, benzotriazole-based compounds and triazine-based compounds are preferred, and hydroxyphenylbenzotriazole-based compounds are more preferred, from the viewpoints of improving the weather resistance of the resulting cured film and preventing discoloration of the cured film.

[0075] Specific examples of the ultraviolet absorber include triazoles such as 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, and 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole; and benzophenones such as 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 2,2'-dihydroxy-4-methoxybenzophenone. ;[2-(4,6-diphenyl-1,3,5-triazin-2,2-yl)-5-[(hexyl)oxy]-phenol, 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[( Hydroxyphenyltriazines such as 2-hydroxy-3-(2'-ethyl)hexyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine; oxalic acid anilides such as (2-ethoxy-2'-ethyloxalic acid bisanilide); phenyl salicylate, pt-butylphenyl salicylate Examples of suitable esters include salicylic acids such as silyl ester and p-octylphenyl salicylate; cyclic imino esters such as 2,2'-p-phenylenebis(3,1-benzoxazin-4-one); cyanoacrylates such as 1,3-bis[(2-cyano-3,3-diphenylacryloyl)oxy]-2,2-bis[[(2-cyano-3,3-diphenylacryloyl)oxy]methyl]propane; and malonic acid esters such as tetraethyl-2,2'-(1,4-phenylenedimethylidyne)bismalonate.

[0076] The ultraviolet absorber may be a commercially available product, and specific examples thereof include TINUVIN (registered trademark) PS, TINUVIN 99-2, TINUVIN 99-DW, TINUVIN 109, TINUVIN 328, TINUVIN 329, TINUVIN 384-2, TINUVIN 400, TINUVIN 400-DW, TINUVIN 405, TINUVIN 460, TINUVIN 477, TINUVIN 477-DW, TINUVIN 479, TINUVIN 900, TINUVIN 928, TINUVIN 1130, and TINUVIN 111FDL (all manufactured by BASF Japan Ltd.), ADK STAB LA-29, LA-31, LA-31RG, LA-31G, LA-32, and LA- 36RG, LA-46, 1413, LA-F70 (all manufactured by ADEKA Corporation), New Coat UVA-101, UVA-102, UVA-103, UVA-104, Vanalesin UVA-5080, UVA-5080(OHV20), UVA-55T, UVA-5MHB, UVA-7075, UVA-7075(OHV20), UVA-73T (all manufactured by Shin-Nakamura Chemical Co., Ltd.), RUVA-93 (manufactured by Otsuka Chemical Co., Ltd.), etc.

[0077] The above ultraviolet absorbents may be used alone or in combination of two or more kinds. The amount of ultraviolet absorber used is preferably 0.1 to 100 parts by mass per 100 parts by mass of the triazine ring-containing hyperbranched polymer. However, in order to further improve the light resistance of the resulting cured film, the lower limit is preferably 1 part by mass, more preferably 5 parts by mass. Furthermore, in order to prevent a decrease in the refractive index of the cured film and coloration, the upper limit is preferably 30 parts by mass, more preferably 20 parts by mass.

[0078] [solvent] It is preferable to add various solvents to the composition of the present invention to dissolve the triazine ring-containing hyperbranched polymer. In this case, the solvent may be the same as or different from the solvent used in polymerization. The solvent is not particularly limited as long as it does not impair compatibility with the polymer.

[0079] Specific examples of usable 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 methyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol 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-octanol, ethylene glycol Licorice, 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, cyclohexanone, ethyl acetate, isopropyl acetate ethanol, n-propyl acetate, isobutyl acetate, n-butyl acetate, ethyl lactate, methanol, ethanol, isopropanol, tert-butanol, allyl alcohol, n-propanol, 2-methyl-2-butanol, isobutanol, n-butanol, 2-methyl-1-butanol, 1-pentanol, 2-methyl-1-pentanol, 2-ethylhexanol, 1-methoxy-2-propanol, tetrahydrofuran, 1,4-dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, 1,Examples of the amine include 3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, and N-cyclohexyl-2-pyrrolidinone. These may be used alone or in combination of two or more.

