JP2012077101A - Composition for forming transparent conductive film, transparent conductive film and antireflection film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition for forming a transparent conductive film that exhibits conductive properties stable with time over a long period of time and good film formability without lowering a coating speed even under high-humidity conditions of 30°C and RH of 85%, and is applied to surfaces of various substrates to form transparent conductive films excellent in transparency, film hardness, scratch resistance and antistatic functions.SOLUTION: The composition for forming transparent conductive films comprises an conductive metal oxide, a metal complex comprising a β-diketone, an active energy ray-curable compound, a photopolymerization initiator and a dispersing medium, where the dispersing medium comprises a dispersing medium A containing at least one carbonyl group and a dispersing medium B containing at least one hydroxy group and exhibits excellent conductive properties. The composition for forming transparent conductive films contains a non-conductive, highly refractive metal oxide in the place of a part of the conductive metal oxide and is excellent in conductive properties and high refractive properties. The transparent conductive films and the antireflection films are manufactured using the composition for forming transparent conductive films.

Description

  The present invention relates to a composition for forming a transparent conductive film, and a transparent conductive film and an antireflection film formed using the composition for forming a transparent conductive film. More specifically, the present invention relates to a storage film having excellent storage stability over time. In addition, it exhibits stable conductive properties, and exhibits good film formability even under high humidity conditions of 30 ° C x RH85% without reducing the coating speed. Furthermore, plastic, metal, wood, paper, glass, A composition for forming a transparent conductive film which can be applied to the surface of various substrates such as slate to form a transparent conductive film excellent in transparency, film hardness, scratch resistance and antistatic function, and using the composition The present invention relates to a transparent conductive film excellent in transparency, film hardness, scratch resistance, and antistatic function, and an antireflection film produced using the composition.

  In recent years, it has excellent coating properties as a protective coating material for preventing scratches (abrasion) on the surfaces of various substrates and preventing contamination, and a binder material for printing inks, and the surface of various substrates has hardness. There is a need for a curable composition capable of forming a cured film excellent in scratch resistance, abrasion resistance, low curling properties, adhesion, transparency, chemical resistance, coating surface appearance, and the like.

  Moreover, in applications to flat panel displays, touch panels, plastic optical components, etc., in addition to the above requirements, a curable composition that can form a cured film such as a transparent conductive film that is excellent in transparency and has an antistatic function. Things are required.

  Furthermore, antireflection films (cured films) are used in image display devices such as liquid crystal displays and cathode ray tube display devices and optical products. In addition to the characteristics of high transparency and low reflectance, the antireflection film is required to have a scratch resistance and a function of preventing adhesion of foreign matters such as dust and dirt. Therefore, the high refractive index layer of the antireflection film is required to have excellent scratch resistance and antistatic properties in addition to high transparency and high refractive index properties.

  As a means for imparting an antistatic function to such a cured film, a method of adding a surfactant, a conductive polymer, or conductive fine particles mainly composed of a metal oxide to the curable composition is known. In particular, in consideration of the purpose of producing a film having a permanent antistatic effect, a method of adding conductive fine particles is common. Further, as a method for adding such conductive fine particles, a method in which a chelating agent is blended in a resin solution or a solvent and an inorganic oxide is dispersed in the blend has been proposed (for example, Patent Document 1). And 2).

  In addition, the present inventors have proposed a method of blending a metal complex in place of a chelating agent in order to prevent corrosion of metal equipment and coating equipment mainly used in the dispersion treatment process. (See Japanese Patent Application No. 2009-217,991)

JP 2001-139,847 Japanese Patent Laid-Open No. 2001-139,889

  By the way, in such a composition for forming a transparent conductive film, in order to improve the productivity, it is excellent in storage stability when stored for a long period of time, and it is necessary that the conductive characteristics do not vary for a long period of time. It is.

  In order to impart a high film hardness of pencil hardness 2H or higher to a transparent conductive film or antireflection film formed using such a composition for forming a transparent conductive film, a dry film of about 2 μm or more is required. Although a thickness is required, in such coating for obtaining a dry film thickness of 2 μm or more, there is a problem that a whitening phenomenon easily occurs in the formed transparent conductive film when the humidity of the atmosphere becomes high. This whitening phenomenon is caused by condensation of moisture in the atmosphere on the surface of the coating film during curing due to the latent heat of evaporation generated when the solvent is volatilized after application of the transparent conductive film-forming composition, and a portion of the coating film components is deposited. It is. Therefore, as a means for solving this whitening phenomenon, methods of coating under a low humidity condition of 25 ° C. × RH 30% or less, addition of a surface conditioner, or addition of a high boiling point solvent are often employed. In the method of coating under humidity conditions, the coating conditions are limited and the productivity is lowered, and in the method of adding a surface conditioner, poor adhesion to the substrate and the topcoat layer is likely to occur. The method of adding causes another problem that the coating speed decreases and the productivity decreases.

  Therefore, the present inventors have intensively studied to solve such problems, and as a result, surprisingly, conductive metal oxides (or conductive metal oxides and nonconductive high refractive index metal oxides). ), A metal complex containing β-diketone, an active energy ray-curable compound, and a photopolymerization initiator, a dispersion medium having at least one carbonyl group (dispersion medium A), and a dispersion medium having at least one hydroxyl group ( Dispersing in a mixed dispersion medium containing dispersion medium B) shows stable conductive characteristics over time for a long time, and also shows good film formability even under high humidity conditions of 30 ° C. × RH 85% or more. As a result, the present invention has been completed.

  Therefore, the object of the present invention is to show stable conductive characteristics over time over a long period of time, exhibit good film formability even under high humidity conditions of 30 ° C. × RH 85% or more without reducing the coating speed, Transparent conductive film formation that can be applied to the surface of various substrates such as plastic, metal, wood, paper, glass, slate, etc. to form a transparent conductive film excellent in transparency, film hardness, scratch resistance and antistatic function It is to provide a composition for use.

  Another object of the present invention is formed by applying such a composition for forming a transparent conductive film to the surface of various substrates, and is transparent with excellent transparency, film hardness, scratch resistance and antistatic function. An object is to provide a conductive film and an antireflection film.

