TWI529225B - A conductive fine particle dispersion liquid, a photohardenable composition containing conductive microparticles, and a hardening film containing conductive microparticles - Google Patents

Description

Conductive fine particle dispersion, photocurable composition containing conductive fine particles, and cured film containing conductive fine particles

The present invention relates to a conductive fine particle dispersion liquid excellent in stability, a photocurable composition containing conductive fine particles, and a cured film containing conductive fine particles obtained from the composition, and more specifically, related to plastics. And a photocurable composition obtained by forming a cured film containing conductive fine particles having excellent transparency and having an antistatic function on the surface of various substrates such as metal, wood, paper, glass, slate, etc., and transparency obtained from the composition A cured film having excellent antistatic properties and a conductive fine particle dispersion excellent in storage stability used for preparing the photocurable composition.

In recent years, in order to prevent the surface of various substrates from being scratched (scratched) or to prevent contamination, the coating material or the printing ink is required to have excellent coating properties and to form hardness on various substrate surfaces. A curable composition of a cured film excellent in scratch resistance, abrasion resistance, low warpage, adhesion, transparency, chemical resistance, and appearance of a coating film surface.

In addition, when used in applications such as flat panel display devices, touch panels, and plastic optical components, in addition to the above requirements, it is required to form a hardenable film of a cured film such as a transparent conductive film having excellent transparency and antistatic function. Things.

Further, in an image display device such as a liquid crystal display device or a cathode tube display device, and an optical product, an antireflection film (cured film) is used. In addition to the characteristics of high transparency and low reflectance, the antireflection film is required to have scratch resistance and prevent adhesion of foreign matter such as dust or garbage. 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 characteristics.

Next, a method of imparting an antistatic function to the cured film is known, and a method of adding a surfactant, a conductive polymer, or a conductive fine particle mainly composed of a metal oxide to the curable composition is known, and in particular, For the purpose of producing a film having a permanent antistatic effect, a method of adding conductive fine particles is generally used. The method of adding the conductive fine particles is a method in which a chelating agent is blended in a resin solution or a solvent, and an inorganic oxide is dispersed in the complex (see, for example, Patent Documents 1 and 2).

[Practical Technical Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2001-139,847

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2001-139,889

The conductive fine particle dispersion liquid and the curable composition used for the above-described use are required to have a small particle diameter of the conductive fine particles and excellent storage stability of the dispersion liquid. In the chelating agents described in Patent Documents 1 and 2, since a metal chelate compound is formed with a metal, there is a problem that a metal machine or a coating machine used during the dispersion treatment is corroded.

The present invention has been made in view of the above problems to provide (1) a cured film which is excellent in transparency and has an antistatic function on the surface of the substrate, and the metal machine or the coating machine used in the dispersion process is not (2) various cured films such as a transparent conductive film obtained from the photocurable composition containing conductive fine particles, and (3) having such a conductive property, a photocurable composition containing conductive fine particles which is corroded, (2) a transparent conductive film obtained from the photocurable composition containing conductive fine particles The display device of the cured film obtained by the photocurable composition of the microparticles, and (4) the conductive fine particle dispersion liquid excellent in storage stability used when preparing the photocurable composition containing the conductive fine particles.

In order to achieve the above various objectives, the inventors of the present invention have further studied the results of the review, and found that by dispersing the conductive fine particles and the metal complex in the dispersion medium, it is possible to obtain a conductive fine particle dispersion having excellent stability. It has been found that by using the conductive fine particle dispersion liquid, a photocurable composition containing conductive fine particles which is not corroded by a metal machine or a coating material during the dispersion treatment can be obtained, and the present invention has been completed.

In other words, the conductive fine particle dispersion of the present invention is characterized by being composed of conductive fine particles, a metal complex, and a dispersion medium. Preferably, the content of the metal complex is 2 per 100 parts by mass of the conductive fine particles. ～45 parts by mass, the content of the dispersion medium is 40 to 1000 parts by mass.

Further, in the present invention, in addition to the transparent conductive property, high refractive index characteristics are required, and the conductive fine particle dispersion is characterized by high refractive index fine particles having a refractive index of 1.8 or more, conductive fine particles, and no alkoxylation. The metal complex and the dispersion medium are formed, and the water content is 3% by mass or less. Preferably, the content of the conductive fine particles is from 30 to 900 parts by mass, and the content of the metal complex is contained per 100 parts by mass of the high refractive index fine particles. The content is from 3 to 450 parts by mass and the dispersion medium is from 60 to 9000 parts by mass.

Next, the photocurable composition containing conductive fine particles of the present invention is characterized by being composed of conductive fine particles, a metal complex, an active energy ray-curable compound, a photopolymerization initiator, and a dispersion medium, preferably each The content of the metal complex in 100 parts by mass of the conductive fine particles is 2 to 45 parts by mass, the content of the dispersion medium is 40 to 1000 parts by mass, and the content of the active energy ray-curable compound is 10 to 1000 parts by mass, and each In 100 parts by mass of the active energy ray-curable compound, the content of the photopolymerization initiator is from 0.1 to 20 parts by mass.