[0080] In this case, the solid content concentration in the composition is not particularly limited as long as it does not affect storage stability, and may be appropriately set depending on the target film thickness. Specifically, from the viewpoints of solubility and storage stability, the solid content concentration is preferably 0.1 to 50 mass %, more preferably 0.2 to 40 mass %.

[0081] [Initiator] The composition of the present invention can also contain an initiator appropriate for each crosslinking agent. As mentioned above, when a polyfunctional epoxy compound and / or a polyfunctional (meth)acrylic compound is used as the crosslinking agent, photocuring proceeds to give a cured film without the use of an initiator, but in this case, the use of an initiator is not an issue.

[0082] When a polyfunctional epoxy compound is used as a crosslinking agent, a photoacid generator or a photobase generator can be used. The photoacid generator may be appropriately selected from known photoacid generators, and for example, onium salt derivatives such as diazonium salts, sulfonium salts, and iodonium salts may be used. Specific examples thereof include aryl diazonium salts such as phenyl diazonium hexafluorophosphate, 4-methoxyphenyl diazonium hexafluoroantimonate, and 4-methylphenyl diazonium hexafluorophosphate; diaryliodonium salts such as diphenyl iodonium hexafluoroantimonate, di(4-methylphenyl) iodonium hexafluorophosphate, and di(4-tert-butylphenyl) iodonium hexafluorophosphate; triphenyl sulfonium hexafluoroantimonate, tris(4-methoxyphenyl) sulfonium hexafluorophosphate, diphenyl-4-thiophenoxyphenyl sulfonium hexafluoroantimonate, and diphenyl-4-thiophenoxyphenyl sulfonium hexafluorophosphate. and triarylsulfonium salts such as 4,4'-bis(diphenylsulfonio)phenylsulfide-bishexafluoroantimonate, 4,4'-bis(diphenylsulfonio)phenylsulfide-bishexafluorophosphate, 4,4'-bis[di(β-hydroxyethoxy)phenylsulfonio]phenylsulfide-bishexafluoroantimonate, 4,4'-bis[di(β-hydroxyethoxy)phenylsulfonio]phenylsulfide-bis-hexafluorophosphate, 4-[4'-(benzoyl)phenylthio]phenyl-di(4-fluorophenyl)sulfonium hexafluoroantimonate, and 4-[4'-(benzoyl)phenylthio]phenyl-di(4-fluorophenyl)sulfonium hexafluorophosphate.

[0083] These onium salts may be commercially available products, and specific examples thereof include San-Aid SI-60, SI-80, SI-100, SI-60L, SI-80L, SI-100L, SI-L145, SI-L150, SI-L160, SI-L110, and SI-L147 (all manufactured by Sanshin Chemical Industry Co., Ltd.), UVI-6950, UVI-6970, UVI-6974, UVI-6990, and UVI-6992 (all manufactured by Union Carbide Corporation), CPI-100P, CPI-100A, CPI-200K, and CPI-200S (all manufactured by San-Apro Co., Ltd.), and Adeka Optomer SP-150 and SP-151. , SP-170, SP-171 (all manufactured by Asahi Denka Kogyo Co., Ltd.), Irgacure 261 (manufactured by BASF), CI-2481, CI-2624, CI-2639, CI-2064 (all manufactured by Nippon Soda Co., Ltd.), CD-1010, CD-1011, CD-1012 (all manufactured by Sartomer), DS-100, DS-101, DAM-101, DAM-102, DAM-105, DAM-201, DSM-301, NAI-100, NAI-101, NAI-105, NAI-106, SI-100, SI-101, SI-105, SI-106, PI-105, NDI-105, BENZOIN Examples of suitable antibacterial agents include TOSYLATE, MBZ-101, MBZ-301, PYR-100, PYR-200, DNB-101, NB-101, NB-201, BBI-101, BBI-102, BBI-103, and BBI-109 (all manufactured by Midori Chemical Co., Ltd.), PCI-061T, PCI-062T, PCI-020T, and PCI-022T (all manufactured by Nippon Kayaku Co., Ltd.), IBPF, and IBCF (manufactured by Sanwa Chemical Co., Ltd.).

