JP5564535B2 - Composition for forming transparent conductive film, transparent conductive film and antireflection film - Google Patents

Description

  The present invention relates to a composition for forming a transparent conductive film and a cured film obtained from the composition. More specifically, the present invention has an antistatic effect by being applied to the surface of various substrates or printed and cured. In addition, a composition capable of forming a transparent conductive film having as little hue absorption as possible, a very high visible light transmittance of the film, and excellent in friction resistance, and a composition formed using such a composition The present invention relates to a transparent conductive film and an antireflection film.

  Transparent conductive films are attracting attention because they are useful as members such as antistatic films and antireflection films in applications such as film-type liquid crystal elements, touch panels, and plastic optical members. As a conductive material added to the composition for forming a transparent conductive film, a conductive filler, a conductive polymer, a surfactant such as a quaternary ammonium salt, an ionic liquid, or the like is used.

  Conventionally, a transparent conductive film is based on, for example, a conductive material made of fine metal particles such as indium tin oxide (ITO), indium oxide, tin oxide, zinc oxide, silver, nickel, or gold by sputtering or vacuum deposition. It was formed by forming a film on the material. However, the production of a transparent conductive film using a sputtering method or a vacuum deposition method has problems of production cost and environmental load. On the other hand, a method for forming a transparent conductive film by applying a coating material containing the conductive material to a base material is relatively simple, and therefore, a transparent conductive film can be produced at low cost, and is used for this purpose. Many conductive material-containing paints have also been proposed (for example, Patent Document 1).

  By the way, in the conductive film containing metal fine particles including metal fine particles as the conductive material, there is a problem that absorption occurs in the transmitted light depending on the light transmission spectrum of the metal fine particles, and coloring occurs due to the absorption of the transmitted light. . In addition, metal oxide-containing conductive films such as indium oxide, ATO, and ITO also have a problem in that they have absorption in the visible light region and high visible light transmittance cannot be obtained. Therefore, it has been difficult to obtain a transparent conductive film having high transparency and low resistance.

  On the other hand, when a surfactant or an ionic liquid is used as the conductive material instead of the conductive metal fine particles or the conductive metal oxide fine particles, a transparent conductive film having almost no absorption in the visible light region can be obtained. There is another problem that the surfactant or ionic liquid bleeds out to the surface of the membrane as time goes by. The antistatic property deteriorates with time and deteriorates, and the antistatic property depends on humidity. There were also problems such as.

  As a method for solving such a problem, an antistatic coating composition containing ionic liquid-containing inorganic fine particles has been proposed (Patent Document 2). However, this method requires a separate manufacturing process for containing the ionic liquid in the inorganic fine particles in order to produce the ionic liquid-containing inorganic fine particles, which not only makes the manufacturing method complicated, but also the ionic liquid contains the inorganic fine particles. There is a problem that the conductivity of the ionic liquid is not sufficiently exhibited because it is contained inside.

JP 2011-065,966 JP 2009-013,198

  Therefore, as a result of intensive studies to solve the various problems in the conventional transparent conductive film, the present inventors applied a transparent conductive film forming composition containing inorganic fine particles, a dispersion stabilizer, an ionic liquid and a binder. In the transparent conductive film obtained by the above, the present inventors have found that the inorganic fine particles stabilized with a specific dispersion stabilizer exhibit an action of suppressing bleed-out of the ionic liquid to the film surface, and have completed the present invention.

  Therefore, an object of the present invention is to form a transparent conductive film which does not require a complicated manufacturing process, can form a transparent conductive film excellent in conductivity, transparency and water resistance, and has no bleed-out problem. The object is to provide a composition, and also to provide a transparent conductive film and an antireflection film which are produced using this transparent conductive film forming composition and are excellent in conductivity, transparency and water resistance.

  That is, this invention is a composition for transparent conductive film formation containing an inorganic fine particle (A), a dispersion stabilizer (B), an ionic liquid (C), and a binder (D).

  In the present invention, the inorganic fine particles (A) include titanium oxide, barium titanate, iron oxide, barium sulfate, zinc sulfide, zinc oxide, tin oxide, zirconium oxide, silicon oxide, aluminum oxide, cerium oxide, indium oxide, five At least one selected from antimony oxide, ITO, and ATO can be mentioned, and examples of the dispersion stabilizer (B) include at least one selected from the group consisting of chelating agents and metal complexes.

  Moreover, the composition for forming a transparent conductive film of the present invention preferably has a dispersion stabilizer (B) content of 2 to 45 parts by mass per 100 parts by mass of the inorganic fine particles (A), and the binder (D). The content is 10 to 1000 parts by mass, and the content of the ionic liquid (C) is 0.001 to the total amount (A + B + D) of the inorganic fine particles (A), the dispersion stabilizer (B), and the binder (D). 30% by mass.