Further, in the present invention, a photocurable composition containing conductive fine particles for forming a transparent conductive film having high refractive index characteristics is characterized by high refractive index fine particles having a refractive index of 1.8 or more, conductive fine particles, and no a metal oxide containing an alkoxide, an active energy ray-curable compound, a photopolymerization initiator, and a dispersion medium, and having a water content of 3% by mass or less, preferably 100 parts by mass of the high refractive index fine particles, and conductive fine particles The content is 30 to 900 parts by mass, the content of the metal complex is 3 to 450 parts by mass, the content of the dispersion medium is 60 to 70,000 parts by mass, and the content of the active energy ray-curable compound is 14 to 10,000 parts by mass, and each In 100 parts by mass of the active energy ray-curable compound, the content of the photopolymerization initiator is from 0.1 to 20 parts by mass.

Further, the cured film containing conductive fine particles of the present invention is characterized in that the photocurable composition containing the above-mentioned conductive fine particles is applied or printed on a substrate, and is cured, preferably having a refractive index of 1.45. 1.90, the light transmittance is 75% or more, the twist is 2.0% or less, and the surface resistance value is 10 ¹² Ω/□ or less.

Further, in the present invention, a cured film containing conductive fine particles for forming a transparent conductive film having high refractive index characteristics is characterized in that the conductive property for forming the above transparent conductive film is coated or printed on a substrate. The photocurable composition of the microparticles is preferably obtained by curing the refractive index of 1.55 to 1.90, the light transmittance of 85% or more, the twist of 1.5% or less, and the surface resistance value of 10 ¹² Ω/□ or less.

[Effect of the invention]

According to the present invention, (1) a conductive fine particle dispersion liquid excellent in storage stability of the dispersion liquid can be provided, and (2) a cured film having excellent transparency and antistatic function can be formed on the surface of the substrate, during the dispersion treatment. The photocurable composition containing conductive fine particles which is not corroded by the metal machine or the coating material to be used, and (3) the hardening of the conductive microparticles which are excellent in transparency and have antistatic properties obtained from the composition membrane.

Further, according to the present invention, it is possible to provide (1) a transparent conductive film which is excellent in transparency and has high refractive index and antistatic function on the surface of the substrate, and the metal machine or the coating machine used in the dispersion process is not (2) a transparent conductive film having excellent transparency and high refractive index and antistatic function, which is obtained by forming a composition for forming a photocurable transparent conductive film which is corroded, and (3) having The display device of the transparent conductive film and (4) a dispersion liquid excellent in storage stability used when preparing the composition for forming a transparent conductive film.

[The best form for implementing the invention]

Hereinafter, embodiments of the present invention will be specifically described.

The conductive fine particle dispersion of the present invention contains conductive fine particles, a metal complex, and a dispersion medium. The shape of the conductive fine particles used in the present invention is not particularly limited. The conductivity of the conductive fine particles is 10 ⁷ Ω ‧ cm or less, preferably 10 ³ Ω ‧ cm or less. Further, as for the size of the conductive fine particles, a primary particle diameter of 1 to 500 nm is usually used, and preferably 10 to 100 nm.

Further, in the present invention, when a transparent conductive film or the like is required to have high refractive index characteristics, the conductive fine particle dispersion liquid contains high refractive index fine particles having a refractive index of 1.8 or more, conductive fine particles, and a metal containing no alkoxide. The complex compound and the dispersion medium have a water content of 3% by mass or less. The shape of the high refractive index fine particles and the conductive fine particles used in the present invention is not particularly limited. Further, as for the size of the high refractive index fine particles and the conductive fine particles, a primary particle diameter of usually 1 to 500 nm, preferably 10 to 100 nm can be used.

The type of the conductive fine particles used in the present invention is not particularly limited as long as it can achieve the object, and a conventional product such as a commercially available product can be used. For example, a metal oxide such as ITO, ATO, tin oxide, zinc oxide, indium oxide, zinc antimonate or antimony pentoxide or a hydroxide constituting a metal of such a metal oxide can be used. For tin oxide, an element doped with phosphorus or the like can also be used. Moreover, regarding zinc oxide, those doped with gallium or aluminum can also be used. Further, it may be metal fine particles such as gold, silver, copper, platinum, or aluminum, and organic conductive fine particles. These conductive fine particles may be used alone or in combination of two or more.

Further, in the present invention, the high refractive index fine particles blended in the conductive fine particle dispersion liquid in the case where the transparent conductive film or the like is particularly required to have high refractive index characteristics are added to control the refractive index of the formed transparent conductive film. It is preferred to use a metal oxide having a refractive index of 1.8 to 3.0. Further, in each document, the refractive index of each of the high refractive index fine particles is described as the original value of the material. When a high refractive index fine particle having a refractive index of less than 1.8 is used, a film having a high refractive index cannot be obtained, and when a high refractive index fine particle having a refractive index of more than 3.0 is used, the transparency of the film tends to be lowered. The type of the high refractive index fine particles used in the present invention is not particularly limited as long as it can achieve the object, and a conventional product such as a commercially available product can be used. For example, zirconium oxide (n = 2.2), titanium oxide (n = 2.76), cerium oxide (= 2.2), or the like can be used. These high-refractive-index fine particles may be used alone or in combination of two or more.