[0084] The photobase generator may be appropriately selected from known ones, and examples thereof include Co-amine complex-based, oxime carboxylic acid ester-based, carbamic acid ester-based, and quaternary ammonium salt-based photobase generators. Specific examples thereof include 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-carbamoylhydroxylamide, O-carbamoyloxime, [[(2,6-dinitrobenzyl)oxy]carbonyl]cyclohexylamine, bis[[(2-nitrobenzyl)oxy]carbonyl]hexane-1,6-diamine, 4-(methylthiobenzoyl)-1-methyl-1-morpholinoethane, and (4-morpholinobenzoyl)-1-benzyl-1-dimethylamine. methylaminopropane, N-(2-nitrobenzyloxycarbonyl)pyrrolidine, hexaamminecobalt(III) tris(triphenylmethylborate), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2,6-dimethyl-3,5-diacetyl-4-(2'-nitrophenyl)-1,4-dihydropyridine, 2,6-dimethyl-3,5-diacetyl-4-(2',4'-dinitrophenyl)-1,4-dihydropyridine, and the like. Furthermore, commercially available photobase generators may be used, and specific examples thereof include TPS-OH, NBC-101, and ANC-101 (all manufactured by Midori Chemical Co., Ltd.).

[0085] When a photoacid generator or photobase generator is used, it is preferably used in the range of 0.1 to 15 parts by mass, more preferably 1 to 10 parts by mass, per 100 parts by mass of the polyfunctional epoxy compound. If necessary, an epoxy resin curing agent may be blended in an amount of 1 to 100 parts by mass per 100 parts by mass of the polyfunctional epoxy compound.

[0086] On the other hand, when a polyfunctional (meth)acrylic compound is used, a photoradical polymerization initiator can be used. The photoradical polymerization initiator may be appropriately selected from known initiators, such as acetophenones, benzophenones, Michler's benzoyl benzoate, amyloxime ester, tetramethylthiuram monosulfide, and thioxanthones.

[0087] In particular, photocleavage-type photoradical polymerization initiators are preferred. Photocleavage-type photoradical polymerization initiators are described in "Latest UV Curing Technology" (page 159, published by Takasuki Kazuhiro, published by Technical Information Association, Inc., published in 1991).

[0088] Examples of commercially available photoradical polymerization initiators include those manufactured by BASF under the trade names Irgacure 127, 184, 369, 379, 651, 500, 819, 907, 784, 2959, OXE01, OXE02, CGI1700, CGI1750, CGI1850, CG24-61, and Darocur 1116 and 1173; those manufactured by BASF under the trade name Lucirin TPO; those manufactured by UCB under the trade name Ubecryl P36; and those manufactured by Fratelli Lamberti under the trade names Ezacure KIP150, KIP65LT, KIP100F, KT37, KT55, KTO46, and KIP75 / B.

[0089] When a photoradical polymerization initiator is used, it is preferably used in the range of 0.1 to 15 parts by mass, more preferably 0.1 to 10 parts by mass, per 100 parts by mass of the polyfunctional (meth)acrylate compound.

[0090] [Crosslinking accelerator] Furthermore, a polyfunctional thiol compound having two or more mercapto groups in the molecule may be added to the composition of the present invention for the purpose of promoting the reaction between the triazine ring-containing hyperbranched polymer and the crosslinking agent. Specifically, polyfunctional thiol compounds represented by the following formula are preferred.

[0091] [ka]

[0092] The above L represents a divalent to tetravalent organic group, preferably a divalent to tetravalent aliphatic group having 2 to 12 carbon atoms or a divalent to tetravalent heterocycle-containing group, and more preferably a divalent to tetravalent aliphatic group having 2 to 8 carbon atoms or a trivalent group having an isocyanuric acid skeleton (1,3,5-triazine-2,4,6(1H,3H,5H)-trione ring) represented by the following formula: The above n represents an integer of 2 to 4 corresponding to the valence of L.