  That is, the present invention includes a conductive metal oxide, a metal complex containing β-diketone, an active energy ray-curable compound, a photopolymerization initiator, and a dispersion medium, wherein the dispersion medium has at least one carbonyl group. A transparent conductive film-forming composition comprising a medium A and a dispersion medium B having at least one hydroxyl group. In the present invention, β-- per 100 parts by weight of the conductive metal oxide The content of the metal complex containing the diketone is 3 to 450 parts by mass, the content of the active energy ray-curable compound is 14 to 10000 parts by mass, and the content of the dispersion medium is 60 to 70000 parts by mass. In addition, the content of the photopolymerization initiator is 0.1 to 20 parts by mass per 100 parts by mass of the active energy ray-curable compound, and the mass ratio (A / B) between the dispersion medium A and the dispersion medium B A composition for forming a transparent conductive film, which is a 90 / 10-10 / 90.

Moreover, the transparent conductive film obtained by applying or printing the above-mentioned composition for forming a transparent conductive film according to the present invention on a substrate and curing it, preferably has a refractive index in the range of 1.45 to 1.90. The light transmittance is 75% or more, the haze is 1.5% or less, and the surface resistance value is 1 × 10 ¹² Ω / □ or less.

  And in this invention, when high refractive index characteristic is calculated | required in addition to a transparent conductive characteristic, it replaces with a part of conductive metal oxide mix | blended in said composition for transparent conductive film formation, and refractive index 1. A high refractive index metal oxide of 8 or more and less than 3.0 can be used. In this case, a conductive metal oxide, a high refractive index metal oxide having a refractive index of 1.8 or more and less than 3.0, a metal complex containing β-diketone, an active energy ray-curable compound, a photopolymerization initiator, and A transparent conductive film-forming composition comprising a dispersion medium, the dispersion medium comprising a dispersion medium A having at least one carbonyl group and a dispersion medium B having at least one hydroxyl group, In this invention, the content of the metal complex containing β-diketone is 3 to 450 parts by mass per 100 parts by mass in total of the conductive metal oxide and the nonconductive high refractive index metal oxide, and the active energy ray The content of the curable compound is 14 to 10,000 parts by mass, the content of the dispersion medium is 60 to 70,000 parts by mass, and the content of the photopolymerization initiator is the active energy ray-curable compound 10. Transparent conductive film formation, characterized in that it is 0.1 to 20 parts by mass per part by mass, and the mass ratio (A / B) between dispersion medium A and dispersion medium B is 90/10 to 10/90 Composition.

Further, the transparent conductive film obtained by applying or printing the above-mentioned composition for forming a transparent conductive film containing a non-conductive high refractive index metal oxide according to the present invention on a substrate and curing it has a high refractive index characteristic. Preferably, the refractive index is in the range of 1.55 to 1.90, the light transmittance is 80% or more, the haze is 1.5% or less, and the surface resistance value Is 1 × 10 ¹² Ω / □ or less.

  According to the present invention, (1) a transparent conductive film which exhibits stable conductive characteristics over time for a long period of time and exhibits good film formability even under high humidity conditions of 30 ° C. × RH 85% or more without reducing coating speed A composition for forming is provided, and (2) a transparent conductive film excellent in transparency, film hardness, scratch resistance and antistatic function obtained from the composition for forming a transparent conductive film is provided. 3) An antireflection film produced using the transparent conductive film is provided. Furthermore, by using a composition for forming a transparent conductive film containing a non-conductive high refractive index metal oxide, a transparent conductive film forming composition having a high refractive index characteristic in addition to a transparent conductive characteristic, a transparent conductive film A membrane and an antireflective film are provided.

The preferred embodiments of the present invention will be specifically described below.
The composition for forming a transparent conductive film of the present invention comprises a conductive metal oxide, a metal complex containing β-diketone, an active energy ray-curable compound, a photopolymerization initiator, and a dispersion medium (dispersion medium having at least one carbonyl group). A) and a dispersion medium (dispersion medium B) having at least one hydroxyl group.

Here, the conductive metal oxide used in the composition for forming a transparent conductive film of the present invention is not particularly limited in shape or the like, but its conductivity is 10 ⁷ Ω · cm as a volume resistivity. In the following, it is preferably 10 ³ Ω · cm or less, and the size is usually 1 nm to 500 nm, preferably 10 nm to 100 nm in terms of the primary particle size. When the volume resistivity of the conductive metal oxide exceeds 10 ⁷ Ω · cm, there arises a problem that it is difficult to obtain the conductivity necessary to achieve the object, and when the primary particle size is less than 1 nm, the pencil hardness is increased. In addition, the scratch resistance is remarkably lowered, and if it exceeds 500 nm, it becomes difficult to obtain a transparent conductive film.

  Such a conductive metal oxide is not particularly limited as long as the above object can be achieved, and a commercially available product such as a commercially available product can be used. For example, metal oxides such as ITO, ATO, tin oxide, zinc oxide, indium oxide, zinc antimonate, and antimony pentoxide can be used. Here, tin oxide doped with an element such as phosphorus can be used, and zinc oxide doped with gallium or aluminum can be used. These conductive metal oxides may be used alone or in combination of two or more.

  In the present invention, when a high refractive index characteristic is required in addition to the transparent conductive characteristic, a nonconductive high refractive index of 1.8 or more and less than 3.0 is substituted for a part of the conductive metal oxide. Refractive index metal oxides can be used. This non-conductive high refractive index metal oxide is for controlling the refractive index of the formed transparent conductive film, and has a refractive index of 1.8 or more and less than 3.0, preferably 2.0 or more and 2. A non-conductive high refractive index metal oxide of 8 or less is used, and the size thereof is usually from 1 nm to 500 nm, preferably from 10 nm to 100 nm in terms of primary particle size. In addition, the refractive index of each nonelectroconductive high refractive index metal oxide is a value intrinsic | native to material, and is described in various literature. Here, when a metal oxide having a refractive index of less than 1.8 is used, a transparent conductive film having a high refractive index cannot be obtained, and a high refractive index metal oxide having a refractive index exceeding 3.0 is used. If so, the transparency of the transparent conductive film tends to decrease. Further, when the primary particle diameter of the high refractive index metal oxide is less than 1 nm, the pencil hardness and the scratch resistance are remarkably lowered, and when it exceeds 500 nm, it becomes difficult to obtain a transparent film.