In the conductive fine particle dispersion of the present invention, a metal complex is blended in a dispersion medium in addition to the above-mentioned conductive fine particles and high refractive index fine particles to be blended in the application of high refractive index properties. The metal complex compound can function as a dispersing agent in the dispersion liquid, and can obtain a conductive fine particle dispersion liquid excellent in storage stability of the dispersion liquid. Moreover, the metal complex is almost completely free of the case where the metal machine or coating machine used in the dispersion process is corroded.

The metal complex used in the present invention is a metal group selected from the group consisting of zirconium, titanium, chromium, manganese, iron, cobalt, nickel, copper, vanadium, aluminum, zinc, indium, tin, and platinum. In the case of a small amount of color, preferably, for example, a metal selected from the group consisting of zirconium, titanium, aluminum, zinc, indium, and tin, and a ligand selected from the group consisting of β-diketones (preferably Selected from trimethylethyl fluorenylacetone, ethyl acetophenone It is formed by a group of ketones, acetylacetone trifluoride and hexamethylene acetonide, and more preferably an alkoxide-free metal complex. When a metal complex containing no alkoxide is used, the alkoxide reacts with the water contained in the solvent or the moisture in the air, and the conductive fine particle dispersion and the transparent conductive film are formed to have conductivity. The storage stability of the photocurable composition of the fine particles and the tendency of the film properties to be lowered.

In the present invention, a metal complex compound to be used in the case where a transparent conductive film or the like is particularly required to have a high refractive index property is used, and a metal complex containing no alkoxide is used. When a metal complex containing no alkoxide is used, the alkoxide reacts with the water contained in the solvent or the moisture in the air, and the conductive fine particle dispersion and the transparent conductive film are formed to contain conductivity. The storage stability and film properties of the photocurable composition of the microparticles are lowered.

Further, in order to further improve the storage stability of the dispersion, another dispersant may be additionally added as a dispersing aid. The type of the dispersing aid is not particularly limited, and the dispersing agent is, for example, a phosphate-based nonionic dispersing agent having a polyoxyethylene alkyl structure.

The dispersing medium used in the present invention, for example, an alcohol such as water, methanol, ethanol, isopropanol, n-butanol, 2-butanol or octanol; acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexane Ketones, ketones such as 4-hydroxy-4-methyl-2-pentanone; ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Esters such as acid esters; ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene; dimethylformamide, N An indoleamine such as N-dimethylethendylacetamide or N-methylpyridinone. Among these, ethanol, isopropanol, n-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 preferred, and methyl ethyl ketone, butanol, xylene, ethylbenzene and toluene are more preferred. In the present invention, one type may be used alone or two or more types may be used in combination as a dispersion medium.

In the present invention, the dispersing medium to be used in the case where the transparent conductive film or the like is required to have a high refractive index characteristic, and the photocuring property of the conductive microparticles for preventing the formation of the conductive fine particle dispersion or the transparent conductive film When the particle diameter of the fine particles contained in the composition is increased over time, the amount of water contained is 3% by mass or less, preferably 1% by mass or less, and more preferably 0.5% by mass or less.

In the conductive fine particle dispersion of the present invention, the mixing ratio of each component can be appropriately set depending on the use of the conductive fine particle dispersion, and the content of the metal complex is 2 to 45 mass per 100 parts by mass of the conductive fine particles. The amount is preferably 5 to 20 parts by mass, and the content of the dispersion medium is 40 to 1000 parts by mass, preferably 60 to 600 parts by mass. When the amount of the metal complex is less than the above lower limit, the dispersion of the conductive fine particles becomes poor, and when the upper limit is more than the above upper limit, the metal complex does not dissolve in the dispersion medium to cause precipitation. . In addition, when the amount of the dispersion medium is less than the above lower limit, the dissolution of the metal complex and the dispersion of the conductive fine particles are insufficient, and when the amount is more than the above upper limit, the concentration of the conductive fine particle dispersion When it is too thin, it has no practical value.

Further, in the conductive fine particle dispersion liquid in the case where the transparent conductive film or the like is particularly required to have a high refractive index property, the content of the conductive fine particles per 100 parts by mass of the high refractive index fine particles is 30 to 900 parts by mass. (preferably 40 to 500 parts by mass), the content of the metal complex is 3 to 450 parts by mass (preferably 7 to 200 parts by mass), and the content of the dispersion medium is 60 to 9000 parts by mass (preferred It is 10 to 5000 parts by mass). When the amount of the conductive fine particles is less than the above lower limit, the refractive index of the formed film becomes high, but the conductivity is lowered. On the other hand, when the amount of the conductive fine particles is higher than the above upper limit, the conductivity of the formed film becomes high, but the refractive index is lowered. Further, when the amount of the metal complex is less than the above lower limit, the dispersibility of the high refractive index fine particles and the conductive fine particles becomes poor, and when the upper limit is more than the above upper limit, the metal complex does not It is dissolved in a dispersion medium to cause precipitation. Further, when the amount of the dispersion medium is less than the above lower limit, the dissolution of the metal complex, the high refractive index, and the dispersion of the conductive fine particles are insufficient, and when the amount is more than the above upper limit, the high refractive index is high. The concentration of the fine particles and the conductive fine particles is too thin, and there is no practical value.

