WO2020022410A1

WO2020022410A1 - Composition for forming protective film for transparent conductive film

Info

Publication number: WO2020022410A1
Application number: PCT/JP2019/029115
Authority: WO
Inventors: 浩康田村; 直也西村
Original assignee: 日産化学株式会社
Priority date: 2018-07-26
Filing date: 2019-07-25
Publication date: 2020-01-30
Also published as: TW202020019A; JPWO2020022410A1

Abstract

A composition comprising a triazine ring-containing hyperbranched polymer capped with a fluorine atom-containing arylamino group, e.g., a polymer represented by formula [4], a cross-linking agent A having a molecular weight of 1,000 or more and an ultraviolet ray absorber. The composition has excellent light resistance, can provide a film capable of improving the visibility of a transparent conductive film, and is therefore suitable as a composition for forming a protective film for a transparent conductive film.

Description

Composition for forming protective film for transparent conductive film

The present invention relates to a composition for forming a protective film for a transparent conductive film.

In recent years, electronic devices such as liquid crystal displays, organic electroluminescence (EL) displays, touch panels, optical semiconductor (LED) devices, solid-state imaging devices, organic thin-film solar cells, dye-sensitized solar cells, and organic thin-film transistors (TFTs) have been developed. At that time, high-performance polymer materials have been required.
Specific characteristics required include 1) heat resistance, 2) transparency, 3) high refractive index, 4) high solubility, 5) low volume shrinkage, 6) high temperature and high humidity resistance, and 7) high film hardness. And the like.
In view of this point, the present inventors have found that a polymer containing a repeating unit having a triazine ring and an aromatic ring has a high refractive index, and the polymer alone has high heat resistance, high transparency, high refractive index, and high solubility. It has already been found that it can achieve low volume shrinkage and is suitable as a film-forming composition for producing an electronic device (Patent Document 1).

By the way, indium tin oxide (ITO), indium zinc oxide (IZO), and the like have been mainly used as the transparent conductive film material, and these are standard materials showing good optical transparency and conductivity. It has become. However, in order to obtain these inorganic oxide films, complicated processes such as sputtering, high vacuum, and high temperature annealing are required. Therefore, there is a problem that a special device is required and the cost is high.
In recent years, electronic devices are becoming more flexible and lighter by using plastic substrates and the like, and are required to have durability against physical stress such as bending. Techniques for forming ITO and IZO films on flexible substrates are also being studied, but the fragility and fragility of inorganic oxides has not been improved.

With the progress of the above-mentioned flexibility, a transparent conductive film having a conductive nanostructure (percolation structure of metal nanoparticles or metal nanowires, metal mesh structure, etc.) has been developed as a material having excellent durability against physical stress. I have.
These transparent conductive films have the advantage that, in addition to flexibility, they can be prepared by a wet process using metal nanoparticles or metal nanowire dispersions (Patent Documents 1 to 3), and only increase the amount of metal contained. It has the advantage that its electrical resistance can be reduced.
On the other hand, when the amount of metal in the film is increased to reduce the resistance, the film becomes cloudy due to irregular reflection of light, not only loses its optical transparency, but also deteriorates the surface due to the metal and deteriorates the structure. There is a problem that the conductivity is reduced by the destruction.

International Publication No. 2010/128661 JP 2009-505358 A JP 2013-77234 A JP 2010-108877 A WO 2015/093510

The present invention has been made in view of the above circumstances, and has an object to provide a protective film forming composition for a transparent conductive film which is excellent in light resistance and provides a film capable of improving the visibility of the transparent conductive film. I do.

The present inventors have already reported a composition containing a triazine ring-containing hyperbranched polymer and providing a film capable of improving the visibility of a transparent conductive film (Patent Document 5). As a result of intensive studies from the viewpoint of improvement and the like, a composition comprising a predetermined triazine ring-containing hyperbranched polymer blocked with a fluorine atom-containing arylamino group, a crosslinking agent having a molecular weight of 1,000 or more, and an ultraviolet absorber However, they have found that they provide a film having excellent light resistance and capable of improving the visibility of a transparent conductive film, and completed the present invention.

That is, the present invention
1. A triazine ring-containing hyper having a repeating unit structure represented by the following formula (1), having at least one triazine ring terminal, and at least a part of the triazine ring terminal being blocked with a fluorine atom-containing arylamino group. A protective film forming composition for a transparent conductive film, comprising: a branch polymer; a crosslinking agent A having a molecular weight of 1,000 or more; and an ultraviolet absorber.

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 is selected from the group consisting of groups represented by formulas (2) to (13). At least one group represented by

[Wherein, R ¹ to R ⁹² independently represent 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, and R ⁹³ and R ⁹² 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 are each When each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ⁹⁵ and R ⁹⁶ are both alkyl groups, they may be bonded to each other to form a ring together with the carbon atom to which they are bonded. ), —C (O) —, —O—, —S—, —S (O) —, —S (O) ₂ — or —N (R ⁹⁷ ) — (R ⁹⁷ is a hydrogen atom or carbon atom 1 represents an alkyl group of 1-10.) represents, X ¹ and X ² are each independently a single bond, one carbon atom It represents a 10 alkylene group or a group represented by the formula (14) of.

(Wherein, R ⁹⁸ to R ¹⁰¹ each independently represent 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 ¹ ² independently represent a single bond or an alkylene group having 1 to 10 carbon atoms.)]｝
2. Wherein the fluorine atom-containing arylamino group is a protective film forming composition for a transparent conductive film represented by the formula (15):

(In the formula, R ¹⁰² represents a fluorine atom or a fluoroalkyl group having 1 to 10 carbon atoms.)
3. Wherein the fluorine atom-containing arylamino group is a protective film forming composition for a transparent conductive film represented by the formula (16):

(In the formula, R ¹⁰² represents the same meaning as described above.)
4. R ² is a perfluoroalkyl group having 1 to 10 carbon atoms, wherein the composition for forming a protective film for a transparent conductive film is 2 or 3;
5. Ar is a protective film forming composition for a transparent conductive film according to any one of 1 to 4, represented by formula (17):

6. The composition for forming a protective film 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 composition for forming a protective film 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. Any one of 1 to 7, which comprises a crosslinking agent B having a molecular weight of less than 1,000,
9. 8. 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. Any one of 1 to 9, wherein the protective film-forming composition for a transparent conductive film comprises a solvent;
11. A protective film for a transparent conductive film obtained from the composition for forming a protective film for a transparent conductive film according to any one of 1 to 10;
12. 11, a protective film for a transparent conductive film, which is for a transparent conductive film having a conductive nanostructure,
13. The conductive nanostructure is a protective film for a transparent conductive film of 12, which is a silver nanowire,
14． A transparent electrode comprising a transparent conductive film, and 11 transparent conductive film protective films formed on the transparent conductive film;
15. An electronic device comprising: a transparent conductive film; and 11 transparent conductive film protective films formed on the transparent conductive film.
16. There are provided 15 electronic devices that are organic electroluminescent displays.