[0093] [ka] (In the formula, "·" represents the bond to the oxygen atom.)

[0094] Specific compounds include 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, pentaerythritol tetrakis(3-mercaptobutyrate), trimethylolpropane tris(3-mercaptobutyrate), trimethylolethane tris(3-mercaptobutyrate), and the like. These polyfunctional thiol compounds are also available as commercially available products, such as Karenz MT-BD1, Karenz MT NR1, Karenz MT PE1, TPMB, and TEMB (all manufactured by Showa Denko KK). These polyfunctional thiol compounds may be used alone or in combination of two or more.

[0095] When a polyfunctional thiol compound is used, the amount added is not particularly limited as long as it does not adversely affect the resulting protective film, but in the present invention, the amount is preferably 0.01 to 10 mass %, and more preferably 0.1 to 6 mass %, based on 100 mass % of the solid content.

[0096] [Other ingredients] The film-forming composition of the present invention may contain other components, such as a leveling agent, a surfactant, etc., as long as the effects of the present invention are not impaired. Examples of leveling agents or surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkyl aryl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether; polyoxyethylene-polyoxypropylene block copolymers; sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate; polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as sorbitan acrylate; trade names: F-Top EF301, EF303, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd. (formerly JEMCO Co., Ltd.)), trade names: Megafac F171, F173, R-08, R-30, R-40, R-43, F-553, F-554, F-556, F-559, RS-75, RS-72-K (manufactured by DIC Corporation), Fluorad FC430, FC431 (manufactured by Sumitomo 3M Limited). Fluorine-based surfactants such as Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, and SC106 (manufactured by Asahi Glass Co., Ltd.); organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), BYK-302, BYK-307, BYK-322, BYK-323, BYK-330, BYK-333, BYK-370, BYK-375, and BYK-378 (manufactured by BYK Japan KK).

[0097] These may be used alone or in combination of two or more. The amount of the surfactant used is preferably 0.001 to 5 parts by mass, more preferably 0.01 to 5 parts by mass, and even more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the triazine ring-containing hyperbranched polymer. The above other components can be added at any step during the preparation of the composition of the present invention.

[0098] [Protective film for transparent conductive film] The protective film for a transparent conductive film of the present invention can be formed by applying the above-mentioned protective film-forming composition for a transparent conductive film to a transparent conductive film, heating the composition as needed to evaporate the solvent, and then heating or irradiating the composition with light. In this case, the thickness of the protective film is preferably 10 to 1,000 nm, more preferably 50 to 200 nm. The lower limit of the refractive index range of the protective film is preferably 1.45, more preferably 1.50, and even more preferably 1.55. The upper limit is not particularly limited, but is about 1.95 to 2.00.

[0099] The haze value of the transparent conductive film having the protective film of the present invention formed thereon is preferably 1.5% or less, more preferably 1.0% or less.

[0100] The composition may be applied by any method, and examples of methods that can be used include spin coating, dipping, flow coating, inkjet coating, spraying, bar coating, gravure coating, slit coating, roll coating, transfer printing, brush coating, blade coating, and air knife coating.

[0101] Examples of transparent conductive films include ITO films, IZO films, and transparent conductive films having conductive nanostructures such as metal nanoparticles, metal nanowires, and metal nanomesh. Transparent conductive films having conductive nanostructures such as metal nanoparticles, metal nanowires, and metal nanomesh are preferred. The metal constituting the conductive nanostructure is not particularly limited, but examples include silver, gold, copper, nickel, platinum, cobalt, iron, zinc, ruthenium, rhodium, palladium, cadmium, osmium, iridium, and alloys thereof. That is, transparent conductive films having silver nanoparticles, silver nanowires, silver nanomesh, gold nanoparticles, gold nanowires, gold nanomesh, copper nanoparticles, copper nanowires, copper nanomesh, and the like are preferred, with transparent conductive films having silver nanowires being particularly preferred.