The conductive fine particle dispersion of the present invention is prepared by adding conductive fine particles, a metal complex, a dispersion medium, and a high refractive index fine particle to be used in a case where high refractive index characteristics are particularly required. Made by mixing. Usually, conductive fine particles or high refractive index fine particles are dispersed in a dispersion medium in which a metal complex is dissolved. It is also possible to carry out a pre-dispersion operation before the dispersion operation. In the dispersion medium in which the metal complex is dissolved, the conductive fine particles or the high refractive index fine particles are gradually added by stirring with a disperser or the like, and it is visually confirmed that there is no conductive fine particles or high refractive index fine particles. The blocks were uniformly stirred until they were. Further, when high refractive index fine particles are blended, a dispersion liquid composed of high refractive index fine particles, a metal complex, and a dispersion medium can be prepared in advance and dispersed by conductive fine particles, a metal complex, and a dispersion medium. The liquid is then prepared by mixing the dispersions.

For the dispersion operation of the conductive fine particles or the high refractive index fine particles, a paint mixer, a ball mill, a sand mill, a centrifugal mill (Centrimill) or the like can be used. In the dispersion operation, it is preferred to use dispersed beads such as glass beads, zirconium beads or the like. The bead diameter is not particularly limited and is usually about 0.05 to 1 mm, preferably 0.05 to 0.65 nm. When the high refractive index fine particles are blended, it is more preferably 0.08 to 0.65 nm, and most preferably 0.08 to 0.5 mm.

In the conductive fine particle dispersion of the present invention, the particle diameter of the conductive fine particles or the high refractive index fine particles is preferably 120 nm or less, and more preferably 80 nm or less. When the median diameter is equal to or greater than this value, the degree of twist of the cured film containing conductive fine particles obtained from the photocurable composition containing conductive fine particles tends to be high.

In the conductive fine particle dispersion liquid of the present invention, the conductive fine particles or the high refractive index fine particles are stably dispersed after a long period of time, and since the ethylene acetylacetone which corrodes the metal is not contained, it can be stored in a metal container. in.

The conductive fine particle dispersion of the present invention can be used in a protective film-forming composition, a composition for preventing reflection film formation, an adhesive, a sealing material, a bonding material, and the like, and is particularly suitable for forming an anti-reflection film having an antistatic function. The composition is used.

The photocurable composition containing conductive fine particles of the present invention contains conductive fine particles, a metal complex, an active energy ray-curable compound, a photopolymerization initiator, and a dispersion medium, and conductive fine particles, a metal complex, and a dispersion medium. As mentioned above.

Further, the photocurable composition containing conductive fine particles for forming a transparent conductive film of the present invention contains high refractive index fine particles having a refractive index of 1.8 or more, conductive fine particles, a metal complex containing no alkoxide, and activity. The energy ray-curable compound, the photopolymerization initiator, and the dispersion medium have a water content of 3% by mass or less, and the high refractive index fine particles, the conductive fine particles, and the dispersion medium are as described above.

Further, in the photocurable composition containing conductive fine particles of the present invention, the cured film is provided with scratch resistance, abrasion resistance, low warpage, adhesion, transparency, refractive index, chemical resistance, and resistance. In the case of static electricity, fine particles other than the above-mentioned conductive fine particles can be used. The type of the fine particles is not particularly limited as long as it can achieve the purpose, and a conventional product such as a commercially available product can be used. For example, inorganic fine particles such as zirconia, titanium oxide, aluminum oxide, and cerium oxide, or organic fine particles. These fine particles may be used alone or in combination of two or more.

The active energy ray-curable compound used in the present invention may be, for example, a radical polymerizable monomer or a radical polymerizable oligomer.

Specific examples of the radical polymerizable monomer are, for example, methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (A) Butyl acrylate, cyclohexyl (meth) acrylate, tetrahydrofuran (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, mono (methyl) Polyethylene glycol acrylate, methoxypolyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, polyethylene glycol polypropylene glycol mono(meth)acrylate, mono (methyl) a monofunctional (meth) acrylate such as poly(ethylene glycol) polytetramethylene glycol acrylate, glycidyl (meth) acrylate, etc.; ethylene glycol di(meth)acrylate, di(meth)acrylic acid Diethylene glycol ester, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate Ester, neopentyl bis(meth)acrylate, allyl bis(meth)acrylate, bisphenol A di(meth)acrylate, oxyethylene modified bisphenol A di(meth)acrylate, two (methyl) propyl Acid polyoxyethylene modified bisphenol A ester, di(meth)acrylic acid oxyethylene modified bisphenol S ester, di(meth)acrylic acid bisphenol S ester, di(meth)acrylic acid 1,4-butanediol Difunctional (meth) acrylate such as ester, 1,3-butylene glycol di(meth)acrylate; trimethylolpropane tris(meth)acrylate; glycerol tri(meth)acrylate , pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ethylene modified trimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, hexa(methyl) a trifunctional or higher (ethyl) acrylate such as dipentaerythritol acrylate; a radical polymerizable monomer such as styrene, vinyl toluene, vinyl acetate, N-vinylpyrrolidone, acrylonitrile or allyl alcohol.