The protective film formed by using the composition for forming a protective film for a transparent conductive film of the present invention is excellent in light resistance, and has high transparency and refractive index. Therefore, the protective film is used as a protective film for a transparent conductive film such as ITO and silver nanowires. By using, the visibility can be improved and the deterioration can be suppressed.

1 is a ¹ H-NMR spectrum of a polymer compound [4] obtained in Synthesis Example 1.

[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).

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, both are preferably hydrogen atoms. .
In the present invention, the number of carbon atoms of the alkyl group is not particularly limited, but is preferably 1 to 20, and more preferably 1 to 10 in consideration of further increasing the heat resistance of the polymer. Is even more preferred. Further, the structure may be any of a chain, a branch, and a ring.

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-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-pe Tyl, 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-cyclo Butyl, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl-cyclobutyl, 2,4-dimethyl-cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl , 2-n-propyl-cyclopropyl, 1-isopropyl-cyclopropyl, 2-isopropyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2 3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl, 2-ethyl-3-methyl-cyclopropyl And the like.

The carbon number of the alkoxy group is not particularly limited, but is preferably 1 to 20, and more preferably 1 to 10 and more preferably 1 to 3 in consideration of further increasing the heat resistance of the polymer. . The structure of the alkyl moiety may be any of a chain, a branch, and a ring.

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, 3-methyl-n-pentyloxy, 4-methyl-n-pentyloxy, 1,1-dimethyl-n-butoxy, 1,2-dimethyl-n-butoxy, 1,3-dimethyl-n-butoxy, 2,2-dimethyl-n-butoxy, 2,3-dimethyl-n-butoxy 3,3-dimethyl-n-butoxy, 1-ethyl-n-butoxy, 2-ethyl-n-butoxy, 1,1,2-trimethyl-n-propoxy, 1,2,2-trimethyl-n- And propoxy, 1-ethyl-1-methyl-n-propoxy and 1-ethyl-2-methyl-n-propoxy groups.

Although the carbon number of the aryl group is not particularly limited, it is preferably 6 to 40, and more preferably 6 to 16 carbon atoms, and still more preferably 6 to 13 in consideration of further increasing the heat resistance of the polymer. .
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, 9-phenanthryl group and the like.

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

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

R ¹ to R ⁹² each independently represent a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group which may have a branched structure having 1 to 10 carbon atoms, or a branched chain having 1 to 10 carbon atoms. R ⁹³ and R ⁹⁴ represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a branched structure, and W ¹ and W ² represent Each independently represents a single bond, CR ⁹⁵ R ⁹⁶ (R ⁹⁵ and R ⁹⁶ each independently represent a hydrogen atom or an alkyl group which may have a branched structure having 1 to 10 carbon atoms (provided that these are taken together; , C ＝ O, O, S, SO, SO ₂ , or NR ⁹⁷ (R ⁹⁷ is a hydrogen atom or a branched structure having 1 to 10 carbon atoms. Represents an alkyl group which may be possessed).
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
In addition, as an alkyl group and an alkoxy group, the same thing as the above is mentioned.
X ¹ and X ² each independently represent a single bond, an alkylene group having 1 to 10 carbon atoms which may have a branched structure, or a group represented by the formula (14).

R ⁹⁸ to R ¹⁰¹ each independently represent a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group which may have a branched structure having 1 to 10 carbon atoms, or a branched chain having 1 to 10 carbon atoms. Represents an alkoxy group which may have a structure, and Y ¹ and Y ² each independently represent a single bond or an alkylene group which may have a branched structure having 1 to 10 carbon atoms. Examples of the halogen atom, alkyl group, and alkoxy group include the same as those described above.
Examples of the alkylene group which may have a branched structure having 1 to 10 carbon atoms include methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, and the like.

Among them, R ¹ to R ⁹² and R ⁹⁸ to R ^{101 each} represent a hydrogen atom, a halogen atom, a sulfo group, an alkyl group which may have a branched structure having 1 to 5 carbon atoms, or a 1 to 5 carbon atom. An alkoxy group which may have a branched structure of 5 is preferable, and a hydrogen atom is more preferable.

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

中でも Among these, an aryl group represented by the following formula is more preferable because a polymer having a higher refractive index can be obtained.

{Circle around (2)} In particular, in consideration of further increasing the solubility of the polymer in an organic solvent such as a low-polarity solvent, Ar is preferably an m-phenylene group represented by the formula (17).

The triazine ring-containing hyperbranched polymer used in the present invention has at least one triazine ring terminal, and at least a part of the triazine ring terminal is blocked with a fluorine atom-containing arylamino group.
Examples of the aryl group include the same as described above, and a phenyl group is particularly preferable.
Examples of the fluorine atom-containing group include a fluorine atom-containing hydrocarbon group such as a fluorine atom and a fluoroalkyl group, and a fluorine atom and a fluoroalkyl group having 1 to 10 carbon atoms are preferable.
The fluoroalkyl group having 1 to 10 carbon atoms may be linear, branched or cyclic, and includes, for example, a trifluoromethyl group, a pentafluoroethyl group, a 2,2,2-trifluoroethyl group, a heptafluoropropyl group 2,2,3,3,3-pentafluoropropyl group, 2,2,3,3-tetrafluoropropyl group, 2,2,2-trifluoro-1- (trifluoromethyl) ethyl group, nonafluoro Butyl group, 4,4,4-trifluorobutyl group, undecafluoropentyl group, 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, 2,2,3,3 , 4,4,5,5-octafluoropentyl group, tridecafluorohexyl group, 2,2,3,3,4,4,5,5,6,6,6-undecafluorohexyl group, 2, 2,3,3,4,4 5,5,6,6- decafluoro hexyl group, 3,3,4,4,5,5,6,6,6-nonafluorohexyl group, and the like.

In particular, in consideration of enhancing the solubility of the triazine ring-containing hyperbranched polymer in a low-polar solvent while maintaining the refractive index, a perfluoroalkyl group having 1 to 10 carbon atoms is preferable, and particularly a perfluoroalkyl group having 1 to 5 carbon atoms is preferable. Perfluoroalkyl groups are more preferred, and trifluoromethyl groups are most preferred.

The number of fluorine atom-containing groups is not particularly limited, and may be any number that can be substituted on the aryl group. However, considering the balance between the maintenance of the refractive index and the solubility in a solvent, 1 to 4 Are preferred, 1-2 are more preferred, and 1 is even more preferred.

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

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

(Wherein, R ¹⁰² has the same meaning as described above.)