And this invention is a transparent conductive film obtained by apply | coating or printing the said composition for transparent conductive film on a base material, or making it harden | cure, Preferably, refractive index 1.45-1.90, light It is a transparent conductive film having a transmittance of 80% or more, a haze of 2.0% or less, and a surface resistance value of 1 × 10 ¹⁴ Ω / □ or less, and an antireflection produced using the transparent conductive film forming composition. It is a film.

  The composition for forming a transparent conductive film of the present invention does not require a complicated manufacturing process and can form a transparent conductive film excellent in conductivity, transparency and water resistance. Moreover, the refractive index obtained by adjusting the relative compounding amount of the inorganic fine particles can be controlled, and can be suitably applied not only to the optical field but also to various other uses.

  Hereinafter, the composition for forming a transparent conductive film of the present invention will be described in more detail and specifically.

  The inorganic fine particles (A) used in the present invention are added for various purposes such as improving the film hardness of the transparent conductive film or controlling the film refractive index. As such inorganic fine particles, conventionally known inorganic fine particles can be used. For example, titanium oxide, barium titanate, iron oxide, barium sulfate, zinc sulfide, zinc oxide, tin oxide, zirconium oxide, silicon oxide, Examples thereof include aluminum oxide, cerium oxide, indium oxide, ITO, ATO, and antimony pentoxide. Of these inorganic fine particles, zirconium oxide, silicon oxide, aluminum oxide, and antimony pentoxide are more preferable from the viewpoint of high transparency. The primary particle diameter of these inorganic fine particles is preferably 0.2 μm or less, and if it is 0.2 μm or more, the film tends to be white and cloudy.

  Examples of the dispersion stabilizer (B) used in the present invention include metal complexes and chelating agents.

  Here, the metal complex is a metal selected from the group consisting of zirconium, titanium, chromium, manganese, iron, cobalt, nickel, copper, vanadium, aluminum, zinc, indium, tin and platinum, preferably the color of the dispersion. A ligand selected from the group consisting of at least one metal selected from the group consisting of zirconium, titanium, aluminum, zinc, indium and tin and a β-diketone, preferably pivaloyltrifluoroacetone And a metal complex composed of at least one ligand selected from the group consisting of acetylacetone, trifluoroacetylacetone, and hexafluoroacetylacetone.

  Examples of the chelating agent include polyamines such as ethylenediamine, diethylenetriamine, and triethylenetetramine; β-diketones such as dipivaloylmethane, pivaloyltrifluoroacetone, acetylacetone, trifluoroacetylacetone, and hexafluoroacetylacetone; Dimethylglyoxime, oxine, iminodiacetic acid, ethylenediaminetetraacetic acid, succinic acid, etc., preferably dipivaloylmethane, pivaloyltrifluoroacetone, acetylacetone, trifluoroacetylacetone, hexafluoroacetylacetone, etc. β-diketones.

  In the composition for forming a transparent conductive film of the present invention, the amount of the dispersion stabilizer (B) is 2 to 45 parts by mass, preferably 5 parts by mass per 100 parts by mass of the inorganic fine particles (A). The amount is preferably 20 parts by mass or less. When the amount is less than 2 parts by mass, it is difficult to disperse and stabilize the inorganic fine particles, and it is difficult to suppress bleed out of the ionic liquid to the film. On the other hand, when it is more than 45 parts by mass, the dispersion stabilizer tends to precipitate without being completely dissolved in the composition for forming a transparent conductive film.

  In the present invention, in order to further improve the storage stability of the composition for forming a transparent conductive film, in addition to the above dispersion stabilizer (B), another dispersant is further added as a dispersion aid. Also good. The type of such a dispersion aid is not particularly limited, but preferably, a phosphate ester-based nonionic dispersant having a polyoxyethylene alkyl structure can be mentioned.

  Furthermore, the binder (D) used by this invention can use the arbitrary binder generally used with the coating material without a restriction | limiting especially. Preferably, it is an active energy ray-curable binder.

  Examples of such binder (D) include alkyd resin, polyester resin, unsaturated polyester resin, polyurethane resin, acrylic resin, epoxy resin, phenol resin, vinyl resin, silicone resin, fluorine resin, phthalic acid resin, amino resin. , Polyamide resin, polyacryl silicone resin, melamine resin, urea resin, binder resin modified by these, etc. can be exemplified, and only one of them can be used alone or in combination of two or more. it can.

  Furthermore, the binder may contain a crosslinking agent as necessary. Examples of such a crosslinking agent include basic functional groups such as amino groups, neutral functional groups such as OH groups, carboxyls, and the like. An arbitrary functional group having two or more reactive functional groups such as an isocyanate functional group such as an isocyanate group in one molecule can be exemplified.