  The non-conductive high refractive index metal oxide used for this purpose is not particularly limited as long as the object can be achieved, and a commercially available product such as a commercial product can be used. Examples of the non-conductive high refractive index metal oxide that can be suitably used include zirconium oxide (n = 2.4), titanium oxide (n = 2.76), cerium oxide (n = 2.2), and the like. Only one of them may be used, or two or more may be used in combination.

  In such a composition for forming a transparent conductive film containing a non-conductive high-refractive-index metal oxide, the non-conductive high-refractive-index metal oxide is mixed with the non-conductive conductive oxide. Although it can be suitably selected according to the electrical conductivity and refractive index required for the transparent conductive film formed using the composition for forming a transparent conductive film containing a high refractive index metal oxide, The mass ratio with the conductive high refractive index metal oxide (conductive material / high refractive index) is usually within the range of 30/70 to 90/10, preferably 35/65 to 85/15. It should be within the range. When the mass ratio (conductive material / high refractive index) between the conductive metal oxide and the non-conductive high refractive index metal oxide is lower than 30/70, the refractive index of the formed film increases, but the conductivity is high. There is a tendency to decrease. On the other hand, if it is higher than 90/10, the conductivity of the formed film will be high, but it will be difficult to obtain a high refractive index film.

  In the present invention, the metal complex containing β-diketone functions as a dispersant for the conductive metal oxide or the non-conductive high refractive index metal oxide in the transparent conductive film forming composition. Gives the product excellent storage stability. The metal complex includes one or more metals selected from the group consisting of zirconium, titanium, chromium, manganese, iron, cobalt, nickel, copper, vanadium, aluminum, zinc, indium, tin, and platinum. , A metal complex formed with a ligand selected from the group consisting of β-diketones, and from the viewpoint of the storage stability of the composition for forming a transparent conductive film, It is more preferable to use a metal complex that does not contain a reacting alkoxide.

  Also, for these metal complexes, those that do not cause coloration in the composition for forming a transparent conductive film are suitable. From this viewpoint, the metal complex is selected from the group consisting of zirconium, titanium, aluminum, zinc, indium, and tin. A ligand selected from the group consisting of one or more metals and β-diketone, preferably selected from the group consisting of pivaloyltrifluoroacetone, acetylacetone, trifluoroacetylacetone, and hexafluoroacetylacetone. It is preferable to use a metal complex formed with one or two or more kinds of ligands. These metal complexes are in a state in which β-diketone is already coordinated to the metal, and hardly corrode metal equipment and coating equipment used in the dispersion process.

  In addition, for the purpose of further improving the storage stability of the composition for forming a transparent conductive film, another dispersant may be added as a dispersion aid. The dispersing aid used for this purpose is not particularly limited, and examples thereof include phosphate ester type dispersing agents.

  In the present invention, at least two types of dispersion media are used as the dispersion medium, one of which is a dispersion medium (dispersion medium A) having at least one carbonyl group, and the other is a dispersion medium having at least one hydroxyl group. It is a medium (dispersion medium B), and a third dispersion medium may be blended if necessary. Here, the dispersion medium A having a carbonyl group shows a high affinity for the metal complex having a β-diketone, and the dispersion medium B having a hydroxyl group exhibits the activity of the functional group on the surface of the conductive metal oxide fine particles. It exerts the action of suppressing and preventing aggregation after dispersion, and thereby gives the composition for forming a transparent conductive film stable conductive characteristics over a long period of time and good film formability under high humidity.

  Such a dispersion medium A preferably has a boiling point of 200 ° C. or lower, and examples thereof include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc., and in particular, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone is used. Is preferred. The dispersion medium B preferably has a boiling point of 200 ° C. or lower, and examples thereof include methanol, ethanol, isopropanol, normal butanol, isobutanol, ethylene glycol monomethyl ether, and propylene glycol monomethyl ether. In particular, it is preferable to use isopropanol, isobutanol, or propylene glycol monomethyl ether. These dispersion media A and B are preferably selected in consideration of the drying temperature at the time of film formation according to the use of the composition for forming a transparent conductive film, and two or more types of dispersion media A are used. It is also possible to use two or more types of dispersion medium B.

  In the present invention, the mixing ratio of the two types of dispersion media A and B to be used can be appropriately selected depending on the use of the composition for forming a transparent conductive film. The mass mixing ratio (A / B) is usually in the range of 90/10 to 10/90, preferably in the range of 85/15 to 15/85. When the mixing ratio of the dispersion medium A is higher than 90/10, the effect of adding the dispersion medium B becomes small, and it becomes difficult to obtain storage stability over a long period of time. The effect of adding A is reduced, and the long-term stable conductive properties and film formability under high humidity are reduced.

  In the present invention, in addition to the above dispersion media A and B, the third dispersion medium used as a dispersion medium as necessary may be mixed with these dispersion media A and B. As long as it does not hinder the activity of the functional group on the surface of the conductive metal oxide fine particles due to the affinity between the metal complex and the dispersion medium B, it is not particularly limited. For example, ethyl acetate, butyl acetate, etc. Esters, N-methylpyrrolidone, amides such as dimethylacetamide, hydrocarbons such as toluene, m-xylene, ethers such as diethyl ether, dioxane, tetrahydrofuran, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, Propylene glycol monoethyl ether acetate, propylene glycol monoe Examples include tilether acetate.

Examples of the active energy ray-curable compound used in the present invention include radical polymerizable monomers and radical polymerizable oligomers.
Specific examples of the radical polymerizable monomer include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) Acrylate, tetrahydrofurfuryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, methoxy polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) ) Acrylate, polyethylene glycol polypropylene glycol mono (meth) acrylate, polyethylene glycol polytetramethylene glycol mono (meth) acrylate, glycidyl (meth) acrylate, etc. Monofunctional (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene Glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, allyl di (meth) acrylate, bisphenol A di (meth) acrylate, ethylene oxide modified bisphenol A di (meth) acrylate, polyethylene oxide modified bisphenol A di (meth) Acrylate, ethylene oxide modified bisphenol S di (meth) acrylate, bisphenol S di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,3-butylene glycol Bifunctional (meth) acrylates such as cold di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ethylene modified tri Trifunctional or higher functional (meth) acrylates such as methylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, styrene, vinyl toluene, vinyl acetate, N-vinyl pyrrolidone, Other radical polymerizable monomers such as acrylonitrile and allyl alcohol can be mentioned.