Specific examples of the fluorine atom-containing arylamino group include those represented by the following formula, but are not limited thereto.

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 the fluorine atom-containing arylamino compound include 4-fluoroaniline, 4-trifluoromethylaniline, 4-pentafluoroethylaniline and the like.

特に In the present invention, particularly preferred triazine ring-containing hyperbranched polymers include those represented by formulas (18) to (21).

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

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

(Wherein, R ¹⁰² has the same meaning as described above.)

(Wherein, R ¹⁰² has the same meaning as described above.)

The weight average molecular weight of the triazine ring-containing hyperbranched polymer is not particularly limited, but is preferably from 500 to 500,000, more preferably from 500 to 100,000. 2,000 or more is preferred, and 50,000 or less is preferred, 30,000 or less is more preferred, and 10,000 or less is preferred from the viewpoint of increasing solubility and decreasing the viscosity of the obtained solution. Is even more preferred.
In addition, 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.

The triazine ring-containing hyperbranched polymer of the present invention can be produced according to the method disclosed in Patent Document 1 described above.
For example, as shown in the following Scheme 1, a triazine ring-containing hyperbranched polymer (20) is obtained by reacting a triazine compound (22) and an aryldiamino compound (23) in an appropriate organic solvent, And a fluorine atom-containing aniline compound (24).

(Wherein, X independently represents a halogen atom, and R ¹⁰² has the same meaning as described above.)

In the above reaction, the charge ratio of the aryldiamino compound (23) is arbitrary as long as the desired polymer can be obtained. However, 0.01 to 10 equivalents of the aryldiamino compound (23) is added to 1 equivalent of the triazine compound (22). Is preferred, and 1 to 5 equivalents is more preferred.
The aryldiamino compound (23) may be added neat or in a solution dissolved in an organic solvent, but the latter method is preferable in consideration of easiness of operation and control of the reaction. .
The reaction temperature may be appropriately set in the range from the melting point of the solvent used to the boiling point of the solvent, but is preferably about -30 to 150 ° C, more preferably -10 to 100 ° C.

As the organic solvent, various solvents usually used in this type of reaction can be used, and examples thereof include tetrahydrofuran, dioxane, dimethyl sulfoxide; 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-dimethylpropionamide, N, N-dimethylisobutylamide, N-methylformamide, N, N'-dimethylpropyleneurea Amide solvents, and mixtures thereof.
Among them, N, N-dimethylformamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, and a mixture thereof are preferable, and particularly, N, N-dimethylacetamide, N-methyl-2-pyrrolidone Is preferred.

In the first-stage reaction of the above scheme 1, various bases usually used during or after the polymerization may be added.
Specific examples of the base include potassium carbonate, potassium hydroxide, sodium carbonate, sodium hydroxide, sodium hydrogen carbonate, sodium ethoxide, sodium acetate, lithium carbonate, lithium hydroxide, lithium oxide, potassium acetate, magnesium oxide, oxide Calcium, 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 and the like.
The amount of the base to be added is preferably 1 to 100 equivalents, more preferably 1 to 10 equivalents, per 1 equivalent of the triazine compound (22). These bases may be used in the form of an aqueous solution.
It is preferable that no raw material components remain in the obtained polymer, but some raw materials may remain as long as the effects of the present invention are not impaired.
After completion of the reaction, the product can be easily purified by a reprecipitation method or the like.

As a terminal blocking method using the fluorine atom-containing aniline compound (24), a known method may be adopted.
In this case, the amount of the terminal blocking agent used is preferably about 0.05 to 10 equivalents, more preferably 0.1 to 5 equivalents, per equivalent of the halogen atom derived from the excess triazine compound not used in the polymerization reaction. Preferably, 0.5 to 2 equivalents are even more preferred.
As the reaction solvent and the reaction temperature, the same conditions as described in the first-stage reaction of the above scheme 1 can be mentioned, and the terminal blocking agent may be charged at the same time as the aryl diamino compound (23).
Note that an end-capping may be performed with two or more kinds of groups using an arylamino compound having no fluorine atom. Examples of the aryl group of the arylamino compound having no substituent include the same ones as described above.

[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, more preferably 1,500 or more. Thereby, the film density of the protective film can be increased, and the resistance to high temperature and high humidity can be improved.
In addition, the composition of the present invention preferably contains a crosslinking agent B having a molecular weight of less than 1,000 together with the crosslinking agent A. By adding the crosslinking agent B, the film density of the protective film can be further increased, and the resistance to high temperature and high humidity can be further improved. The molecular weight of the crosslinking agent B is preferably 900 or less, more preferably 800 or less.

Examples of the cross-linking agents A and B include a melamine compound having a cross-linking group such as a methylol group or a methoxymethyl group as a cross-linking group, a substituted urea compound, a compound containing a cross-linking group such as an epoxy group or an oxetane group, and a block. Compounds containing fluorinated isocyanates, compounds having acid anhydrides, compounds having (meth) acryloyl groups, aminoplast compounds, phenoplast compounds and the like. Among these, compounds containing an epoxy group, a blocked isocyanate group, and a (meth) acryl group are preferable from the viewpoint of heat resistance and storage stability, and in particular, a compound having a blocked isocyanate group and photocuring without using an initiator. Polyfunctional epoxy compounds and / or polyfunctional (meth) acrylic compounds which give possible compositions are preferred.
Note that these polyfunctional compounds need to have at least two cross-linking groups, but preferably have three or more cross-linking groups.

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

Further, as commercial products, epoxy resins YH-434 and YH434L (manufactured by Toto Kasei Co., Ltd.) having at least two epoxy groups, Epolide GT-401 and GT-403 which are epoxy resins having a cyclohexene oxide structure are available. GT-301, GT-302, celloxide 2021, 3000 (manufactured by Daicel Chemical Industries, Ltd.), Epicoat (currently jER) 1001, bisphenol A type epoxy resin, 1002, 1003, 1004, 1007, 1009, 1010, and 828 (all manufactured by Japan Epoxy Resin Co., Ltd.), Epicoat (currently jER) 807, a bisphenol F type epoxy resin (produced by Japan Epoxy Resin Co., Ltd.), phenol novolak type Epicoat, an epoxy resin (currently jER 152 and 154 (all manufactured by Japan Epoxy Resins Co., Ltd.), EPPN201 and 202 (all manufactured by Nippon Kayaku Co., Ltd.), EOCN-102 which is a cresol novolac type epoxy resin, 103S and 104S, and 1020, 1025, and 1027 (all manufactured by Nippon Kayaku Co., Ltd.), Epicoat (currently jER) 180S75 (manufactured by Japan Epoxy Resin Co., Ltd.), and Denacol EX-252 (Nagasechem, an alicyclic epoxy resin) Tex Corp.), CY175, CY177, CY179 (all made by CIBA-GEIGY @ AG), Araldite CY-182, CY-192, and CY-184 (all made by CIBA-GEIGY @ AG) Epicron 200, 400 (above, manufactured by DIC Corporation), Epicoat (currently jER) 871, 87 (The above products are manufactured by Japan Epoxy Resins Co., Ltd.), ED-5661, ED-5662 (these products are manufactured by Celanese Coating Co., Ltd.), and Denacol EX-611, EX-612, and EX which are aliphatic polyglycidyl ethers. -614, EX-622, EX-411, EX-512, EX-522, EX-421, EX-313, EX-314, EX-321 (manufactured by Nagase ChemteX Corporation) ) Can also be used.