  Here, the binder (D) may be a radical polymerizable monomer, and if it is a monomer having a radical polymerizable unsaturated group (α, β-ethylenically unsaturated group), an amino group Any of those having a basic functional group such as those having a neutral functional group such as an OH group, those having an acidic functional group such as a carboxyl group, or those not having such a functional group may be used.

  In the present invention, examples of the active energy ray-curable binder that can be used as the binder (D) include an acrylate or methacrylate compound, a radical polymerizable monomer, and a radical polymerizable oligomer. Here, if the radical polymerizable monomer is a monomer having a radical polymerizable unsaturated group (α, β-ethylenically unsaturated group), one having a basic functional group such as an amino group, an OH group Any of those having a neutral functional group such as those having an acidic functional group such as a carboxyl group, or those having no functional group may be used.

  Specific examples of the radical polymerization monomer include, for example, radical polymerizable monomers other than acrylate or methacrylate such as styrene, vinyl toluene, vinyl acetate, N-vinyl pyrrolidone, acrylonitrile, allyl alcohol, methyl acrylate or methyl methacrylate, ethyl acrylate. Or ethyl methacrylate, isopropyl acrylate or isopropyl methacrylate, 2-ethylhexyl acrylate or 2-ethylhexyl methacrylate, butyl acrylate or butyl methacrylate, cyclohexyl acrylate or cyclohexyl methacrylate, tetrahydrofurfuryl acrylate or tetrahydrofurfuryl methacrylate, N-vinylpyrrolidone, 2-hydroxy Ethyl acrylate or 2-hydroxyethyl methacrylate Chryrate, 2-hydroxypropyl acrylate or 2-hydroxypropyl methacrylate, polyethylene glycol monoacrylate or polyethylene glycol monomethacrylate, methoxypolyethylene glycol monoacrylate or methoxypolyethylene glycol monomethacrylate, polypropylene glycol monoacrylate or polypropylene glycol monomethacrylate, polyethylene glycol polypropylene glycol Monoacrylate or polyethylene glycol Polypropylene glycol monomethacrylate, polyethylene glycol polytetramethylene glycol monoacrylate or polyethylene glycol polytetramethylene glycol monomethacrylate, glycidyl acrylate or glycidyl methacrylate Monofunctional acrylates or methacrylates such as acrylate, ethylene glycol diacrylate or ethylene glycol methacrylate, diethylene glycol diacrylate or diethylene glycol dimethacrylate, triethylene glycol diacrylate or triethylene glycol dimethacrylate, tetraethylene glycol diacrylate or tetraethylene glycol dimethacrylate , Polyethylene glycol diacrylate or polyethylene dimethacrylate, polypropylene glycol diacrylate or polypropylene glycol dimethacrylate, neopentyl glycol diacrylate or neopentyl glycol dimethacrylate, allyl diacrylate or allyl dimethacrylate, bisphenol A di Chryrate or bisphenol A dimethacrylate, ethylene oxide modified bisphenol A diacrylate or ethylene oxide modified bisphenol methacrylate, polyethylene oxide modified bisphenol A diacrylate or polyethylene oxide modified bisphenol A dimethacrylate, ethylene oxide modified bisphenol A diacrylate or ethylene oxide modified bisphenol A Dimethacrylate, bisphenol S diacrylate or bisphenol S dimethacrylate, 1,4-butanediol S diacrylate or 1,4-butanediol S dimethacrylate, 1,3-butylene glycol diacrylate or 1,3-butylene glycol dimethacrylate Bifunctional acrylate or methacrylate such as trimethylol group Pantriacrylate or trimethylolpropane trimethacrylate, glycerol triacrylate or glycerol trimethacrylate, pentaerythritol triacrylate or pentaerythritol trimethacrylate, pentaerythritol tetraacrylate or pentaerythritol tetramethacrylate, ethylene modified trimethylolpropane triacrylate or ethylene modified trimethylol Mention may be made of trifunctional or higher functional acrylates and methacrylates such as propane trimethacrylate, dipentaerythritol hexaacrylate or dipentaerythritol hexamethacrylate.

  Specific examples of the radical polymerization oligomer include, for example, polyester acrylate or polyester methacrylate, polyurethane acrylate or polyurethane methacrylate, epoxy acrylate or epoxy methacrylate, polyether acrylate or polyether methacrylate, oligoacrylate or oligomethacrylate, alkyd acrylate or alkyd. Mention may be made of prepolymers having at least one acryloyl group or methacryloyl group such as methacrylate, polyol acrylate or polyol methacrylate, silicone acrylate or silicone methacrylate. Particularly preferred radical polymerization oligomers are polyester, epoxy, polyurethane acrylates or methacrylates.