  Specific examples of the radical polymerizable oligomer include, for example, polyester (meth) acrylate, polyurethane (meth) acrylate, epoxy (meth) acrylate, polyether (meth) acrylate, oligo (meth) acrylate, and alkyd (meth) acrylate. And prepolymers having at least one (meth) acryloyl group such as polyol (meth) acrylate and silicone (meth) acrylate. Particularly preferred radical polymerizable oligomers are (meth) acrylates of polyester, epoxy, and polyurethane. In the present invention, the active energy ray-curable compound can be used alone or in combination of two or more.

  Since the composition for forming a transparent conductive film of the present invention contains a photopolymerization initiator (photosensitizer), the composition for forming a transparent conductive film can be cured by irradiation with a small amount of active energy rays. .

  Examples of the photopolymerization initiator (photosensitizer) used in the present invention include 1-hydroxycyclohexyl phenyl ketone, benzophenone, benzyl dimethyl ketone, benzoin methyl ether, benzoin ethyl ether, p-chlorobenzophenone, 4-benzoyl-4 -Methyldiphenyl sulfide, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, etc. Can be mentioned. The photopolymerization initiator can be used alone or in combination of two or more.

  In the composition for forming a transparent conductive film of the present invention, the blending ratio of each component can be appropriately set according to the use of the composition for forming a transparent conductive film, but per 100 parts by weight of the conductive metal oxide (also transparent conductive). When high refractive index characteristics are required in addition to the characteristics, the total amount of conductive metal oxide and non-conductive high refractive index metal oxide is 100 parts by mass), and the content of the metal complex containing β-diketone is 3 The content of the active energy ray-curable compound is 14 parts by mass or more and 10,000 parts by mass or less, more preferably 35 parts by mass or more and 2000 parts by mass or more. The content of the dispersion medium is 60 parts by mass or more and 70000 parts by mass or less, more preferably 100 parts by mass or more and 50000 parts by mass or less, and the active energy ray is hardened. Object 100 parts by weight per 20 parts by weight preferably at least 0.1 part by weight content of the photopolymerization initiator or less, more preferably not more than 15 parts by 1 part by mass or more.

  When the amount of the metal complex containing β-diketone is less than the above lower limit value, the dispersion of the conductive metal oxide particles and the nonconductive high refractive index metal oxide particles tends to be poor, and the above upper limit value. When the amount is larger, the metal complex containing β-diketone may not be dissolved in the dispersion medium and precipitation may occur. When the amount of the dispersion medium is less than the above lower limit value, the dissolution of the metal complex containing β-diketone and the dispersion of the metal oxide particles tend to be insufficient. The concentration of the film-forming composition is too thin to be practical. When the amount of the active energy ray-curable compound is less than the above lower limit value, the transparency tends to decrease. When the amount is more than the above upper limit value, the film hardness and scratch resistance are insufficient. In addition, when the amount of the photopolymerization initiator is less than the above lower limit value, the curing rate of the photocurable composition tends to decrease, and even if the amount exceeds the above upper limit value, an effect commensurate with it cannot be obtained. .

  Furthermore, you may mix | blend various conventional additives other than the above in the range which does not impair the objective to 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 coupling agent.

  The composition for forming a transparent conductive film of the present invention dissolves a metal complex containing β-diketone in a part of a dispersion medium, and in the dispersion medium containing the obtained metal complex, a conductive metal oxide, and further high refraction. Disperse the non-conductive high refractive index metal oxide to be blended for applications requiring rate characteristics, then add the active energy ray-curable compound, photopolymerization initiator and the remaining dispersion medium, and stir well Can be manufactured. In addition, a metal complex containing β-diketone is dissolved in the dispersion medium, and the resulting metal complex contains a conductive metal oxide, a non-conductive high refractive index metal oxide, an active energy ray-curable compound. And a photopolymerization initiator can be simultaneously added and dispersed.

  When a nonconductive high refractive index metal oxide is blended, a dispersion composed of a nonconductive high refractive index metal oxide, a metal complex and a part of a dispersion medium, and a conductive metal oxide or metal A dispersion composed of a complex and a part of the dispersion medium is prepared in advance, and then these dispersions are mixed, and the active energy ray-curable compound, the photopolymerization initiator, and the remaining dispersion medium are mixed in the obtained mixed dispersion. Can be added and stirred sufficiently. Also, a non-conductive high refractive index metal oxide, a metal complex, an active energy ray-curable compound, a dispersion comprising a photopolymerization initiator and a part of the dispersion medium, and an electroconductive metal oxide, metal complex, active energy ray It is also possible to prepare a dispersion liquid composed of a curable compound, a photopolymerization initiator and the remaining dispersion medium in advance, mix these dispersion liquids, and sufficiently stir them.

  Here, the dispersion medium at the time of dispersion may be set so that the ratio of the dispersion medium A and the dispersion medium B is finally in the range of 90/10 to 10/90, and before the dispersion operation is performed. It is even better to perform a pre-dispersion operation. This pre-dispersion operation is a non-conductive high-refractive index metal oxide compounded in a dispersion medium in which a metal complex containing β-diketone is dissolved in a conductive metal oxide or an application requiring high refractive index characteristics. While dispersing the product, while stirring with a disper, etc., gradually add these conductive metal oxides and non-conductive high refractive index metal oxides, conductive metal oxides and non-conductive high refractive index metals This is done by stirring well until no oxide lumps are visible.

  Further, the dispersion operation of the conductive metal oxide or the nonconductive high refractive index metal oxide can be performed using a paint shaker, a ball mill, a sand mill, a centrimill or the like. In the dispersion operation, it is preferable to use dispersed beads such as glass beads and zirconia beads. The bead diameter is not particularly limited, but is usually about 0.05 to 1 mmφ, preferably 0.1 to 0.65 mmφ.