Further, specific examples of the radical polymerizable oligomer, such as polyester (meth) acrylate, polyurethane (meth) acrylate, (meth) acrylate epoxy, polyether (methyl At least one of acrylate, oligo(meth) acrylate, alkylated (meth) acrylate, (meth) acrylate polyol, poly methoxy (meth) acrylate, etc. a prepolymer of acrylonitrile. More preferably, the radical polymerizable oligomer is a (meth) acrylate of a polyester, an epoxy group or a polyurethane. In the present invention, the active energy ray-curable compounds may be used alone or in combination of two or more.

In the photocurable composition containing conductive fine particles of the present invention, since a photopolymerization initiator (photosensitizer) is contained, a small amount of active energy rays can be irradiated to harden the photocurable composition containing conductive fine particles. .

Photopolymerization initiator (photosensitizer) used in the present invention, for example, 1-hydroxycyclohexyl benzophenone, benzophenone, benzyl ketone, benzoin methyl ether, benzoin ether, p-chloride Benzophenone, 4-benzylidene-4-methyldiphenyl sulfide, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butyl Keto-1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylacetone-1. The photopolymerization initiator may be used alone or in combination of two or more.

In the photocurable composition containing conductive fine particles of the present invention, the blending ratio of each component can be appropriately set depending on the use of the photocurable composition containing conductive fine particles, and the metal is contained per 100 parts by mass of the conductive fine particles. The content of the complex compound is preferably 2 to 45 parts by mass (more preferably 5 to 20 parts by mass), and the content of the dispersion medium is preferably 40 to 1000 parts by mass (more preferably 60 to 600 parts by mass). The content of the energy ray-curable compound is preferably from 10 to 1,000 parts by mass (more preferably from 25 to 150 parts by mass), and the content of the photopolymerization initiator is from 0.1 to 20 per 100 parts by mass of the active energy ray-curable compound. The mass fraction is preferably (more preferably from 1 to 15 parts by mass).

Here, when the amount of the metal complex is less than the above lower limit, the dispersibility of the conductive fine particles tends to be poor, and when the amount is more than the above upper limit, the metal complex is not dissolved in the dispersion. A situation in which precipitation occurs in the medium. When the amount of the dispersion medium is less than the above lower limit, the metal complex is dissolved and the dispersibility of the conductive fine particles tends to be insufficient. When the amount of the dispersion medium is more than the above upper limit, the concentration of the conductive fine particle dispersion is increased. When it is too thin, the effect of adding conductive fine particles tends to be insufficient. When the amount of the active energy ray-curable compound is too small as compared with the above lower limit, the refractive index of the cured film is increased, and the transparency tends to be lowered. When the amount is more than the above upper limit, the refractive index of the cured film is less likely to become desired. The high value of the degree. In addition, when the amount of the photopolymerization initiator is less than the above lower limit, the curing rate of the photocurable composition tends to decrease, and when it is more than the above upper limit, a satisfactory effect cannot be obtained.

Further, in the photocurable composition containing conductive fine particles for forming a transparent conductive film, the content of the conductive fine particles is preferably 30 to 900 parts by mass per 100 parts by mass of the high refractive index fine particles (more preferably 40 to 500). The content of the metal complex is preferably from 3 to 450 parts by mass (more preferably from 7 to 200 parts by mass), and the content of the dispersion medium is preferably from 60 to 70,000 parts by mass (more preferably from 100 to 50,000 parts). The content of the active energy ray-curable compound is preferably from 14 to 10,000 parts by mass (more preferably from 35 to 2000 parts by mass), and per 100 parts by mass of the active energy ray-curable compound, the photopolymerization initiator The content is preferably 0.1 to 20 parts by mass (more preferably 1 to 15 parts by mass).

In the photocurable composition containing conductive fine particles for forming the transparent conductive film, when the amount of the conductive fine particles is less than the above lower limit value, the conductivity is lowered. On the other hand, when the amount of the conductive fine particles is higher than the above upper limit value, the conductivity of the formed film becomes high and the refractive index is lowered. When the amount of the metal complex is less than the above lower limit, the dispersion of the high refractive index fine particles and the conductive fine particles tends to be poor, and when the amount is larger than the above upper limit, the metal complex is not dissolved. A situation in which a precipitate is formed in a dispersion medium. When the amount of the dispersion medium is less than the above lower limit value, the dissolution of the metal complex, the dispersion of the high refractive index fine particles and the conductive fine particles tend to be poor, and when the amount is more than the above upper limit, the photohardening occurs. The concentration of the sexual composition is too thin to become practical. When the amount of the active energy ray-curable compound is less than the above lower limit, the refractive index of the transparent conductive film is increased, and the transparency tends to be lowered. When the amount is more than the above upper limit, the refractive index of the transparent conductive film cannot be obtained. The high value of the degree of demand is achieved, and the antistatic function becomes 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 when it is too large as compared with the above upper limit value, a satisfactory effect cannot be obtained.

Further, in the photocurable composition containing conductive fine particles of the present invention, various additives conventionally used in addition to the above may be blended insofar as the object is not impaired. The additive is, for example, a polymerization agent, a curing catalyst, an antioxidant, a leveling agent, a coupling agent, or the like.