  In the present invention, the blending amount of the binder (D) is preferably 10 parts by mass or more and 1000 parts by mass or less, more preferably 20 parts by mass or more and 400 parts by mass or less, per 100 parts by mass of the inorganic fine particles (A). When the amount is less than 10 parts by mass, the adhesion to the substrate tends to be lowered, and when the amount is more than 1000 parts by mass, the effect of adding inorganic fine particles tends to be difficult to obtain.

  In the present invention, when an active energy ray-curable binder is used as the binder (D), a polymerization initiator and / or a photosensitizer is added to the composition in order to obtain a useful active energy ray-curable binder. Is desirable. By adding a polymerization initiator or a photosensitizer, the composition can be cured by irradiation with a small amount of active energy rays. However, the composition for forming a transparent conductive film of the present invention is a case where it can be thermally cured, and when the binder (D) is used as a thermosetting binder, it is changed to a photosensitizer. A suitable radical polymerization initiator (for example, azobisisobutyronitrile) may be blended.

  Examples of the polymerization initiator used for such purpose include 1-hydroxycyclohexyl phenyl ketone, benzophenone, benzyl dimethyl methyl ketone, benzoin methyl ether, benzoin ethyl ether, p-chlorobenzophenone, 4-benzoyl-4-methyldiphenyl. Mention of sulfide, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, etc. Can do. A polymerization initiator may be used individually by 1 type, and may use 2 or more types together.

  In this invention, the compounding quantity of the polymerization initiator used for such a purpose is 0.1-20 mass parts normally per 100 mass parts of binders (D).

  In addition, you may mix | blend various conventional additives other than the above in the range which does not impair the objective in the composition for transparent conductive film formation of this invention. Examples of such additives include a polymerization inhibitor, a curing catalyst, an antioxidant, and a leveling agent.

  Furthermore, as the ionic liquid (C) used in the present invention, any commonly used ionic liquid can be used without particular limitation. The ionic liquid used in the present invention is a salt that exhibits a molten state in a wide temperature range including room temperature. Preferably, the thing compatible with the binder (D) and dispersion stabilizer (B) used for the composition for transparent conductive film formation of this invention is preferable.

  Here, as a cation constituting the ionic liquid, for example, ammonium-based, pyridinium-based, imidazolium-based, pyrrolidinium-based, piperidinium-based, pyrazolium-based, organic nitrogen-based cations, phosphonium-based organic phosphorus-based, etc. Although organic sulfur type cations, such as a cation and a sulfonium type | system | group, can be mentioned, It is not restrict | limited to these. In particular, from the viewpoint of conductivity and water resistance, an organic nitrogen cation or an organic phosphorus cation is more preferable. Moreover, said ionic liquid can be used individually by 1 type, and can also use 2 or more types together.

  Examples of the anion constituting the ionic liquid include halogens such as bromide ions and bis (trifluoromethanesulfonic acid) imide, borons such as tetrafluoroborate, and phosphoruss such as hexafluorophosphate. However, it is not limited to these.

  In the present invention, the blending amount of the ionic liquid (C) is preferably 0.001% by mass to 30% by mass with respect to the total amount of the inorganic fine particles (A), the dispersion stabilizer (B), and the binder (D). Hereinafter, it is more preferably 0.001% by mass to 25% by mass. When the amount of the ionic liquid (C) is less than 0.001% by mass, it is difficult to obtain the effect of adding the ionic liquid. On the other hand, when the amount is more than 30% by mass, the transparency of the film tends to decrease. Furthermore, bleeding out to the surface of the film becomes remarkable, and the water resistance tends to decrease.

  You may mix | blend a dispersion medium with the composition for transparent conductive film formation of this invention suitably. Examples of the dispersion medium include alcohols such as water, methanol, ethanol, isopropanol, normal butanol, 2-butanol, octanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone. Ketones such as ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, esters such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate, ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether, , Aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene, and amides such as dimethylformamide, N, N-dimethylacetoacetamide and N-methylpyrrolidone And the like. Among them, ethanol, isopropanol, normal butanol, 2-butanol, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, ethyl acetate, butyl acetate, toluene, xylene, and ethylbenzene are preferable, and methyl ethyl ketone Butanol, xylene, ethylbenzene, and toluene are more preferable. In the present invention, only one type of dispersion medium can be used alone, or two or more types can be used in combination.