  In the composition for forming a transparent conductive film of the present invention, the particle diameter of the conductive metal oxide or nonconductive high refractive index metal oxide used is preferably a median diameter of 120 nm or less, more preferably 80 nm or less. Is good. When the median diameter is larger than that, the haze of the transparent conductive film obtained from the composition for forming a transparent conductive film increases.

  The composition for forming a transparent conductive film of the present invention is a plastic (polycarbonate, polymethyl methacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triacetyl cellulose resin, polyethylene terephthalate, ABS resin, AS resin, norbornene resin, etc. ), Coated or printed on the surface of various substrates such as metal, wood, paper, glass, slate, etc., and cured to form a transparent conductive film on the surface of these substrates. For example, plastic optical components , Touch panels, film-type liquid crystal elements, plastic containers, flooring materials as building interior materials, wall materials, artificial marble, etc., as protective coating materials for preventing scratches (scratching) and preventing contamination, and film-type liquid crystal elements , Touch panel, anti-reflection of plastic optical parts, etc. As a film, it is used as an adhesive for various base materials, a sealing material, a binder material for printing ink, etc., for various applications, and particularly suitable as a composition for forming a high refractive index film as an antireflection film. Can be used.

Application | coating or printing of the composition for transparent conductive film formation to a base material can be performed by methods, such as roll coating, spin coating, and screen printing, according to a conventional method. If necessary, the dispersion medium (solvent) is evaporated by heating, the coating film is dried, and then irradiated with active energy rays (ultraviolet rays or electron beams). 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, an ultraviolet ray source such as an LED, and an electron beam accelerator can be used. The irradiation amount of the active energy ray is suitably within the range of 50 to 3000 mJ / cm ² in the case of ultraviolet rays and 0.2 to 1000 μC / cm ² in the case of electron beams. By irradiation with this active energy ray, the active energy ray-curable compound is polymerized, and a conductive metal oxide or a non-conductive high-refractive-index metal oxide particle added as necessary is transparent with a resin. A conductive film is formed. The film thickness of this transparent conductive film is generally in the range of 0.1 μm to 10.0 μm, preferably 0.2 μm to 5.0 μm. When the transparent conductive film is thinner than 0.1 μm, there is a problem that the conductivity and the film hardness are lowered. On the other hand, when it is thicker than 10.0 μm, the problem that the transparency is lowered is likely to occur.

The transparent conductive film obtained by curing the composition for forming a transparent conductive film of the present invention has conductive metal oxide and fine particles of non-conductive high refractive index metal oxide added as needed in the transparent conductive film. It is characterized by being uniformly dispersed, having a controllable refractive index, high transparency, low haze, and low surface resistance. Specifically, when high conductive properties are mainly required and only conductive metal oxide is used, the refractive index is usually 1.45 to 1.90, and the light transmittance is 75% or more. The haze is 1.5% or less, the surface resistance value is 10 ¹² Ω / □ or less, and a high refractive index characteristic is required in addition to the high conductive characteristic. When a non-conductive high refractive index metal oxide is used, the refractive index is usually 1.55 to 1.90, the light transmittance is 80% or more, the haze is 1.5% or less, The surface resistance value is 10 ¹² Ω / □ or less. Here, in order to control the refractive index, the amount of the nonconductive high refractive index metal oxide and the conductive metal oxide and the amount of the active energy ray-curable compound blended in the composition for forming a transparent conductive film. You can adjust the ratio. The transparent conductive film having high conductive characteristics and high refractive index characteristics can be suitably used for applications such as conductive antireflection materials and display surfaces of displays.

  The present invention will be specifically described below with reference to examples and comparative examples. In Examples and Comparative Examples, “parts” are all “parts by mass”.

[Examples 1 to 10 and Comparative Examples 1 to 4]
The components used in Examples and Comparative Examples are as follows.
<Conductive metal oxide>
ATO (refractive index 2.0, powder resistance 10Ω · cm, primary particle size 0.03μm)
Tin oxide (refractive index 2.0, powder resistance 50Ω · cm, primary particle size 0.03μm)
Zinc oxide (refractive index 2.0, powder resistance 100Ω · cm, primary particle size 0.04μm)
Antimony pentoxide (refractive index 1.64, powder resistance 100Ω · cm, primary particle size 0.05μm)

<Non-conductive high refractive index metal oxide>
Zirconium oxide (refractive index 2.4, primary particle size 0.02μm)
Titanium oxide (refractive index 2.76, primary particle diameter 0.02μm)

<Metal complex containing β-diketone>
Zirconium acetylacetonate (Zr (C ₅ H ₇ O ₂ ) ₄ )
Dibutyl-tin bisacetylacetonate ((C ₄ H ₉ ) ₂ Sn (C ₅ H ₇ O ₂ ) ₂ )
Zinc acetylacetonate (Zn (C ₅ H ₇ O ₂ ) ₂ )
Titanium acetylacetonate (Ti (C ₅ H ₇ O ₂ ) ₄ )

<Dispersing aid>
BYK-142 (NV. 60% or more; trade name manufactured by Big Chemie Japan)
<Active energy ray-curable compound>
Multifunctional (meth) acrylate monomer (Nippon Kayaku Co., Ltd. trade name: KAYARAD DPHA; mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate in a mass ratio of 60:40)
<Photopolymerization initiator>
IRGACURE 184 (trade name, manufactured by Ciba Specialty Chemicals)

<Transparent conductive film forming composition and production of transparent conductive film using the same>
Example 1
In a mixing vessel of a paint shaker, as shown in Table 1, with respect to 100 parts of ATO (conductive metal oxide), 20 parts of dibutyl-tin bisacetylacetonate (metal complex containing β-diketone), 10 parts of BYK-142 (dispersion aid), 75 parts of cyclohexanone (dispersion medium A), 75 parts of propylene glycol monomethyl ether (dispersion medium B), and 800 parts of 0.60 mmφ glass beads were charged and kneaded for 7 hours. did. After completion of the kneading, the glass beads were removed to obtain a dispersion of conductive metal oxide fine particles. Next, 23 parts of KAYARAD DPHA (active energy ray-curable compound), 2.3 parts of IRGACURE 184 (photopolymerization initiator), 49 parts of cyclohexanone (dispersion medium A), and 49 parts of this dispersion were used. Propylene glycol monomethyl ether (dispersion medium B) was added to obtain a photocurable composition for forming a transparent conductive film of Example 1.