[0102] The heating temperature is not particularly limited for the purpose of evaporating the solvent, and can be, for example, 40 to 400°C. The heating method is not particularly limited, and for example, the solvent can be evaporated using a hot plate or oven in an appropriate atmosphere such as air, an inert gas such as nitrogen, or a vacuum. The baking temperature and baking time can be selected according to the processing steps of the target electronic device, and baking conditions can be selected such that the physical properties of the resulting film conform to the required characteristics of the electronic device.

[0103] The conditions for light irradiation are not particularly limited, and appropriate irradiation energy and time may be selected depending on the triazine ring-containing hyperbranched polymer and crosslinking agent used. For example, 50 to 1,000 mJ / cm 2 The light irradiation is preferably carried out in air or an inert gas atmosphere such as nitrogen.

[0104] The protective film of the present invention is particularly suitable as a protective film for a transparent conductive film having a conductive nanostructure. Transparent conductive films having a conductive nanostructure tend to become cloudy due to the diffuse reflection of light caused by the conductive nanostructure, which can result in poor visibility. The protective film of the present invention has high transparency and refractive index, and can therefore prevent clouding caused by the diffuse reflection of light in transparent conductive films using conductive nanostructures, thereby improving visibility. Furthermore, the protective film has light resistance, high heat resistance, and resistance to high temperatures and humidity, which can also contribute to preventing deterioration of the transparent conductive film. [Example]

[0105] The present invention will be described in more detail below with reference to synthesis examples, production examples, examples, and comparative examples, but the present invention is not limited to the following examples. The measuring devices used in the examples are as follows.

[0106] [ 1 H-NMR] Equipment: Varian NMR System 400NB(400MHz) JEOL-ECA700(700MHz) Measurement solvent: DMSO-d6 Reference substance: tetramethylsilane (TMS) (δ 0.0 ppm) [GPC] Apparatus: Tosoh HLC-8200 GPC Column: Shodex KF-804L + KF-805L Column temperature: 40℃ Solvent: tetrahydrofuran (THF) Detector: UV (254 nm) Calibration curve: Standard polystyrene [Ellipsometer] Apparatus: J.A. Woollam Japan, Inc., multi-angle spectroscopic ellipsometer VASE [Xenon light resistance tester] Equipment: Q-SUN Xe-1-B manufactured by Q-Lab Corporation [Spectrophotometer] Device: Konica Minolta Japan, Inc. CM-3700A

[0107] The compounds used in the following examples are as follows: DPHA: Dipentaerythritol penta- and hexaacrylate (KAYARAD DN-0075, manufactured by Nippon Kayaku Co., Ltd.) ATM35E: Ethoxylated pentaerythritol tetraacrylate (NK Ester ATM-35E, manufactured by Shin-Nakamura Chemical Co., Ltd.) I2959: 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one (Irgacure 2959, manufactured by BASF Japan Ltd.) NR1: 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (KarenzMT NR1, manufactured by Showa Denko K.K.) F559: Surfactant (MEGAFAC F-559, manufactured by DIC Corporation) T900: UV absorber (BASF Japan Ltd., Tinuvin 900)

[0108] [1] Synthesis of triazine ring-containing hyperbranched polymers [Synthesis Example 1] Synthesis of polymer compound [4] [ka]