  For the composition for forming a transparent film of the present invention, the inorganic fine particles (A), the dispersion stabilizer (B), the ionic liquid (C) and the binder (D) are added in any order or simultaneously and mixed thoroughly. Can be manufactured. A dispersion medium can be added as needed. Specifically, for example, a method of adding and dispersing inorganic fine particles in a solution in which a dispersion stabilizer and an ionic liquid are mixed, or a solution diluted by adding a dispersion medium as necessary, and then adding a binder. In addition, the inorganic fine particles, the dispersion stabilizer, the ionic liquid and the binder may be further mixed with a dispersion medium if necessary, and mixed and dispersed at the same time. The inorganic fine particles and the dispersion stabilizer may be further mixed with a dispersion medium as necessary. In addition, there is a method of adding an ionic liquid and a binder after mixing and dispersing, but is not limited thereto. About said dispersion | distribution operation, it can carry out with a paint shaker, a ball mill, a sand mill, a sentry mill, or a three roll etc. by a conventional method.

  The substrate on which the transparent conductive film-forming composition of the present invention is applied or printed to form the transparent conductive film of the present invention on the surface is widely used in various fields including electronic equipment. And various materials formed of various synthetic resins, glass, ceramics, and the like, and these may be any shape such as a sheet, a film, and a plate. Specific examples of the synthetic resin include, but are not limited to, polyethylene, polypropylene, polycarbonate, acrylic resin, methacrylic resin, polyvinyl chloride, polyester resin, polyamide resin, and phenol resin.

In addition, as a method for applying or printing the transparent conductive film forming composition of the present invention on the surface of the substrate, it can be performed by a conventional method, for example, a method such as roll coating, spin coating, or screen printing. . Thereafter, if the binder is not an active energy ray curable type, the solvent is evaporated by heating if necessary, and the coating film is dried and cured. When the binder is an active energy ray curable type, the solvent is evaporated by heating if necessary, the coating film is dried, and then the active energy ray (ultraviolet ray or electron beam) is irradiated. Here, as the active energy ray source, a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, a xenon lamp, an excimer laser, a dye laser, or an ultraviolet ray source, and an electron beam accelerator can be used. in the case of in the range of 50 to 3000 mJ / cm ^2, but also, in the case of the electron beam is suitably in the range of 0.2~1000μC / cm ^2.

About the film thickness of the transparent conductive film obtained by hardening the composition for transparent conductive film formation of this invention, Preferably it exists in the range of 0.1 to 10.0 micrometer, More preferably, 0.3 to 5.0 micrometer The inorganic fine particles are uniformly dispersed in the cured film, the light transmittance is 80% or more, preferably 83% or more, and the haze is 2.0% or less, preferably 1 0.5% or less, and the surface resistance value should be 1 × 10 ¹⁴ Ω / □ or less, preferably 1 × 10 ¹² Ω / □ or less, in terms of transparency, electrical conductivity, and water resistance. Excellent.

In the present invention, the refractive index of the transparent conductive film can be controlled by adjusting the ratio between the amount of the inorganic fine particles and the amount of the binder. Specifically, the refractive index is 1.45-1. It is possible to control in the range of 90. Here, in order to control the refractive index to a relatively low value, the blending ratio of the inorganic fine particles and the binder may be adjusted in the direction of the binder. On the contrary, in order to control the refractive index to a relatively high value. This blending ratio may be adjusted in the direction of the inorganic fine particles.
In addition, since the refractive index of the transparent conductive film is also affected by the refractive index of the inorganic fine particles and the binder, not only the ratio of the amount of the inorganic fine particles and the amount of the binder is controlled, but also the types of the inorganic fine particles and the binder are optimal. You may choose.

  Hereinafter, the contents of the present invention will be described more specifically based on examples and comparative examples. Here, the components used in Examples and Comparative Examples are as follows, and “parts” used in Examples and Comparative Examples are “parts by mass”.

<Inorganic fine particles>
・ Zirconium oxide (refractive index 2.2, primary particle diameter 20 nm)
Aluminum oxide (refractive index 1.76, primary particle size 20 nm)
ATO (antimony-doped tin oxide) (refractive index 2.00, primary particle diameter 30 nm)

<Dispersion stabilizer>
Acetyl acetone (C ₅ H ₇ O ₂ )
Zirconium acetylacetonate _{([Zr (C 5 H 7} O 2) 4])
Titanium acetylacetonate _{([Ti (C 5 H 7} O 2) 4])
Aluminum acetylacetonate _{([Al (C 5 H 7} O 2) 3])
Zinc acetylacetonate _{([Zn (C 5 H 7} O 2) 2])
Indium acetylacetonate ([In (C ₅ H ₇ O ₂ ) ₃ ])
Dibutyl-tin bisacetylacetonate ([(C ₄ H ₉ ) Sn (C ₅ H ₇ O ₂ ) ₂ ])

