WO2020022410A1 - Composition pour former un film protecteur pour film conducteur transparent - Google Patents

Composition pour former un film protecteur pour film conducteur transparent Download PDF

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WO2020022410A1
WO2020022410A1 PCT/JP2019/029115 JP2019029115W WO2020022410A1 WO 2020022410 A1 WO2020022410 A1 WO 2020022410A1 JP 2019029115 W JP2019029115 W JP 2019029115W WO 2020022410 A1 WO2020022410 A1 WO 2020022410A1
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transparent conductive
group
conductive film
protective film
composition
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PCT/JP2019/029115
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Japanese (ja)
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浩康 田村
直也 西村
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日産化学株式会社
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/805—Electrodes
    • H10K59/8052—Cathodes
    • H10K59/80524—Transparent cathodes, e.g. comprising thin metal layers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/48—Stabilisers against degradation by oxygen, light or heat
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/26—Light sources with substantially two-dimensional radiating surfaces characterised by the composition or arrangement of the conductive material used as an electrode
    • H05B33/28—Light sources with substantially two-dimensional radiating surfaces characterised by the composition or arrangement of the conductive material used as an electrode of translucent electrodes

Definitions

  • the present invention relates to a composition for forming a protective film for a transparent conductive film.
  • 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).
  • ITO indium tin oxide
  • IZO indium zinc oxide
  • the transparent conductive film material 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • compositions containing a triazine ring-containing hyperbranched polymer and providing a film capable of improving the visibility of a transparent conductive film Patent Document 5
  • Patent Document 5 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
  • 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.
  • 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.
  • R and R ′ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or an aralkyl group
  • Ar is selected from the group consisting of groups represented by formulas (2) to (13).
  • 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
  • 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
  • R 97 is a hydrogen atom or carbon atom 1 represents an alkyl group of 1-10.
  • 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.
  • 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.
  • 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.
  • 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.
  • a protective film for a transparent conductive film which is for a transparent conductive film having a conductive nanostructure
  • 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;
  • An electronic device comprising: a transparent conductive film; and 11 transparent conductive film protective films formed on the transparent conductive film. 16.
  • 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.
  • 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).
  • 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.
  • 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.
  • the structure may be any of a chain, a branch, and a ring.
  • alkyl group examples 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,
  • 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.
  • alkoxy group examples 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-ethoxy,
  • 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, ⁇ -naphthyl, ⁇ -naphthyl, o-biphenylyl, m-biphenylyl, p-biphenylyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4 -Phenanthryl, 9
  • 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, ⁇ -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
  • 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).
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • an aryl group represented by the following formula is more preferable because a polymer having a higher refractive index can be obtained.
  • 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.
  • a fluorine atom-containing arylamino group examples include the same as described above, and a phenyl group is particularly preferable.
  • 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,
  • 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.
  • R 102 represents a fluorine atom or a fluoroalkyl group having 1 to 10 carbon atoms.
  • fluorine atom-containing arylamino group examples 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.
  • particularly preferred triazine ring-containing hyperbranched polymers include those represented by formulas (18) to (21).
  • 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.
  • 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.
  • 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).
  • the charge ratio of the aryldiamino compound (23) is arbitrary as long as the desired polymer can be obtained.
  • 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.
  • 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.
  • 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.
  • various bases usually used during or after the polymerization may be added.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • cross-linking agents A and B examples 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.
  • 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 such as an epoxy group or an oxetane group
  • a compound containing a cross-linking group such as an epoxy group or an oxetane group
  • a block examples 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
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • EBECRYL600, 605, 645, 648, 860, 1606, 3500, 3603, and 3608 which are epoxy acrylates.
  • 3700, 3701, 3702, 3703, 708, the 6040 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.
  • 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.
  • an isocyanate group (—NCO)
  • the protecting group block portion
  • the generated isocyanate group causes a cross-linking reaction with the resin.
  • 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.
  • 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.
  • the blocking agent examples 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 ⁇ -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.
  • 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
  • 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.
  • 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.
  • phenoplast compound examples 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, ⁇ , ⁇ -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.
  • 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,
  • 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
  • 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.
  • 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.
  • 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.
  • 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
  • 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.
  • 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
  • the ultraviolet absorber examples include 2- (5-methyl-2-hydroxyphenyl) benzotriazole and 2- [2-hydroxy-3,5-bis ( ⁇ , ⁇ -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
  • UV 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
  • 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.
  • 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. .
  • composition of the present invention is preferably used by adding various solvents to dissolve the triazine ring-containing hyperbranched polymer.
  • 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.
  • 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, diethylene
  • 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.
  • an initiator corresponding to each crosslinking agent may be blended.
  • 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.
  • an initiator may be used.
  • 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.
  • 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 hex
  • 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 Nippo
  • the photobase generator may be appropriately selected from known ones and used.
  • 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) tri
  • a photoacid generator or a photobase generator 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.
  • a photoradical polymerization initiator 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.
  • 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).
  • 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.
  • a photoradical polymerization initiator 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.
  • 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.
  • 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.
  • 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.
  • a polyfunctional thiol compound 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.
  • 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.
  • a 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.
  • 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.
  • 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.
  • 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.
  • the transparent conductive film examples 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.
  • 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.
  • 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.
  • 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.
  • DPHA dipentaerythritol penta and hexaacrylate
  • ATM35E ethoxylated pentaerythritol tetraacrylate
  • 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 absorb
  • 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.
  • DMAc dimethylacetamide
  • M-phenylenediamine [2] was dissolved in DMAc.
  • 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.
  • 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.
  • 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).
  • 3M Optically Clear Adhesive 8146-2 manufactured by attaching the protective film surface and the glass via an adhesive sheet of 3M Optically Clear Adhesive 814
  • 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.