[0109] A 200 mL four-neck flask was charged with m-phenylenediamine [2] (6.00 g, 0.055 mol, AminoChem) and 78.88 g of dimethylacetamide (DMAc, Junsei Chemical Co., Ltd.). The atmosphere was then purged with nitrogen, and m-phenylenediamine [2] was dissolved in DMAc. The flask was then cooled to -10 °C in an ethanol-dry ice bath, and 2,4,6-trichloro-1,3,5-triazine [1] (9.22 g, 0.05 mol, Eponic Degussa) was added, ensuring that the bath temperature did not exceed 0 °C. After stirring for 1 hour, the reaction solution was added dropwise to a 500 mL four-neck flask containing 64.16 g of DMAc, which had been previously purged with nitrogen, and set in an oil bath at 85 °C. After stirring for 1 hour, 4-trifluoromethylaniline [3] (23.90 g, 0.15 mol, manufactured by Tianjin Jiahan Chemical Co., Ltd.) was added dropwise and stirred for 3 hours. The mixture was then cooled to room temperature, and n-propylamine (13.0 g, manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise. After stirring for 1 hour, stirring was stopped. The reaction solution was added dropwise to ion-exchanged water (910 g) to cause reprecipitation. The precipitate was filtered and redissolved in THF (73.75 g). The solution was added dropwise to a mixed solution of methanol (300 g) and ion-exchanged water (200 g) to cause reprecipitation again. The resulting precipitate was filtered and dried in a vacuum dryer at 120°C for 6 hours to obtain 16.7 g of the target polymer compound [4] (hereinafter referred to as TDF111). 1 The results of H-NMR spectrum measurement are shown in Figure 1. The weight average molecular weight Mw of TDF111 measured by GPC in terms of polystyrene was 3,300, and the polydispersity Mw / Mn was 4.4.

[0110] [2] Preparation of silver nanowire solution [Manufacturing Example 1] ClearOhm INK-N G4-01 (manufactured by Cambrios Technologies Corporation), ClearOhm Diluent-N 02 (manufactured by Cambrios Technologies Corporation), and ClearOhm SFT-E 02 (manufactured by Cambrios Technologies Corporation) were mixed in a mass ratio of 37.6 / 37.6 / 24.8 and stirred overnight to prepare a silver nanowire solution.

[0111] [3] Preparation of silver nanowire-coated film [Manufacturing Example 2] The silver nanowire solution obtained in Production Example 1 was spin-coated onto a 100 x 100 mm PET substrate (Lumirror T60 (TORAY Corporation)) using a spin coater at 200 rpm for 5 seconds and then at 800 rpm for 60 seconds, and then dried at 120°C for 5 minutes using a hot plate to produce a silver nanowire-coated film.

[0112] [4] Preparation of protective film-forming composition for transparent conductive film [Example 1-1 and Comparative Examples 1-1 and 1-2] Each component was dissolved in a mixed solvent of normal propyl acetate (NPAC) and propylene glycol monomethyl ether (PGME) (mass ratio 70 / 30) according to the formulation shown in Table 1 below to prepare a composition with a solids concentration (all components in the composition other than the solvent component) of 5 mass %. Note that each blend amount in Table 1 is expressed in parts by mass.

[0113] [Table 1]

[0114] [5] Preparation of protective film for transparent conductive film [Example 2-1 and Comparative Examples 2-1 and 2-2] Each of the compositions obtained in Example 1-1, Comparative Example 2-1, and Comparative Example 2-2 was stirred at room temperature (approximately 25°C) for 30 minutes, and then spin-coated onto the silver nanowire-coated film obtained in Production Example 2 using a spin coater at 200 rpm for 5 seconds and at 1,500 rpm for 30 seconds, and then dried at 80°C for 1 minute using a hot plate. Thereafter, the coating was exposed to light in the atmosphere at a dose of 400 mJ / cm. 2 The coating was then photocured by irradiating it with UV light to form a protective film. Subsequently, the protective film surface was attached to glass via an adhesive sheet of 3M Optically Clear Adhesive 8146-2 (manufactured by 3M Company) to prepare a substrate for light resistance testing.

[0115] [Lightfastness test evaluation] A xenon light resistance test was carried out on each of the protective films obtained above. Light was incident on the glass surface at an illuminance of 0.55 W / m 2 The light was irradiated at a temperature of 60°C, and the transmittance was measured with a spectrophotometer to determine the difference in the irradiation time. * The results are shown in Table 2.

[0116] [Table 2]

[0117] As shown in Table 2, the protective film prepared in Example 2-1 exhibited a b * The rate of increase is low, indicating excellent light resistance.