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, and ethoxylated glycerin tri (meth) acrylate. Acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, ethoxylated isocyanuric acid tri (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, ε-caprolactone Modified tris- (2- (meth) acryloxyethyl) isocyanurate, polyglycerin monoethylene oxide poly (meth) acrylate, polyglycerin polyethylene Coal 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.

The polyfunctional (meth) acrylic compound can be obtained as a commercial product, and specific examples thereof include NK esters A-200, A-400, A-600, A-1000, and A-9300. A-9300-1CL, A-TMPT, A-TMM-3, A-TMM-3L, A-TMP, A-TMMT, A-DPH, UA-53H, 1G, 2G, 3G, 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- MPT-3EO, A-TMPT-9EO, ATM-4E, ATM-35E, AT-20E (all manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD (registered trademark) DPEA-12, PEG400DA, THE-330, RP-1040 (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 M-405, M-406, M-408, M-450, M-452, M-460 (all manufactured by Toagosei Co., Ltd.), KAYARAD (registered trademark) DPHA, NPGDA , PET30 (or more, Japan NK Ester @ A-DPH, A-TMPT, A-DCP, A-HD-N, TMPT, DCP, NPG, HD-N (Shin-Nakamura Chemical Industry) NK Oligo @ U-15HA (manufactured by Shin-Nakamura Chemical Co., Ltd.), NK Polymer @ vanaresin GH-1203 (manufactured by Shin-Nakamura Chemical Co., Ltd.), EBECRYL11, 40, 135, 140 145, 150, 180, 1142, OTA480, IRR214-K, and PEG400DA-D (all manufactured by Daicel Ornex).

As the polyfunctional (meth) acrylic compound, 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, 8465, 8296, 8307, 8402, 8311, 8411, 8701, 8800, 8804, 8807, 9260, 9270, 9277EA, KRM7735, 8200, 8452, 8528, 8667, 8904 (daicel Ornex, Inc. )), UV-1700B, UV-6300B, UV-7 10B, UV-7550V, UV-7550B, UV-7600B, UV-7605B, UV-7610B, UV-7620EA, UV-7630B, UV-7640B, UV-7650B (all manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) EBECRYL 436, 438, 446, 450, 524, 525, 800, 810, 811, 812, 812, 1830, 846, 851, 852, and 853, which are polyfunctional polyester acrylates. EBECRYL600, 605, 645, 648, 860, 1606, 3500, 3603, and 3608 which are epoxy acrylates. , 3700, 3701, 3702, 3703, 708, the 6040 (or, Daicel Orunekusu Ltd.) can also be used like.

The acid anhydride compound is not particularly limited as long as it is a carboxylic anhydride obtained by dehydrating and condensing two molecules of carboxylic acid. Specific examples thereof include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, maleic anhydride, succinic anhydride, Octyl succinic anhydride, dodecenyl succinic anhydride, etc. having one acid anhydride group in the molecule; 1,2,3,4-cyclobutanetetracarboxylic dianhydride, pyromellitic anhydride, 3,4 -Dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic dianhydride, bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic dianhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 1,2,3,4- Tantetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2-bis ( (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, etc. having two acid anhydride groups in the molecule And the like.

A compound containing a blocked isocyanate has two or more blocked isocyanate groups in one molecule in which an isocyanate group (—NCO) is blocked by an appropriate protecting group, and when exposed to a high temperature during thermosetting, There is no particular limitation as long as the protecting group (block portion) is thermally dissociated and comes off, and the generated isocyanate group causes a cross-linking reaction with the resin. For example, two of the groups represented by the following formula per molecule may be used. Compounds having the above (these groups may be the same or different) may be mentioned.

(In the formula, R _b represents an organic group in the block portion.)

Such a compound can be obtained, for example, by reacting a compound having two or more isocyanate groups per molecule with a suitable blocking agent.

Examples of the compound having two or more isocyanate groups in one molecule include polyisocyanates such as isophorone diisocyanate, 1,6-hexamethylene diisocyanate, methylene bis (4-cyclohexyl isocyanate), and trimethylhexamethylene diisocyanate, and dimers thereof. And trimers, and reaction products thereof with diols, triols, diamines or triamines.

Examples of the blocking agent include alcohols such as methanol, ethanol, isopropanol, n-butanol, 2-ethoxyhexanol, 2-N, N-dimethylaminoethanol, 2-ethoxyethanol and cyclohexanol; phenol, o-nitrophenol Phenols such as p-chlorophenol, 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.

The compound containing the blocked isocyanate is also available as a commercial product, and specific examples thereof include B-830, B-815N, B-842N, B-870N, B-874N, B-882N, and B-882N. 7005, B-7030, B-7075, B-5010 (all manufactured by Mitsui Chemicals Polyurethanes Inc.), Duranate (registered trademark) 17B-60PX, TPA-B80E, MF-B60X, MF-K60X, E402-B80T (above, manufactured by Asahi Kasei Chemicals Corporation), Karenz MOI-BM (registered trademark) (above, manufactured by Showa Denko KK) and the like.

The aminoplast compound is not particularly limited as long as it has two or more methoxymethylene groups in one molecule. For example, Cymel series such as hexamethoxymethyl melamine {CYMEL (registered trademark) 303, tetrabutoxymethyl glycoluril} 1170, tetramethoxymethyl benzoguanamine {1123 (all manufactured by Nippon Cytec Industries Co., Ltd.), and methylated melamine resins. Nikarac (registered trademark) MW-30HM, MW-390, MW-100LM, MX-750LM, methylated urea resins MX-270, MX-280, MX-290 And melamine-based compounds such as Nikalac series (manufactured by Sanwa Chemical Co., Ltd.).

The oxetane compound is not particularly limited as long as it has two or more oxetanyl groups in one molecule. For example, OXT-221, OX-SQ-H, and OX-SC containing oxetane group (these are Toa Gosei Co., Ltd. )).