<Ionic liquid>
・ Ammonium-based ionic liquid [Kanto Chemical Co., Ltd., Tributylmethylammonium bis (trifluoromethanesulfonyl) imide]
・ Phosphonium-based ionic liquid [Kanto Chemical Co., Ltd., Tributylmethylphosphonium bis (trifluoromethanesulfonyl) imide]
・ Imidazolium-based ionic liquid [Kanto Chemical Co., Ltd., 1-Hexyl-3-methylimidazolium tetrafluoroborate]
・ Pyrrolidinium ionic liquid [Kanto Chemical Co., Ltd., 1-Ethyl-1-methylpyrrolidinium hexafluorophosphate]
・ Sulphonium-based ionic liquid (Kanto Chemical Co., Ltd., Dimethylmethylsulfonium bis (trifluoromethanesulfonyl) imide)

<Binder>
DPHA (dipentaerythritol hexaacrylate, refractive index 1.49)

<Photopolymerization initiator>
IC-184 (BASF, 1-hydroxycyclohexyl phenyl ketone)

[Example 1]
Paint shaker with 100 parts of zirconium oxide powder containing all components in a ratio of 12 parts zirconium acetylacetonate, 16 parts ammonium ionic liquid, 180 parts 2-butanol, and 800 parts glass beads. And kneaded for 4 hours. After kneading, the glass beads were removed to obtain a zirconium oxide fine particle dispersion. 33 parts of DPHA and 3 parts of IC-184 were added to this dispersion and uniformly dissolved to obtain a transparent conductive film forming composition. Using a roll coater, this transparent conductive film-forming composition was applied onto a PET film, the organic solvent was evaporated, and then irradiated with 300 mJ / cm ² of light using a high-pressure mercury lamp in the air, and the thickness was 2 μm. A cured film (transparent conductive film) was prepared.

[Example 2]
A cured film having a thickness of 2 μm was produced in the same manner as in Example 1 except that 12 parts of acetylacetone was blended in place of 12 parts of zirconium acetonate.

Example 3
A cured film having a thickness of 2 μm was produced in the same manner as in Example 2 except that 37 parts of the sulfonium-based ionic liquid was blended instead of 16 parts of the ammonium-based ionic liquid.

Example 4
A cured film having a thickness of 2 μm was produced in the same manner as in Example 3 except that 40 parts of acetylacetone was blended in place of 12 parts of acetylacetone.

Example 5
In 100 parts of zirconium oxide powder, 12 parts of zirconium acetylacetonate, 50 parts of ammonium-based ionic liquid, 340 parts of 2-butanol, and 800 parts of glass beads are added to all components in a container, and a paint shaker And kneaded for 4 hours. After kneading, the glass beads were removed to obtain a zirconium oxide fine particle dispersion. 100 parts of DPHA and 10 parts of IC-184 were added to this dispersion and dissolved uniformly to obtain a composition for forming a transparent conductive film. Thereafter, a cured film (transparent conductive film) having a thickness of 2 μm was produced in the same manner as in Example 1.

Example 6
Paint shaker with 100 parts of zirconium oxide powder containing all components in a ratio of 12 parts zirconium acetylacetonate, 150 parts ammonium ionic liquid, 750 parts 2-butanol, and 800 parts glass beads. And kneaded for 4 hours. After kneading, the glass beads were removed to obtain a zirconium oxide fine particle dispersion. 500 parts of DPHA and 50 parts of IC-184 were added to this dispersion and dissolved uniformly to obtain a composition for forming a transparent conductive film. Thereafter, a cured film (transparent conductive film) having a thickness of 2 μm was produced in the same manner as in Example 1.

Example 7
Paint shaker with 100 parts of aluminum oxide powder containing all components in a ratio of 12 parts zirconium acetylacetonate, 16 parts ammonium ionic liquid, 180 parts 2-butanol, and 800 parts glass beads. And kneaded for 4 hours. After kneading, the glass beads were removed to obtain an aluminum oxide fine particle dispersion. 33 parts of DPHA and 3 parts of IC-184 were added to this dispersion and uniformly dissolved to obtain a transparent conductive film forming composition. Thereafter, a cured film (transparent conductive film) having a thickness of 2 μm was produced in the same manner as in Example 1.

Example 8
A cured film having a thickness of 2 μm was prepared in the same manner as in Example 7 except that 32 parts of the ammonium-based ionic liquid was blended instead of 16 parts of the ammonium-based ionic liquid.

Example 9
In 100 parts of ATO powder, 12 parts of zirconium acetylacetonate, 50 parts of ammonium-based ionic liquid, 340 parts of 2-butanol, and 800 parts of glass beads are added to all components in a container. Kneaded for 4 hours. After kneading, the glass beads were removed to obtain an ATO fine particle dispersion. 100 parts of DPHA and 10 parts of IC-184 were added to this dispersion and dissolved uniformly to obtain a composition for forming a transparent conductive film. Thereafter, a cured film (transparent conductive film) having a thickness of 2 μm was produced in the same manner as in Example 1.