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Abstract

Composition comprenant un polymère hyper-ramifié contenant un cycle triazine coiffé d'un groupe arylamino contenant un atome de fluor, par exemple un polymère représenté par la formule [4], un agent de réticulation A ayant un poids moléculaire de 1 000 ou plus et un absorbeur de rayons ultraviolets. La composition présente une excellente résistance à la lumière, peut fournir un film capable d'améliorer la visibilité d'un film conducteur transparent, et est par conséquent appropriée en tant que composition pour former un film protecteur pour un film conducteur transparent.
PCT/JP2019/029115 2018-07-26 2019-07-25 Composition pour former un film protecteur pour film conducteur transparent WO2020022410A1 (fr)

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WO2022228449A1 (fr) * 2021-04-29 2022-11-03 上海瑞暨新材料科技有限公司 Procédé de préparation de résine de polyimide et film mince de celle-ci

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JP2008155387A (ja) * 2006-12-21 2008-07-10 Nippon Synthetic Chem Ind Co Ltd:The 積層体
WO2016194926A1 (fr) * 2015-06-03 2016-12-08 日産化学工業株式会社 Polymère contenant un cycle triazine, et composition pour l'utilisation de formation de film le contenant
WO2017094643A1 (fr) * 2015-11-30 2017-06-08 日産化学工業株式会社 Polymère à cycle triazine et composition filmogène le contenant
JP2017187775A (ja) * 2016-04-05 2017-10-12 凸版印刷株式会社 調光シート

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JP2008155387A (ja) * 2006-12-21 2008-07-10 Nippon Synthetic Chem Ind Co Ltd:The 積層体
WO2016194926A1 (fr) * 2015-06-03 2016-12-08 日産化学工業株式会社 Polymère contenant un cycle triazine, et composition pour l'utilisation de formation de film le contenant
WO2017094643A1 (fr) * 2015-11-30 2017-06-08 日産化学工業株式会社 Polymère à cycle triazine et composition filmogène le contenant
JP2017187775A (ja) * 2016-04-05 2017-10-12 凸版印刷株式会社 調光シート

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WO2022228449A1 (fr) * 2021-04-29 2022-11-03 上海瑞暨新材料科技有限公司 Procédé de préparation de résine de polyimide et film mince de celle-ci

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