The phenoplast compound has two or more hydroxymethylene groups in one molecule, and when exposed to a high temperature during thermosetting, a crosslinking reaction proceeds with a hyperbranched polymer used in the present invention by a dehydration condensation reaction. Is what you do. Examples of the phenoplast compound include 2,6-dihydroxymethyl-4-methylphenol, 2,4-dihydroxymethyl-6-methylphenol, bis (2-hydroxy-3-hydroxymethyl-5-methylphenyl) methane, Bis (4-hydroxy-3-hydroxymethyl-5-methylphenyl) methane, 2,2-bis (4-hydroxy-3,5-dihydroxymethylphenyl) propane, bis (3-formyl-4-hydroxyphenyl) methane And bis (4-hydroxy-2,5-dimethylphenyl) formylmethane, α, α-bis (4-hydroxy-2,5-dimethylphenyl) -4-formyltoluene and the like.

The phenoplast compound is also available as a commercial product, and specific examples thereof include 26DMPC, 46DMOC, DM-BIPC-F, DM-BIOC-F, TM-BIP-A, BISA-F, BI25X-DF, BI25X-TPA (all manufactured by Asahi Organic Materials Industry Co., Ltd.) and the like.

The crosslinking agent A preferably has a molecular weight of 1,000 or more due to a long chain length between crosslinking groups, and specifically has a polyether structure, a polyester structure, a polyurethane structure, or the like. It is preferred that the length of the chain between the cross-linking groups becomes longer. Among the crosslinking agents described above, examples of the crosslinking agent A include NK esters A-GLY-20E, ATM-35E, AT-20E, 23G, A-BPE-20, BPE-900, and BPE-1300N ( Above, Shin Nakamura Chemical Industry Co., Ltd.), EBECRYL 204, 205, 210, 215, 230, 244, 245, 270, 284, 285, 264, 265, 294 / 25HD, 1259, 1290, 4820, 8254, 8301R, 8405, 8465, 8296, 8307, 8411, 8701, 8800, 8804, 9260, 9277EA, KRM8200, 8452, 8528, 8667, 8904, 436, 438, 446, 450, 525, 183 , 846, 1870, 884, 885, 860, 3708 (all manufactured by Daicel Ornex), UV-1700B, UV-6300B, UV-7510B, UV-7550V, UV-7550B, UV-7600B, UV-7605B, UV-7610B, UV-7620EA, UV-7630B, UV-7640B, UV-7650B, and the like (all manufactured by Nippon Synthetic Chemical Co., Ltd.). Of these, NK esters A-GLY-20E and ATM-35E are preferred.

Among the above crosslinking agents, Alonix M-303, M-305, M-305, M-306, M-400, and M-402 are examples of the crosslinking agent B having a molecular weight of less than 1,000. M-403, M-404, M-405, M-406, M-450, M-452 (all manufactured by Toagosei Co., Ltd.), NK ester A-9300, and A- 9300-1CL, A-TMM-3, 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 (or more, EBECRYL # 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, 6040 OTA 480 (all manufactured by Daicel Ornex Co., Ltd.) ), KAYARAD @ DN-0075 (manufactured by Nippon Kayaku Co., Ltd.) and the like. 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, M-452 (all manufactured by Toagosei Co., Ltd.), NK ester A-9300, A-9300-1CL (all manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD DN-0075 (manufactured by Nippon Kayaku Co., Ltd.) and the like are preferable.

多 As the cross-linking agents A and B, polyfunctional (meth) acrylic compounds are preferred because they can suppress a decrease in the refractive index due to the blending of the cross-linking agent, and the curing reaction proceeds rapidly.

The crosslinking agents A and B may be used alone or in combination of two or more.
The amount of the crosslinking agent A to be used is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the triazine ring-containing hyperbranched polymer, but considering solvent resistance, the lower limit is preferably 1 part by mass, more preferably The upper limit is preferably 5 parts by mass, and more preferably 20 parts by mass in consideration of controlling the refractive index.
The amount of the crosslinking agent B to be used is preferably from 100 to 3,000 parts by mass, more preferably from 1,000 to 2,000 parts by mass, based on 100 parts by mass of the crosslinking agent A from the viewpoint of further improving the optical properties of the transparent conductive film and preventing a remarkable decrease in the refractive index. Parts by mass are more preferred.

[UV absorber]
The composition of the present invention contains an ultraviolet absorber in addition to the above-described triazine ring-containing hyperbranched polymer and a crosslinking agent. Thereby, the deterioration of the triazine ring-containing hyperbranched polymer in the cured film due to the influence of ultraviolet rays or the like can be suppressed, and the light resistance can be improved.
As the ultraviolet absorber, for example, organic compounds such as benzotriazole-based compounds, benzophenone-based compounds, triazine-based compounds, cyclic iminoester-based compounds, cyanoacrylate-based compounds, malonic ester compounds, and salicylic acid phenylester-based compounds, and titanium oxide Examples include inorganic particles that absorb ultraviolet light, such as fine particles, zinc oxide fine particles, and tin oxide fine particles.
Among these, a benzotriazole-based compound and a triazine-based compound are preferred, and a hydroxyphenylbenzotriazole-based compound is more preferred, from the viewpoint of improving the weather resistance of the obtained cured film and also preventing coloring of the cured film.

Specific examples of the ultraviolet absorber include 2- (5-methyl-2-hydroxyphenyl) benzotriazole and 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzo. Triazoles such as triazole and 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole; 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2,2 ′ Benzophenones such as -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-[(2-hydroxy-3- (2'-ethyl) hexyl) oxy] -2-hydroxyphenyl] -4,6-bis (2 , 4-Dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3 Hydroxyphenyltriazines such as 1,5-triazine; oxalic anilides such as (2-ethoxy-2'-ethyloxalic acid bisanilide); phenylsalicylate, pt-butylphenyl Salicylic acids such as salicylate and p-octylphenyl salicylate; cyclic iminoesters such as 2,2'-p-phenylenebis (3,1-benzoxazin-4-one); 1,3-bis [(2-cyano Cyanoacrylates such as -3,3-diphenylacryloyl) oxy] -2,2-bis [[(2-cyano-3,3-diphenylacryloyl) oxy] methyl] propane; tetraethyl-2,2 '-(1 , 4-phenylenedimethylidyne) bismalonate and the like.

Commercially available ultraviolet absorbers may be used. Specific examples thereof include TINUVIN (registered trademark) PS, 99-2, 99-DW, 109, 328, 329, 384-2, and 384-2. 400, 400-DW, 405, 460, 477, 477-DW, 479, 900, 928, 1130, 111FDL (all manufactured by BASF Japan Ltd.), ADK STAB LA-29 LA-31, LA-31RG, LA-31G, LA-32, LA-36RG, LA-46, 1413, LA-F70 (all manufactured by ADEKA Corporation), Newcoat UVA-101, UVA-102, UVA-103, UVA-104, Vanaresin UVA-5080, UVA-5080 (OHV20), UVA-55T, UV -5MHB, the UVA-7075, the UVA-7075 (OHV20), the UVA-73T (Shin-Nakamura Chemical Co., Ltd.), RUVA-93 (manufactured by Otsuka Chemical Co., Ltd.), and the like.