Next, the photocurable composition of Example 1 was placed on a PET film having a film thickness of 75 μm (trade name: A4300, manufactured by Toyobo Co., Ltd .; light transmittance 91%, haze 0.5%) using a roll coater at 30 ° C. and RH85. After coating under the condition of% and evaporating the organic solvent, a 300 mJ / cm ² light was irradiated in air using a high pressure mercury lamp to produce a transparent conductive film having a thickness of 3 μm. Under the present circumstances, preparation of the transparent conductive film was performed immediately after preparation of a photocurable composition, 6 months after preparation, and 9 months after preparation, and the storage stability was investigated.
The results are shown in Table 1.

Example 2

As shown in Table 1, in a mixing vessel of a paint shaker, 20 parts of dibutyl-tin bisacetylacetonate (a metal complex containing β-diketone) and 10 parts of tin oxide (conductive metal oxide), 10 7 parts BYK-142 (dispersion aid), 75 parts methyl isobutyl ketone (dispersion medium A), 75 parts propylene glycol monomethyl ether (dispersion medium B), and 800 parts 0.60 mmφ glass beads Kneaded. After completion of the kneading, the glass beads were removed to obtain a dispersion of conductive metal oxide fine particles. To this dispersion, 23 parts KAYARAD DPHA (active energy ray curable compound), 2.3 parts IRGACURE 184 (photopolymerization initiator), 49 parts methyl isobutyl ketone (dispersion medium A), and 49 parts propylene Glycol monomethyl ether (dispersion medium B) was added to obtain a photocurable composition for forming a transparent conductive film of Example 2. Thereafter, a transparent conductive film having a thickness of 3 μm was produced by the same method as in Example 1, and the storage stability was examined.

Example 3
As shown in Table 1, in a mixing vessel of a paint shaker, 5 parts of zinc acetylacetonate (metal complex containing β-diketone), 10 parts of BYK with respect to 100 parts of zinc oxide (conductive metal oxide) -142 (dispersion aid), 90 parts of methyl isobutyl ketone (dispersion medium A), 60 parts of isobutanol (dispersion medium B), and 800 parts of 0.60 mmφ glass beads were charged and kneaded for 7 hours. After completion of the kneading, the glass beads were removed to obtain a dispersion of conductive metal oxide fine particles. To this dispersion was added 23 parts KAYARAD DPHA (active energy ray curable compound), 2.3 parts IRGACURE 184 (photopolymerization initiator), 59 parts methyl isobutyl ketone (dispersion medium A), and 39 parts isoform. Butanol (dispersion medium B) was added to obtain a photocurable composition for forming a transparent conductive film of Example 3. Thereafter, a transparent conductive film having a thickness of 3 μm was produced by the same method as in Example 1, and the storage stability was examined.

Example 4
As shown in Table 1, in a mixing vessel of a paint shaker, 10 parts for a total of 100 parts of 50 parts of ATO (conductive metal oxide) and 50 parts of zirconium oxide (nonconductive high refractive index metal oxide) Zirconium acetylacetonate (metal complex containing β-diketone), 10 parts BYK-142 (dispersion aid), 45 parts cyclohexanone (dispersion medium A), 105 parts propylene glycol monomethyl ether (dispersion medium B), And 800 parts of 0.60 mmφ glass beads were charged and kneaded for 7 hours. After completion of the kneading, the glass beads were removed to obtain a dispersion of conductive metal oxide fine particles. To this dispersion, 23 parts KAYARAD DPHA (active energy ray curable compound), 2.3 parts IRGACURE 184 (photopolymerization initiator), 29 parts cyclohexanone (dispersion medium A), and 69 parts propylene glycol monomethyl. Ether (dispersion medium B) was added to obtain a photocurable composition for forming a transparent conductive film of Example 4. Thereafter, a transparent conductive film having a thickness of 3 μm was produced by the same method as in Example 1, and the storage stability was examined.

Example 5
As shown in Table 1, for a total of 100 parts of antimony pentoxide (conductive metal oxide) 70 parts and titanium oxide (non-conductive high refractive index metal oxide) 30 parts in the paint shaker mixing container, 10 parts titanium acetylacetonate (metal complex containing β-diketone), 10 parts BYK-142 (dispersion aid), 105 parts methyl isobutyl ketone (dispersion medium A), 45 parts isopropanol (dispersion medium B) And 800 parts of 0.60 mmφ glass beads were charged and kneaded for 7 hours. After completion of the kneading, the glass beads were removed to obtain a dispersion of conductive metal oxide fine particles. 33 parts of KAYARAD DPHA (active energy ray-curable compound), 3.3 parts of IRGACURE 184 (photopolymerization initiator), 80.5 parts of methyl isobutyl ketone (dispersion medium A), and 34. 5 parts of isopropanol (dispersion medium B) was added to obtain a photocurable composition for forming a transparent conductive film of Example 5. Thereafter, a transparent conductive film having a thickness of 3 μm was produced by the same method as in Example 1, and the storage stability was examined.

Example 6
As shown in Table 1, in a mixing vessel of a paint shaker, for 100 parts in total of 40 parts of antimony pentoxide (conductive metal oxide) and 60 parts of zirconium oxide (non-conductive high refractive index metal oxide), 25 parts zirconium acetylacetonate (metal complex containing β-diketone), 5 parts BYK-142 (dispersion aid), 105 parts methyl isobutyl ketone (dispersion medium A), 45 parts isobutanol (dispersion medium B) ) And 800 parts of 0.60 mmφ glass beads were charged and kneaded for 7 hours. After completion of the kneading, the glass beads were removed to obtain a dispersion of conductive metal oxide fine particles. To this dispersion, 20 parts KAYARAD DPHA (active energy ray curable compound), 2.0 parts IRGACURE 184 (photopolymerization initiator), 80.5 parts methyl isobutyl ketone (dispersion medium A), and 34. 5 parts of isopropanol (dispersion medium B) was added to obtain a photocurable composition for forming a transparent conductive film of Example 5. Thereafter, a transparent conductive film having a thickness of 3 μm was produced by the same method as in Example 1, and the storage stability was examined.