Example 10
Paint shaker with 100 parts of zirconium oxide powder containing all components in a ratio of 12 parts indium acetylacetonate, 16 parts ammonium ionic liquid, 180 parts 2-butanol, and 800 parts glass beads. And kneaded for 4 hours. After kneading, the glass beads were removed to obtain a zirconium oxide fine particle dispersion. 33 parts of DPHA and 3 parts of IC-184 were added to this dispersion and uniformly dissolved to obtain a transparent conductive film forming composition. Thereafter, a cured film (transparent conductive film) having a thickness of 2 μm was produced in the same manner as in Example 1.

Example 11
A cured film having a thickness of 2 μm was produced in the same manner as in Example 10 except that 2.5 parts of zinc acetylacetonate was blended instead of 12 parts of indium acetylacetonate.

Example 12
A cured film having a thickness of 2 μm was produced in the same manner as in Example 10, except that 12 parts of titanium acetylacetonate was blended instead of 12 parts of indium acetylacetonate.

Example 13
A cured film having a thickness of 2 μm was prepared in the same manner as in Example 10 except that 10 parts of tin acetylacetonate was blended instead of 12 parts of indium acetylacetonate.

Example 14
A cured film having a thickness of 2 μm was produced in the same manner as in Example 10 except that 2.5 parts of aluminum acetonate was blended instead of 12 parts of indium acetylacetonate.

Example 15
A cured film having a thickness of 2 μm was produced in the same manner as in Example 2 except that 16 parts of the phosphonium ionic liquid was blended instead of 16 parts of the ammonium ionic liquid.

Example 16
A cured film having a thickness of 2 μm was prepared in the same manner as in Example 2 except that 16 parts of the imidazolium-based ionic liquid was blended instead of 16 parts of the ammonium-based ionic liquid.

Example 17
A cured film having a thickness of 2 μm was prepared in the same manner as in Example 2 except that 16 parts of pyrrolidinium ionic liquid was blended instead of 16 parts of ammonium ionic liquid.

Example 18
Put all the ingredients in a container at a ratio of 12 parts acetylacetone, 16 parts ammonium ionic liquid, 180 parts 2-butanol, and 800 parts glass beads to 60 parts ATO powder and 40 parts zirconium oxide powder, Kneaded for 4 hours with a paint shaker. After kneading, the glass beads were removed to obtain an ATO / zirconium oxide fine particle dispersion. 33 parts of DPHA and 3 parts of IC-184 were added to this dispersion and uniformly dissolved to obtain a transparent conductive film forming composition. Thereafter, a cured film (transparent conductive film) having a thickness of 2 μm was produced in the same manner as in Example 1.

Example 19
A cured film having a thickness of 2 μm was produced in the same manner as in Example 18 except that 40 parts of aluminum oxide powder was blended instead of 40 parts of zirconium oxide powder.

Example 20
Put all the ingredients in a container in a ratio of 12 parts acetylacetone, 16 parts ammonium ionic liquid, 180 parts 2-butanol, and 800 parts glass beads to 80 parts zirconium oxide powder and 20 parts aluminum oxide powder. Kneaded for 4 hours with a paint shaker. After kneading, the glass beads were removed to obtain a zirconium oxide / aluminum oxide fine particle dispersion. 33 parts of DPHA and 3 parts of IC-184 were added to this dispersion and dissolved uniformly to obtain a composition for forming a transparent conductive film. Thereafter, a cured film (transparent conductive film) having a thickness of 2 μm was produced in the same manner as in Example 1.

[Comparative Example 1]
All components were placed in a container at a ratio of 12 parts zirconium acetylacetonate, 12 parts ammonium-based ionic liquid, 180 parts 2-butanol, and 800 parts glass beads, and kneaded in a paint shaker for 4 hours. After kneading, the glass beads were removed to obtain a dispersion. 33 parts of DPHA and 3 parts of IC-184 were added to this dispersion and uniformly dissolved to obtain a transparent conductive film forming composition. Thereafter, a cured film (transparent conductive film) having a thickness of 2 μm was produced in the same manner as in Example 1.

[Comparative Example 2]
All components were put into a container at a ratio of 17 parts of ammonium-based ionic liquid, 180 parts of 2-butanol, and 800 parts of glass beads to 100 parts of zirconium oxide powder, and kneaded for 4 hours with a paint shaker. The dispersion thickened after kneading.

[Comparative Example 3]
All components were put into a container in a ratio of 12 parts of zirconium acetylacetonate, 180 parts of 2-butanol, and 800 parts of glass beads with respect to 100 parts of the zirconium oxide powder, and kneaded with a paint shaker for 4 hours. After kneading, the glass beads were removed to obtain a zirconium oxide fine particle dispersion. 33 parts of DPHA and 3 parts of IC-184 were added to this dispersion and uniformly dissolved to obtain a transparent conductive film forming composition. Thereafter, a cured film (transparent conductive film) having a thickness of 2 μm was produced in the same manner as in Example 1.