The UV absorbers may be used alone or in combination of two or more.
The amount of the ultraviolet absorber to be used is preferably 0.1 to 100 parts by mass with respect to 100 parts by mass of the triazine ring-containing hyperbranched polymer. However, in consideration of further increasing the light resistance of the obtained cured film, the lower limit thereof is as follows. It is preferably 1 part by mass, more preferably 5 parts by mass, and further from the viewpoint of preventing the refractive index of the cured film from lowering and preventing coloring, the upper limit is preferably 30 parts by mass, more preferably 20 parts by mass. .

[solvent]
The composition of the present invention is preferably used by adding various solvents to dissolve the triazine ring-containing hyperbranched polymer. In this case, the solvent may be the same as or different from the solvent used during the polymerization. This solvent is not particularly limited as long as compatibility with the polymer is not impaired.

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, dip Pyrene 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, hexylene glycol, trimethylene glycol, -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 Ton, diethyl ketone, methyl isobutyl ketone, methyl n-butyl ketone, cyclohexanone, ethyl acetate, isopropyl acetate, n-propyl acetate, isobutyl acetate, n-butyl acetate, ethyl lactate, methanol, ethanol, isopropanol, tert-butanol, allyl alcohol , N-propanol, 2-methyl-2-butanol, isobutanol, n-butanol, 2-methyl-1-butanol, 1-pentanol, 2-methyl-1-pentanol, 2-ethylhexanol, 1-methoxy -2-propanol, tetrahydrofuran, 1,4-dioxane, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethylsulfoxide, N-cyclo Cyclohexyl-2-pyrrolidinone, and the like. These may be used alone or in combination of two or more.

At this time, the solid content concentration in the composition is not particularly limited as long as it does not affect storage stability, and may be appropriately set according to the thickness of the target film. Specifically, from the viewpoint of solubility and storage stability, the solid concentration is preferably 0.1 to 50% by mass, more preferably 0.2 to 40% by mass.

[Initiator]
In the composition of the present invention, an initiator corresponding to each crosslinking agent may be blended. As described above, when a polyfunctional epoxy compound and / or a polyfunctional (meth) acrylic compound is used as a crosslinking agent, photocuring proceeds without using an initiator to give a cured film. In some cases, an initiator may be used.

When a polyfunctional epoxy compound is used as a crosslinking agent, a photoacid generator or a photobase generator can be used.
The photoacid generator may be appropriately selected from known ones and used, and for example, onium salt derivatives such as diazonium salts, sulfonium salts and iodonium salts can be used. Specific examples thereof include aryldiazonium salts such as phenyldiazonium hexafluorophosphate, 4-methoxyphenyldiazonium hexafluoroantimonate, and 4-methylphenyldiazonium hexafluorophosphate; diphenyliodonium hexafluoroantimonate, di (4-methylphenyl) Diaryliodonium salts such as iodonium hexafluorophosphate and di (4-tert-butylphenyl) iodonium hexafluorophosphate; triphenylsulfonium hexafluoroantimonate, tris (4-methoxyphenyl) sulfonium hexafluorophosphate, diphenyl-4-thiophenoxy Phenylsulfonium hexafluoroantimonate, diphenyl-4-thiophenoxy Phenylsulfonium hexafluorophosphate, 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, 4- [4'-(benzoyl) phenylthio] phenyl-di (4-fluorophenyl) sulfonium Triarylsulfonium salts such as hexa fluoro phosphate.

As these onium salts, commercially available products may be used, and specific examples thereof include San-Aid SI-60, SI-80, SI-100, SI-60L, SI-80L, SI-100L, SI-L145, SI-L. L150, SI-L160, SI-L110, SI-L147 (above, manufactured by Sanshin Chemical Industry Co., Ltd.), UVI-6950, UVI-6970, UVI-6974, UVI-6990, UVI-6992 (above, union carbide) Co., Ltd.), CPI-100P, CPI-100A, CPI-200K, CPI-200S (manufactured by Sun Apro Co., Ltd.), Adeka Optomer SP-150, SP-151, SP-170, SP-171 (manufactured by Asahi Denka Kogyo Co., Ltd.), Irgacure 261 (BASF), CI-2481, CI-2624, CI-26 9, 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 @ TOSYLATE, MBZ-101, MBZ-301, PYR-100, PYR-200, DNB-101, NB-101, NB-201, BBI-101, BBI-102, BBI-103, BBI-109 ( As described above, Midori Kagaku Co., Ltd.), PCI-061T, PCI-062T, PCI-020T, CI-022T (manufactured by Nippon Kayaku (Ltd.)), IBPF, IBCF (manufactured by Sanwa Chemical Co., Ltd.), and the like.

The photobase generator may be appropriately selected from known ones and used. For example, a Co-amine complex, oxime carboxylate ester, carbamate ester type, quaternary ammonium salt type photobase generator, or the like may be used. it can. 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, (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane, N- (2-nitrobenzyloxycarbonyl) pyrrolidine, hexaamminecobalt (III) tris (triphenylmethylborate), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2,6-dimethyl- 3,5-di Cetyl-4- (2'-nitrophenyl) -1,4-dihydropyridine, 2,6-dimethyl-3,5-diacetyl-4- (2 ', 4'-dinitrophenyl) -1,4-dihydropyridine and the like No.
The photobase generator may be a commercially available product, and specific examples thereof include TPS-OH, NBC-101, and ANC-101 (all manufactured by Midori Kagaku Co., Ltd.).

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

On the other hand, when a polyfunctional (meth) acrylic compound is used, a photoradical polymerization initiator can be used. The photo-radical polymerization initiator may be appropriately selected and used from known ones, and examples thereof include acetophenones, benzophenones, benzoylbenzoate of Michler, amiloxime ester, tetramethylthiuram monosulfide, and thioxanthone.

Particularly, a photo-cleavable photo-radical polymerization initiator is preferable. The photo-cleavable photo-radical polymerization initiator is described in the latest UV curing technology (p. 159, publisher: Kazuhiro Takasu, publisher: Technical Information Association, 1991).

Commercially available photo-radical polymerization initiators include, for example, trade names: Irgacure 127, 184, 369, 379, 651, 500, 819, 907, 784, 2959, OXE01, OXE02, CGI1700, CGI1750, CGI1850, CG24 manufactured by BASF. -61, Darocure 1116, 1173, manufactured by BASF. Product name: Lucirin TPO, manufactured by UCB. Product name: Jubecryl P36, manufactured by Fratteris Lamberti. B and the like.