Comparative Example 1
In a mixing vessel of a paint shaker, as shown in Table 1, 20 parts of zinc acetylacetonate (metal complex containing β-diketone) and 10 parts with respect to 100 parts of zinc oxide (conductive metal oxide) Of BYK-142 (dispersion aid), 150 parts of isobutanol (dispersion medium), and 800 parts of 0.60 mmφ glass beads were charged and kneaded for 7 hours. After completion of the kneading, the glass beads were removed to obtain a dispersion of conductive metal oxide fine particles. Next, 23 parts of KAYARAD DPHA (active energy ray-curable compound), 2.3 parts of IRGACURE 184 (photopolymerization initiator), and 98 parts of isobutanol (dispersion medium) were added to this dispersion. A photocurable composition for forming a transparent conductive film 1 was obtained. Thereafter, a transparent conductive film having a thickness of 3 μm was produced by the same method as in Example 1, and the storage stability was examined.

Comparative Example 2
In a mixing vessel of a paint shaker, as shown in Table 1, with respect to 100 parts of ATO (conductive metal oxide), 20 parts of dibutyl-tin bisacetylacetonate (metal complex containing β-diketone), 10 parts of BYK-142 (dispersing aid), 150 parts of methyl isobutyl ketone (dispersing medium), and 800 parts of 0.60 mmφ glass beads were charged and kneaded for 7 hours. After completion of the kneading, the glass beads were removed to obtain a dispersion of conductive metal oxide fine particles. Next, 23 parts of KAYARAD DPHA (active energy ray curable compound), 2.3 parts of IRGACURE 184 (photopolymerization initiator), and 98 parts of methyl isobutyl ketone (dispersion medium) were added to this dispersion, and compared. The photocurable composition for transparent conductive film formation of Example 1 was obtained. Thereafter, a transparent conductive film having a thickness of 3 μm was produced by the same method as in Example 1, and the storage stability was examined.

<Evaluation method>
(1) Median diameter of metal oxide particles (nm)
The median diameter of the metal oxide particles dispersed in the composition for forming a transparent conductive film prepared in Examples 1 to 6 and Comparative Examples 1 and 2 described above was immediately after production, after 3 months (stored at 40 ° C.), After 6 months (40 ° C. storage) and 9 months later, the measurement was performed under the following conditions.
Measuring equipment used: Microtrac particle size distribution meter manufactured by Nikkiso Co., Ltd. Measurement conditions: Temperature 20 ° C.
Sample: After the sample is diluted to 5% concentration with a dispersion medium, measurement data analysis conditions: Particle diameter standard, volume standard

(2) Transmissivity (%) and haze (%) of composition for forming transparent conductive film
About the transparent conductive film obtained in said Examples 1-6 and Comparative Examples 1 and 2, the transmittance | permeability and haze were measured using the measuring instrument TC-HIII DPK by Tokyo Denshoku Technical Center. The measured value is a value including the base material.

(3) Surface resistance (Ω / □)
The transparent conductive films obtained in Examples 1 to 6 and Comparative Examples 1 and 2 were measured using a measuring instrument Hiresta IP MCP-HT260 manufactured by Mitsubishi Chemical Corporation.

(4) Pencil hardness The pencil hardness was measured according to JIS K5600-5-4.

(5) Scratch resistance With respect to the scratch resistance, steel wool # 0000 was reciprocated 10 times with a load of 250 g, and the degree of scratch was visually determined according to the following criteria.
A: Almost no scratches are observed.
B: Some scratches are observed.
C: Obvious scratches are observed.
D: Between C and E E: Many scratches are observed.

(6) Brushing (film whitening) evaluation The appearance of the film after film formation was evaluated visually according to the following criteria.
×: Wind pattern whitening ○: Wind pattern whitening

(7) Refractive index About the transparent conductive film obtained by said Examples 1-6 and Comparative Examples 1 and 2, it measured at 20 degreeC using the Abbe refractometer DR-M4 by an Atago company.

Table 1 shows the results of the above measurements and the results of evaluation.

As is clear from the results shown in Table 1, in the case of Examples 1 to 6 using the dispersion medium containing the dispersion medium A and the dispersion medium B, a transparent conductive film is formed under a high humidity condition of 30 ° C. and RH 85%. Nevertheless, whitening of the transparent conductive film did not occur, the transmittance was 80% or more, haze 1.5% or less, surface resistance 1 × 10 ¹² Ω / □ or less, pencil hardness 2H, and scratch resistance. A good transparent conductive film was obtained. Moreover, these compositions for forming a transparent conductive film have good storage stability, and a transparent conductive film having stable characteristics even after 9 months was obtained. On the other hand, in the case of Comparative Example 1 in which the dispersion medium A was not used, a whitening phenomenon was observed in the transparent conductive film obtained under high humidity conditions, and in the case of Comparative Example 2 in which the dispersion medium B was not used. The dispersion stability decreased, the median diameter increased after 6 months, and the transparency of the obtained transparent conductive film decreased.

<Preparation of antireflection film>
Next, on each transparent conductive film obtained in Examples 1 to 6 and Comparative Examples 1 and 2, using a bar coater, a hollow silica fine particle dispersed active energy ray curable compound coating is applied and cured. Thus, an antireflection film in which a low refractive index film was laminated on each transparent conductive film was produced. The film thickness was adjusted so that the dry film thickness was 550 nm and the minimum reflectance was shown.

<Measurement of minimum reflectance>
A spectrophotometer (JASCO Corp.) was prepared by roughening the back surface of an antireflection film produced using the composition for forming a transparent conductive film of Examples 1 to 6 and Comparative Examples 1 and 2 with sandpaper and painting with a black paint. A specular reflection spectrum of 400 to 700 nm was measured by U-BEST 50). And the minimum value of the reflectance was read from the measured reflection spectrum, and it was set as the minimum reflectance.