<Evaluation method>
(1) Transmissivity and haze of transparent conductive film About the transparent conductive films obtained in Examples 1 to 20 and Comparative Examples 1 to 3, the transmittance (%) and haze (%) were measured using a haze meter (Nippon Denshoku Industries ( NDH5000). The measured value is a measured value including the base material.

(2) Surface resistance value of transparent conductive film About the transparent conductive films obtained in Examples 1 to 20 and Comparative Examples 1 to 3, the surface resistance value (Ω / □) was measured with a resistivity meter (Hiresta IP manufactured by Mitsubishi Chemical Corporation). MCP-HT260 surface resistor).

(3) Refractive index of a transparent conductive film About the transparent conductive film obtained in Examples 1-20 and Comparative Examples 1-3, the refractive index was measured with the refractometer. (Atago Co., Ltd. Abbe refractometer DR-M4)

(4) Immersion test About the transparent conductive films obtained in Examples 1 to 20 and Comparative Examples 1 to 3, after being immersed in distilled water for 24 hours, the surface resistance value (Ω / □) was measured with a resistivity meter (Mitsubishi Chemical Corporation). Measured with Hiresta IP MCP-HT260 Surface Resistor).

  Table 1 (Examples 1 to 9), Table 2 (Examples 10 to 16), and Table 3 (Examples 17 to 20 and comparative examples) together with the composition of each of the above measurement results and evaluation results 1-3) respectively.

  As is clear from the results shown in Tables 1 to 3, in the case of Examples 1 to 20 obtained by mixing and dispersing inorganic fine particles, a dispersion stabilizer, and an ionic liquid, an excellent initial surface resistance value was obtained. In addition to showing, an excellent surface resistance value was maintained even after the immersion test.

On the other hand, when no inorganic fine particles are blended (Comparative Example 1), the conductivity is greatly reduced after the immersion test, and when no dispersion stabilizer is added (Comparative Example 2), the viscosity is increased and transparent. When a composition for forming a conductive film was not obtained and no ionic liquid was blended (Comparative Example 3), conductivity having a surface resistance value of 1 × 10 ¹⁴ Ω / □ or less was not exhibited.

Claims (9)

Inorganic fine particles (A), a chelating agent and at least consisting of type dispersion stabilizer selected from the group consisting of a metal complex (B), a transparent conductive film-forming composition comprising an ionic liquid (C) and the binder (D). Chelating agents, polyamines, beta-diketones, polyaminocarboxylic acids, oxycarboxylic acids, oximes, oxine, and transparency according to claim 1, characterized in that it consists of at least one selected from the group consisting of oxalic acid A composition for forming a conductive film. The metal complex is composed of at least one metal selected from the group consisting of zirconium, titanium, chromium, manganese, iron, cobalt, nickel, copper, vanadium, aluminum, zinc, indium, tin, and platinum, and β-diketone. It consists of at least 1 type of ligand chosen from a group, The composition for transparent conductive film formation of Claim 1 or 2 characterized by the above-mentioned. The metal complex is a group consisting of at least one metal selected from the group consisting of zirconium, titanium, aluminum, zinc, indium, and tin, and pivaloyltrifluoroacetone, acetylacetone, trifluoroacetylacetone, and hexafluoroacetylacetone. at least one of claims 1 or 2 for forming a transparent conductive film composition as described in characterized by comprising a ligand selected from. Inorganic fine particles from titanium oxide, barium titanate, iron oxide, barium sulfate, zinc sulfide, zinc oxide, tin oxide, zirconium oxide, silicon oxide, aluminum oxide, cerium oxide, indium oxide, antimony pentoxide, ITO, and ATO It consists of at least 1 type chosen, The composition for transparent conductive film formation in any one of Claims 1-4 characterized by the above-mentioned. The content of the dispersion stabilizer is 2 to 45 parts by mass, the content of the binder is 10 to 1000 parts by mass, and the content of the ionic liquid is inorganic fine particles (A) and the dispersion stabilizer per 100 parts by mass of the inorganic fine particles. (B) the total amount (a + B + D), characterized in that a 0.001% by mass with respect to claim 1 for forming a transparent conductive film composition according to any one of 5 the binder (D). A transparent conductive film obtained by applying the composition for forming a transparent conductive film according to any one of claims 1 to 6 on a substrate, or printing and curing the composition. The refractive index is 1.45 to 1.90, the light transmittance is 80% or more, the haze is 2.0% or less, and the surface resistance value is 1 × 10 ¹⁴ Ω / □ or less. The transparent conductive film according to claim 7 . An antireflection film produced using the composition for forming a transparent conductive film according to any one of claims 1 to 6 .