When a photoradical polymerization initiator is used, it is preferably used in an amount of 0.1 to 15 parts by mass, more preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the polyfunctional (meth) acrylate compound. Range.

[Crosslinking accelerator]
Further, to the composition of the present invention, for the purpose of accelerating the reaction between the triazine ring-containing hyperbranched polymer and the crosslinking agent, a polyfunctional thiol compound having two or more mercapto groups in the molecule is added. Is also good.
Specifically, a polyfunctional thiol compound represented by the following formula is preferable.

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 heterocyclic group, And 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: .
N represents an integer of 2 to 4 corresponding to the valence of L.

(In the formula, “•” indicates a bonding portion with an oxygen atom.)

Specific compounds include 1,4-bis (3-mercaptobutyryloxy) butane and 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), trimethylolethanetris (3-mercaptobutyrate) and the like. Can be
These polyfunctional thiol compounds can also be obtained as commercial products, and examples thereof include 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.

When a polyfunctional thiol compound is used, its addition amount is not particularly limited as long as it does not adversely affect the obtained protective film. % By mass, more preferably 0.1 to 6% by mass.

[Other ingredients]
The film-forming composition of the present invention may contain other components, such as a leveling agent and a surfactant, as long as the effects of the present invention are not impaired.
Examples of the leveling agent or the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether, and polyoxyethylene octyl phenol ether. Polyoxyethylene alkyl allyl ethers such as oxyethylene nonylphenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan Sorbitan fatty acid esters such as tristearate, polyoxyethylene sorbitan monolaurate, Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as oxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; EF301, EF303, EF352 (manufactured by Mitsubishi Materials Denka Kasei Co., Ltd. (formerly manufactured by Gemco)), 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), Florado FC430, FC431 (manufactured by Sumitomo 3M Limited), trade name Asahi Guard AG710, Surflon S-382, SC101, SC102 Fluorinated surfactants such as SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.); organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), BYK-302, BYK-307, BYK-322, BYK- H.323, BYK-330, BYK-333, BYK-370, BYK-375, BYK-378 (manufactured by BYK Japan KK) and the like.

These may be used alone or in combination of two or more. The amount of the surfactant to be used is preferably 0.001 to 5 parts by mass, more preferably 0.01 to 5 parts by mass, and more preferably 0.1 to 2 parts by mass based on 100 parts by mass of the triazine ring-containing hyperbranched polymer. More preferred.
The above-mentioned other components can be added at any step when preparing the composition of the present invention.

[Protective film for transparent conductive film]
The protective film for a transparent conductive film of the present invention is obtained by applying the above-mentioned composition for forming a protective film for a transparent conductive film to a transparent conductive film, heating and evaporating the solvent if necessary, and then heating or irradiating with light. Can be formed by
In this case, the thickness of the protective film is preferably from 10 to 1,000 nm, more preferably from 50 to 200 nm.
The lower limit of the range of the refractive index 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.

The haze value of the transparent conductive film on which the protective film of the present invention is formed is preferably 1.5% or less, more preferably 1.0% or less.

The method of applying the composition is arbitrary, and examples thereof include a spin coating method, a dip method, a flow coating method, an ink jet method, a spray method, a bar coating method, a gravure coating method, a slit coating method, a roll coating method, a transfer printing method, and a brush. Coating, a blade coating method, an air knife coating method and the like can be employed.

Examples of the transparent conductive film include a transparent conductive film having a conductive nanostructure such as an ITO film, an IZO film, a metal nanoparticle, a metal nanowire, and a metal nanomesh. A transparent conductive film having a conductive nanostructure is preferred. The metal constituting the conductive nanostructure is not particularly limited, and examples thereof include silver, gold, copper, nickel, platinum, cobalt, iron, zinc, ruthenium, rhodium, palladium, cadmium, osmium, iridium, and alloys thereof. That is, a transparent conductive film having silver nanoparticles, silver nanowires, silver nanomesh, gold nanoparticle, gold nanowire, gold nanomesh, copper nanoparticle, copper nanowire, copper nanomesh, or the like is preferable, and in particular, a transparent conductive film having silver nanowires is preferable. Membranes are preferred.

The heating temperature is not particularly limited for the purpose of evaporating the solvent, and the heating can be performed, for example, at 40 to 400 ° C. The heating method is not particularly limited, and for example, the solvent may be evaporated using a hot plate or an oven under an appropriate atmosphere such as an atmosphere, an inert gas such as nitrogen, or a vacuum. The sintering temperature and the sintering time may be selected under conditions suitable for the target electronic device process step, and the sintering conditions may be selected so that the physical properties of the obtained film conform to the required characteristics of the electronic device.

The conditions for light irradiation are not particularly limited, and appropriate irradiation energy and time may be employed depending on the triazine ring-containing hyperbranched polymer and the crosslinking agent to be used. For example, it can be performed at 50 to 1,000 mJ / cm ² . Light irradiation is preferably performed in the atmosphere or in an atmosphere of an inert gas such as nitrogen.

保護 The protective film of the present invention is particularly suitable as a protective film for a transparent conductive film having a conductive nanostructure. A transparent conductive film having a conductive nanostructure is liable to be clouded due to irregular reflection of light due to the conductive nanostructure, and may have poor visibility. Since the protective film of the present invention has high transparency and a high refractive index, it is possible to prevent clouding due to irregular reflection of light of the transparent conductive film using the conductive nanostructure, and improve visibility. Furthermore, since it has light resistance, high heat resistance, and high temperature and humidity resistance, it can contribute to prevention of deterioration of the transparent conductive film.

Hereinafter, the present invention will be described more specifically 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.

[ ¹ H-NMR]
Apparatus: Varian NMR System 400NB (400MHz)
JEOL-ECA700 (700MHz)
Measurement solvent: DMSO-d6
Reference substance: tetramethylsilane (TMS) (δ0.0 ppm)
[GPC]
Equipment: Tosoh Corporation HLC-8200 GPC
Column: Shodex KF-804L + KF-805L
Column temperature: 40 ° C
Solvent: tetrahydrofuran (THF)
Detector: UV (254 nm)
Calibration curve: Standard polystyrene [Ellipsometer]
Apparatus: JA Woolam Japan Co., Ltd., multiple incidence angle spectroscopic ellipsometer VASE
[Xenon light fastness tester]
Apparatus: Q-SUN Xe-1-B manufactured by Q-Lab Corporation
[Spectrophotometer]
Equipment: Konica Minolta Japan CM-3700A

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 K.K.)
NR1: 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione (Karenz MT NR1 manufactured by Showa Denko KK) )
F559: Surfactant (megafax F-559, manufactured by DIC Corporation)
T900: UV absorber (Tinuvin 900 manufactured by BASF Japan K.K.)