The photocurable composition containing conductive fine particles of the present invention can be coated or printed on plastic (polycarbonate, polymethyl methacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin). On the surface of various substrates such as triethylenesulfonyl cellulose resin, polyethylene terephthalate, ABS resin, AS resin, raw spinel resin, etc., metal, wood, paper, glass, slate, etc. Hardening to form a film, for example, for plastic optical parts, touch panels, film-type liquid crystal elements, plastic containers, bed materials for building interior materials, wall materials, artificial marble, etc. to prevent scratches (scratches) or to prevent contamination Protective coating material; anti-reflection film for film-type liquid crystal elements, touch panels, plastic optical parts, etc.; adhesives and sealing materials for various substrates; adhesive materials for printing inks, etc., especially suitable for forming antistatic Functional composition of the antireflective film. Further, when a photocurable composition containing conductive fine particles of high refractive index fine particles is blended, it is particularly preferably used for forming a transparent conductive film having a high refractive index.

When the photocurable composition containing conductive fine particles is applied or printed on a substrate, it can be carried out, for example, by a method such as roll coating, spin coating, or screen printing. Heating is carried out as needed, the dispersion medium (solvent) is evaporated, the coating film is dried, and then the active energy ray (ultraviolet light or electron beam) is irradiated. The active energy source may be a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halogen lamp, a xenon lamp, an excimer laser, a pigment laser, or the like, and an electron beam acceleration device. The irradiation amount of the active energy ray is preferably in 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 the electron beam. The active energy ray-curable compound is polymerized by irradiation with the active energy ray to form a film in which conductive fine particles are bonded by a resin. In general, the film thickness of the film is preferably in the range of 0.1 to 10.0 μm.

The conductive fine particle-containing cured film of the present invention obtained by curing the photocurable composition containing conductive fine particles prepared by the conductive fine particle dispersion of the present invention, the conductive fine particles are uniformly dispersed in the cured film, and can be controlled The refractive index, the transparency is high, and the twist is low. Specifically, the refractive index is 1.45 to 1.90, the light transmittance is 75% or more, the twist is 2.0% or less, and the surface resistance is 10 ¹² Ω/□ or less.

Further, in the present invention, the transparent conductive film of the present invention obtained by curing the composition containing conductive fine particles for forming a transparent conductive film having high refractive index characteristics uniformly disperses high refractive index fine particles and conductive in the transparent conductive film. The fine particles can control the refractive index, have a high refractive index, have high transparency, and have low twist. Specifically, the refractive index is 1.55 to 1.90, the light transmittance is 85% or more, the twist is 1.5% or less, and the surface resistance value is It is 10 ¹² Ω/□ or less. In order to control the refractive index, the ratio of the amount of the high refractive index fine particles and the conductive fine particles to the amount of the active energy ray-curable compound can be adjusted. The transparent conductive film can be used for a conductive anti-reflective material or a display surface of a display device or the like.

In the following, the invention will be specifically described by way of examples and comparative examples. Moreover, in the examples and comparative examples, "parts" are all "parts by mass".

[Examples]

[Examples 1 to 5 and Comparative Examples 1 and 2]

The components used in Examples 1 to 5 and Comparative Examples 1 and 2 were as follows.

<Electroconductive microparticles>

ATO (refractive index 2.0, volume resistance value 10 Ω ‧ cm, primary particle diameter 0.05 μm)

ITO (refractive index 2.0, volume resistivity 0.02 Ω ‧ cm, primary particle size 0.04 μm)

Tin oxide (refractive index 2.0, volume resistance 100Ω‧cm, primary particle size 0.06μm)

Zinc oxide (refractive index 1.95, volume resistance 100Ω‧cm, primary particle size 0.06μm)

<Inorganic microparticles>

Alumina (refractive index 1.76, primary particle size 0.04 μm)

<metal complex>

Zirconium acetylacetate [Zr(C ₅ H ₇ O ₂ ) ₄ ]

Titanium acetate acetate [Ti(C ₅ H ₇ O ₂ ) ₄ ]

Zinc acetylacetate [Zn(C ₅ H ₇ O ₂ ) ₂ ]

Dibutyltin diacetate [(C ₄ H ₉ ) ₂ Sn(C ₅ H ₇ O ₂ ) ₂ ]

<Dispersing Aid>

BYK (share) system, BYK-142

<Active energy ray-curable compound>

Nippon Chemical Co., Ltd., KAYARAD DPHA

<Photopolymerization initiator>

Chiba‧Speciality‧Chemicals, IRGACURE 184

<chelating agent>

Daicel Chemical Industry, acetonitrile

[Example 1]

Into the vessel, 20 parts of zirconium ethoxide, 250 parts of methyl ethyl ketone and 400 parts of glass beads were added in total with respect to 100 parts of tin oxide, and kneaded in a hand mixer for 3 hours. After the kneading, the glass beads were taken out to prepare a dispersion. To the dispersion, 43 parts of DPHA, 2 parts of IRGACURE 184 and 65 parts of methyl ethyl ketone were added to prepare a photocurable composition. The photocurable composition was applied onto a PET film (A4100, manufactured by Toyobo Co., Ltd.) having a thickness of 100 μm using a bar coater, and the organic solvent was evaporated, and then irradiated with 300 gJ/cm ² in a high-pressure mercury lamp in the air. Light, a transparent conductive film having a thickness of 3 μm was produced. The film was produced after the photocurable composition and after 6 months.