Claims

1. A protective film-forming composition for a transparent conductive film (excluding cases where a light stabilizer is contained) characterized by comprising a triazine ring-containing hyperbranched polymer having a repeating unit structure represented by the following formula (1), at least one triazine ring terminal, and at least a portion of the triazine ring terminal being blocked with a fluorine atom-containing arylamino group; a crosslinking agent A having a molecular weight of 1,000 or more; a crosslinking agent B having a molecular weight of less than 1,000; and a hydroxyphenylbenzotriazole-based compound that is an ultraviolet absorber. 【Chemistry 1】 wherein R and R′ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group; Ar represents at least one group selected from the group consisting of groups represented by formulas (2) to (13). 【Chemistry 2】 [In the formula, R 1 ~R 92 each independently represents a hydrogen atom, a halogen atom, a carboxyl group, a sulfone group, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms; R 93 and R 94 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, W 1 and W 2 are each independently a single bond, -C(R 95 )(R 96 )-(R 95 and R 96 each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; R 95 and R 96 When both are alkyl groups, they may be bonded to each other to form a ring together with the carbon atoms to which they are bonded.), —C(O)—, —O—, —S—, —S(O)—, —S(O) 2 - or -N(R 97 )-(R 97 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; X 1 and X 2 each independently represents a single bond, an alkylene group having 1 to 10 carbon atoms, or a group represented by formula (14). 【Transformation 3】 (In the formula, R 98 ~R 101 each independently represents a hydrogen atom, a halogen atom, a carboxyl group, a sulfone group, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms; Y 1 and Y 2 each independently represents a single bond or an alkylene group having 1 to 10 carbon atoms.

2. 2. The protective film-forming composition for a transparent conductive film according to claim 1, wherein the fluorine atom-containing arylamino group is represented by formula (15): 【Chemistry 4】 (In the formula, R 102 represents a fluorine atom or a fluoroalkyl group having 1 to 10 carbon atoms.

3. 3. The protective film-forming composition for a transparent conductive film according to claim 2, wherein the fluorine atom-containing arylamino group is represented by formula (16): 【Transformation 5】 (In the formula, R 102 represents the same meaning as above.)

4. The R 102 4. The protective film-forming composition for a transparent conductive film according to claim 2, wherein is a perfluoroalkyl group having 1 to 10 carbon atoms.

5. 5. The protective film-forming composition for a transparent conductive film according to claim 1, wherein Ar is represented by formula (17): 【Transformation 6】

6. 6. The protective film-forming composition for a transparent conductive film according to claim 1, wherein the crosslinking agent A comprises a polyfunctional (meth)acrylic compound.

7. the amount of the crosslinking agent A used is 0.1 to 30 parts by mass relative to 100 parts by mass of the triazine ring-containing hyperbranched polymer, The amount of the crosslinking agent B used is 100 to 3,000 parts by mass relative to 100 parts by mass of the crosslinking agent A. The protective film-forming composition for a transparent conductive film according to any one of claims 1 to 6.

8. 8. The protective film-forming composition for a transparent conductive film according to claim 1, wherein the crosslinking agent B comprises a polyfunctional (meth)acrylic compound.

9. The protective film-forming composition for a transparent conductive film according to any one of claims 1 to 8, which contains a solvent.

10. A protective film for a transparent conductive film obtained from the protective film-forming composition for a transparent conductive film according to any one of claims 1 to 9.

11. The protective film for a transparent conductive film according to claim 10, which is for a transparent conductive film having a conductive nanostructure.

12. The protective film for a transparent conductive film according to claim 11, wherein the conductive nanostructure is a silver nanowire.

13. A transparent electrode comprising a transparent conductive film and the protective film for a transparent conductive film according to claim 10 formed on the transparent conductive film.

14. An electronic device comprising a transparent conductive film and the protective film for a transparent conductive film according to claim 10 formed on the transparent conductive film.

15. 15. The electronic device of claim 14, which is an organic electroluminescent display.

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