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

To a 200 mL four-necked flask were added m-phenylenediamine [2] (6.00 g, 0.055 mol, manufactured by AminoChem) and 78.88 g of dimethylacetamide (DMAc, manufactured by Junsei Chemical Co., Ltd.), and the atmosphere was replaced with nitrogen. , M-phenylenediamine [2] was dissolved in DMAc. Then, the mixture was cooled to −10 ° C. with an ethanol-dry ice bath, and 2,4,6-trichloro-1,3,5-triazine [1] (9.22 g, 0.05 mol, manufactured by Eponic Degussa) was cooled to a bath temperature. It was charged while confirming that the temperature did not reach 0 ° C. or higher. After stirring for 1 hour, 64.16 g of DMAc was previously added to the reaction solution, and after purging with nitrogen, the reaction solution was dropped into a 500 mL four-necked flask set at 85 ° C. in an oil bath. After stirring for 1 hour, 4-trifluoromethylaniline [3] (23.90 g, 0.15 mol, manufactured by Tianjin Jiahan Chemical) was added dropwise, and the mixture was stirred for 3 hours. Thereafter, the temperature was lowered to room temperature, n-propylamine (13.0 g, manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise, and after stirring for 1 hour, the stirring was stopped. The reaction solution was dropped into ion-exchanged water (910 g) to cause reprecipitation. The precipitate was filtered, redissolved in THF (73.75 g), and the solution was dropped into a mixed solution of methanol (300 g) and ion-exchanged water (200 g), and reprecipitated again. The obtained 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). FIG. 1 shows the measurement result of the ¹ H-NMR spectrum of TDF111.
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.

[2] Preparation of silver nanowire liquid [Production 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.org/Template.RTM. 8 and stirred overnight to prepare a silver nanowire solution.

[3] Production of silver nanowire coated film [Production Example 2]
The silver nanowire liquid obtained in Production Example 1 was spin-coated on a 100 × 100 mm PET substrate (Lumirror T60 (manufactured by TORAY)) using a spin coater at 200 rpm for 5 seconds and 800 rpm for 60 seconds, followed by hot coating. It dried at 120 degreeC for 5 minutes using the plate, and produced the silver nanowire coating film.

[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) / propylene glycol monomethyl ether (PGME) (mass ratio 70/30) in the composition shown in Table 1 below, and the solid content (all components other than the solvent component in the composition) was determined. Component) A composition having a concentration of 5% by mass was prepared. In addition, each compounding amount in Table 1 represents a mass part.

[5] Production of protective film for transparent conductive film [Example 2-1 and Comparative Examples 2-1 and 2-2]
Each composition obtained in Example 1-1, Comparative Example 2-1 and Comparative Example 2-2 was stirred at room temperature (about 25 ° C.) for 30 minutes, and then coated with the silver nanowire obtained in Production Example 2. The film was spin-coated at 200 rpm for 5 seconds and 1,500 rpm for 30 seconds using a spin coater, and dried at 80 ° C. for 1 minute using a hot plate. Thereafter, the coating film was irradiated with UV light having an exposure amount of 400 mJ / cm ^{2 in} the atmosphere to be light-cured, thereby producing a protective film.
Subsequently, a substrate for a light resistance test was manufactured by attaching the protective film surface and the glass via an adhesive sheet of 3M Optically Clear Adhesive 8146-2 (manufactured by 3M Company).

[Evaluation of light resistance test]
A xenon light resistance test was performed on each of the protective films obtained above. Light was input from the glass surface, irradiated with light under the conditions of an illuminance of 0.55 W / m ² and a temperature of 60 ° C., and b ^* at the irradiation time was evaluated by transmission measurement using a spectrophotometer. Table 2 shows the results.

As shown in Table 2, it can be seen that the protective film produced in Example 2-1 has a low rate of increase in b ^* after long-time light irradiation and is excellent in light resistance.

Claims

A triazine ring-containing hyper having a repeating unit structure represented by the following formula (1), having at least one triazine ring terminal, and at least a part of the triazine ring terminal being blocked with a fluorine atom-containing arylamino group. A protective film forming composition for a transparent conductive film, comprising a branch polymer, a crosslinking agent A having a molecular weight of 1,000 or more, and an ultraviolet absorber.

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).

[Wherein, R 1 to R 92 each independently represent 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 represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms,
W 1 and W 2 each independently represent a single bond; —C (R 95 ) (R 96 ) — (R 95 and R 96 each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; When 95 and R 96 are both alkyl groups, they may combine with each other to form a ring together with the carbon atom to which they are attached.), —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 represent a single bond, an alkylene group having 1 to 10 carbon atoms or a group represented by the formula (14).

(Wherein, R 98 to R 101 each independently represent 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 represent a single bond or an alkylene group having 1 to 10 carbon atoms. )]｝
The composition for forming a protective film for a transparent conductive film according to claim 1, wherein the fluorine atom-containing arylamino group is represented by the formula (15).

(In the formula, R 102 represents a fluorine atom or a fluoroalkyl group having 1 to 10 carbon atoms.)
The composition for forming a protective film for a transparent conductive film according to claim 2, wherein the fluorine atom-containing arylamino group is represented by the formula (16).

(In the formula, R 102 represents the same meaning as described above.)
4. The protective film forming composition for a transparent conductive film according to claim 2, wherein R 102 is a perfluoroalkyl group having 1 to 10 carbon atoms.
5. The composition for forming a protective film for a transparent conductive film according to claim 1, wherein Ar is represented by the formula (17).
The protective film forming composition for a transparent conductive film according to any one of claims 1 to 5, wherein the ultraviolet absorber is a triazine-based or benzotriazole-based ultraviolet absorber.
7. The composition for forming a protective film for a transparent conductive film according to claim 1, wherein the crosslinking agent A contains a polyfunctional (meth) acrylic compound.
The composition for forming a protective film for a transparent conductive film according to any one of claims 1 to 7, further comprising a crosslinking agent B having a molecular weight of less than 1,000.
The protective film-forming composition for a transparent conductive film according to claim 8, wherein the crosslinking agent B contains a polyfunctional (meth) acrylic compound.
The composition for forming a protective film for a transparent conductive film according to any one of claims 1 to 9, further comprising a solvent.
A protective film for a transparent conductive film obtained from the composition for forming a protective film for a transparent conductive film according to any one of claims 1 to 10.
12. The protective film for a transparent conductive film according to claim 11, which is for a transparent conductive film having a conductive nanostructure.
The protective film for a transparent conductive film according to claim 12, wherein the conductive nanostructure is a silver nanowire.
A transparent electrode comprising: a transparent conductive film; and the transparent conductive film protective film according to claim 11 formed on the transparent conductive film.
An electronic device comprising: a transparent conductive film; and the transparent conductive film protective film according to claim 11 formed on the transparent conductive film.
The electronic device according to claim 15, which is an organic electroluminescence display.