[Embodiment 2]

Adding 10 parts of titanium acetoxyacetate, 10 parts of BYK-142, 250 parts of 2-butanol and 400 parts of glass beads in a total amount relative to 100 parts of ATO in a container, and mixing by hand mixer 3 hours. After the kneading, the glass beads were taken out to prepare a dispersion. To the dispersion, 43 parts of DPHA, 2 parts of IRGACURE 184 and 65 parts of 2-butanol were added to prepare a photocurable composition. Then, a transparent conductive film having a thickness of 3 μm was produced by the same method as in Example 1.

[Example 3]

The amount of 10 parts of dibutyltin bisacetate, 25 parts of 2-butanol, and 400 parts of glass beads was added in a total amount to 100 parts of ATO in a container, and kneaded in a hand mixer for 3 hours. After the kneading, the glass beads were taken out to prepare a dispersion. To the dispersion, 43 parts of DPHA, 2 parts of IRGACURE 184 and 65 parts of 2-butanol were added to prepare a photocurable composition. Then, a transparent conductive film having a thickness of 3 μm was produced by the same method as in Example 1.

[Example 4]

Add 50 parts of ITO, 10 parts of dibutyltin bisacetate, 250 parts of 2-butanol and 400 parts of glass beads to 50 parts of ATO in a container, and mix by hand mixer. 3 hours. After the kneading, the glass beads were taken out to prepare a dispersion. To the dispersion, 43 parts of DPHA, 2 parts of IRGACURE 184 and 65 parts of 2-butanol were added to prepare a photocurable composition. Then, a transparent conductive film having a thickness of 3 μm was produced by the same method as in Example 1.

[Example 5]

In a container, 40 parts of alumina, 25 parts of dibutyltin bisacetate, 250 parts of 2-butanol, and 400 parts of glass beads were added in a total amount with respect to 60 parts of ITO, and the mixture was carried out by hand mixer. Mix for 3 hours. After the kneading, the glass beads were taken out to prepare a dispersion. To the dispersion, 67 parts of DPHA, 6.7 parts of IRGACURE 184 and 170 parts of 2-butanol were added to prepare a photocurable composition. Then, a transparent conductive film having a thickness of 3 μm was produced by the same method as in Example 1.

[Comparative Example 1]

The amount of BYK-142, 250 parts of 2-butanol and 400 parts of glass beads was added in a total amount of 100 parts of tin oxide in a container, and kneaded in a hand mixer for 3 hours. The dispersion has a viscosity-increasing condition during the mixing.

[Comparative Example 2]

A transparent conductive film having a thickness of 3 μm was produced in the same manner as in Example 2 except that 20 parts of acetalacetone was added in place of 20 parts of titanium acetoxyacetate.

<Evaluation method>

(1) The diameter of inorganic particles

The median diameter of the inorganic fine particles dispersed in the dispersion liquid and the photocurable composition produced in the examples and the comparative examples was measured by using a Microtrac particle size distribution meter manufactured by Nikkiso Co., Ltd., three months after the production (stored in After 40 months, and after 6 months (stored at 40 ° C), the measurement was carried out under the following conditions.

(2) Transmittance and twist of transparent conductive film

The transparent conductive films obtained in the examples and the comparative examples were measured for transmittance and twist by NDH5000 manufactured by Nippon Denshoku Industries Co., Ltd. The measured value is the value of the substrate.

(3) Surface resistance value

The transparent conductive film obtained in the examples and the comparative examples was measured by Hiresta IP MCP-HT260 manufactured by Mitsubishi Chemical Corporation.

(4) Refractive index

The transparent conductive films obtained in the examples and the comparative examples were measured by an Abbe refractometer DRM4 (20 ° C) manufactured by Atago.

(5) Corrosion status of metal containers

The dispersion prepared in the examples and the comparative examples was placed in a stainless steel container (SUS304; Fe-Cr-Ni-based stainless steel), and the corrosion state of the stainless steel container after standing for one month was visually evaluated.

The above measurement results, evaluation results, and composition of each composition are shown in Table 1.

As is clear from the data shown in Table 1, when the metal complex is contained (Examples 1 to 5), regardless of whether or not the dispersing aid is contained, a dispersion having excellent storage stability can be obtained, even when stored in a metal container. There is still no state in which the metal container is corroded. Further, the transparent conductive film obtained by applying the photocurable composition of the dispersion liquids obtained in Examples 1 to 5 had a refractive index of 1.45 to 1.90, a transmittance of 75%, a twist of 2.0 or less, and a surface resistance value of 10. ¹² Ω/□ or less, it has antistatic function, high transparency, and excellent electrical conductivity. When the metal complex was not added (Comparative Example 1), the dispersion was difficult and a uniform dispersion could not be obtained. Further, when the ethylene glycol was added and the dispersed dispersion (Comparative Example 2) was stored in a metal container, it was confirmed that there was a significant corrosion state of the container.

In the following, the conductive fine particle dispersion liquid for which the high refractive index property is required, the conductive fine particle-containing composition for forming a transparent conductive film, and the transparent conductive film of the present invention will be specifically described by way of examples and reference examples. Moreover, in the examples and comparative examples, "parts" are all "parts by mass".