The measurement result of the minimum reflectance is that the minimum reflectance of the antireflection film produced using the composition for forming a transparent conductive film of Examples 1 to 3 and Example 6 is 1.0%. The antireflection film produced using the composition for forming a transparent conductive film 5 had a minimum reflectance of 0.9%, and an antireflection film having a target minimum reflectance of 1% or less was obtained.
On the other hand, the minimum reflectance of the antireflection film produced using the composition for forming a transparent conductive film of Comparative Example 1 is 1.5%, and the composition for forming a transparent conductive film of Comparative Example 2 is used. The minimum reflectance of the antireflection film produced by using this was 1.0%, and in the case of Comparative Example 1, a desired antireflection film could not be obtained.

Claims (23)

  A conductive metal oxide, a metal complex containing β-diketone, an active energy ray-curable compound, a photopolymerization initiator, and a dispersion medium, wherein the dispersion medium has at least one carbonyl group and at least one dispersion medium A A composition for forming a transparent conductive film, comprising a dispersion medium B having a hydroxyl group.   The composition for forming a transparent conductive film according to claim 1, wherein the dispersion medium A is one or more selected from the group consisting of methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.   The composition for forming a transparent conductive film according to claim 1 or 2, wherein the dispersion medium B is one or more selected from the group consisting of isopropyl alcohol, isobutyl alcohol, and propylene glycol monomethyl ether. object.   The conductive metal oxide is selected from the group consisting of tin-doped indium oxide (ITO), antimony-doped tin oxide (ATO), tin oxide, zinc oxide, indium oxide, zinc antimonate, and antimony pentoxide, or It is 2 or more types, The composition for transparent conductive film formation in any one of Claims 1-3 characterized by the above-mentioned.   The metal complex containing β-diketone is one or more selected from the group consisting of zirconium, titanium, chromium, manganese, iron, cobalt, nickel, copper, vanadium, aluminum, zinc, indium, tin, and platinum And a metal complex formed of one or more ligands selected from the group consisting of pivaloyltrifluoroacetone, acetylacetone, trifluoroacetylacetone, and hexafluoroacetylacetone. The composition for forming a transparent conductive film according to any one of claims 1 to 4.   6. The transparent conductive film according to claim 5, wherein the metal forming the metal complex is one or more metals selected from the group consisting of zirconium, titanium, aluminum, zinc, indium and tin. Forming composition.   The content of the metal complex containing β-diketone is 3 to 450 parts by weight, the content of the active energy ray-curable compound is 14 to 10,000 parts by weight, and the dispersion medium per 100 parts by weight of the conductive metal oxide The content of the photopolymerization initiator is 0.1 to 20 parts by mass per 100 parts by mass of the active energy ray-curable compound, and the dispersion medium A The composition for forming a transparent conductive film according to claim 1, wherein the mass ratio (A / B) to the dispersion medium B is 90/10 to 10/90.   A transparent conductive film obtained by applying or printing the composition for forming a transparent conductive film according to claim 1 on a substrate and curing the composition.   The transparent conductive film according to claim 8, wherein the substrate is a PET film. The refractive index is in the range of 1.45 to 1.90, the total light transmittance is 75% or more, the haze is 1.5% or less, and the surface resistance value is 1 × 10 ¹² Ω / □. The transparent conductive film according to claim 8 or 9, wherein:   An antireflection film produced using the composition for forming a transparent conductive film according to claim 1.   Conductive metal oxide, non-conductive high refractive index metal oxide having a refractive index of 1.8 or more and less than 3.0, metal complex containing β-diketone, active energy ray curable compound, photopolymerization initiator, and dispersion medium And the dispersion medium contains a dispersion medium A having at least one carbonyl group and a dispersion medium B having at least one hydroxyl group.   The composition for forming a transparent conductive film according to claim 12, wherein the dispersion medium A is one or more selected from the group consisting of methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.   The composition for forming a transparent conductive film according to claim 12 or 13, wherein the dispersion medium B is one or more selected from the group consisting of isopropyl alcohol, isobutyl alcohol, and propylene glycol monomethyl ether. object.   The conductive metal oxide is selected from the group consisting of tin-doped indium oxide (ITO), antimony-doped tin oxide (ATO), tin oxide, zinc oxide, indium oxide, zinc antimonate, and antimony pentoxide, or It is 2 or more types, The composition for transparent conductive film formation in any one of Claims 12-14 characterized by the above-mentioned.   The nonconductive high refractive index metal oxide having a refractive index of 1.8 or more and less than 3.0 is one or more selected from the group consisting of zirconium oxide, titanium oxide, and cerium oxide. The composition for transparent conductive film formation in any one of Claims 12-15.   The metal complex containing β-diketone is one or more selected from the group consisting of zirconium, titanium, chromium, manganese, iron, cobalt, nickel, copper, vanadium, aluminum, zinc, indium, tin, and platinum The composition for forming a transparent conductive film according to any one of claims 12 to 16, which is a metal complex formed of a metal selected from the group consisting of β-diketone and a ligand selected from the group consisting of β-diketones.   The metal complex is one or more metals selected from the group consisting of zirconium, titanium, aluminum, zinc, indium, and tin, pivaloyl trifluoroacetone, acetylacetone, trifluoroacetylacetone, and hexafluoro. The composition for forming a transparent conductive film according to claim 17, wherein the composition is formed of one or more ligands selected from the group consisting of acetylacetone.   The content of the metal complex containing β-diketone is 3 to 450 parts by mass per 100 parts by mass in total of the conductive metal oxide and the nonconductive high refractive index metal oxide, and the active energy ray-curable compound is contained. The amount is 14 to 10000 parts by mass, the content of the dispersion medium is 60 to 70000 parts by mass, and the content of the photopolymerization initiator is 0.1 per 100 parts by mass of the active energy ray-curable compound. The mass ratio (A / B) between the dispersion medium A and the dispersion medium B is 90/10 to 10/90, and is 20 to 20 parts by mass. A composition for forming a transparent conductive film.   A transparent conductive film obtained by applying or printing the composition for forming a transparent conductive film according to claim 12 on a substrate and curing the composition.   The transparent conductive film according to claim 20, wherein the substrate is a PET film. The refractive index is in the range of 1.55 to 1.90, the total light transmittance is 80% or more, the haze is 1.5% or less, and the surface resistance value is 1 × 10 ¹² Ω / □. The transparent conductive film according to claim 20 or 21, wherein:   An antireflection film produced using the composition for forming a transparent conductive film according to claim 12.