[Examples 6 to 11 and Reference Examples 1 to 6]

The components used in Examples 6 to 11 and Reference Examples 1 to 6 are as follows.

<High refractive index microparticles>

Zirconia (refractive index 2.2, primary particle size 0.02 μm)

Titanium oxide (refractive index 2.76, primary particle size 0.02 μm)

<Electroconductive microparticles>

ATO (refractive index 2.0, volume resistance value 10 Ω ‧ cm, primary particle diameter 0.06 μm)

Tin oxide (refractive index 2.0, volume resistance 100Ω‧cm, primary particle size 0.06μm)

Zinc oxide (refractive index 1.95, volume resistance 100Ω‧cm, primary particle size 0.06μm)

<metal complex>

Zirconium acetylacetate [Zr(C ₅ H ₇ O ₂ ) ₄ ]

Titanium acetate acetate [Ti(C ₅ H ₇ O ₂ ) ₄ ]

Aluminum acetonitrile acetate [Al(C ₅ H ₇ O ₂ ) ₃ ]

Zinc acetylacetate [Zn(C ₅ H ₇ O ₂ ) ₂ ]

Indium acetate indium [In(C ₅ H ₇ O ₂ ) ₃ ]

Dibutyltin diacetate [(C ₄ H ₉ ) ₂ Sn(C ₅ H ₇ O ₂ ) ₂ ]

Zirconium tributoxyacetate [(C ₄ H ₉ O) ₃ Zr(C ₅ H ₇ O ₂ ) ₂ ]

<Dispersing Aid>

BYK (share) system, BYK-142

<Active energy ray-curable compound>

Nippon Chemical Co., Ltd., KAYARAD DPHA

<Photopolymerization initiator>

Chiba‧Speciality‧Chemicals, IRGACURE 184

<chelating agent>

Daicel Chemical Industry, acetonitrile

[Embodiment 6]

Adding 100 parts of tin oxide, 40 parts of zirconium ethoxide, 500 parts of 2-butanol and 800 parts of glass beads to 100 parts of zirconia in a container, and mixing by hand mixer 7 hour. After the kneading, the glass beads were taken out to prepare a dispersion. To the dispersion, 86 parts of DPHA, 4.3 parts of IRGACURE 184 and 130 parts of 2-butanol were placed to prepare a photocurable composition. The photocurable composition was applied onto a PET film (A4100, manufactured by Toyobo Co., Ltd.) having a thickness of 100 μm using a roll coater, and the organic solvent was evaporated, and then irradiated with 300 mJ/cm ² in a high-pressure mercury lamp in the air. Light, a transparent conductive film having a thickness of 3 μm was produced. The film was produced after the photocurable composition and after 6 months.

[Embodiment 7]

Adding 43 parts of ATO, 0.6 parts of titanium acetylate, 14.3 parts of BYK-142, 500 parts of 2-butanol and 800 parts of glass beads to 100 parts of titanium oxide in a total amount. All ingredients were mixed in a manual mixer for 7 hours. After the kneading, the glass beads were taken out to prepare a dispersion. To the dispersion, 143 parts of DPHA, 7.2 parts of IRGACURE 184 and 160 parts of 2-butanol were added to prepare a photocurable composition. Then, a transparent conductive film having a thickness of 3 μm was produced by the same method as in Example 6.

[Embodiment 8]

Adding 233 parts of tin oxide, 33 parts of aluminum acetoxyacetate, 880 parts of 2-butanol and 800 parts of glass beads to 100 parts of ATO in a container, and mixing by hand mixer 7 hour. After the kneading, the glass beads were taken out to prepare a dispersion. To the dispersion, 143 parts of DPHA, 7.2 parts of IRGACURE 184 and 160 parts of 2-butanol were added to prepare a photocurable composition. Then, a transparent conductive film having a thickness of 3 μm was produced by the same method as in Example 6.

[Embodiment 9]

Adding 100 parts of zinc oxide, 20 parts of zinc acetoxyacetate, 500 parts of 2-butanol and 800 parts of glass beads to 100 parts of titanium oxide in a container, and mixing by hand mixer 7 hours. After the kneading, the glass beads were taken out to prepare a dispersion. To the dispersion, 86 parts of DPHA, 4.3 parts of IRGACURE 184 and 130 parts of 2-butanol were placed to prepare a photocurable composition. Then, a transparent conductive film having a thickness of 3 μm was produced by the same method as in Example 6.

[Embodiment 10]

A transparent conductive film having a thickness of 3 μm was produced by the same treatment as in Example 9 except that 20 parts of dibutyltin diacetate was substituted for 20 parts of zinc acetoxyacetate.

[Example 11]

A transparent conductive film having a thickness of 3 μm was produced by the same treatment as in Example 9 except that 20 parts of indium phthalate was added in place of 20 parts of zinc acetoxyacetate.

[Reference Example 1]

Add 100 parts of tin oxide, 20 parts of BYK-142, 60 parts of 2-butanol and 800 parts of glass beads to 100 parts of zirconia in a total amount, and mix for 7 hours in a hand mixer. . In the kneading, the dispersion produces a viscosity-increasing condition.

[Reference Example 2]

A transparent conductive film having a thickness of 3 μm was produced by the same treatment as in Example 7 except that 6 parts of acetaminoacetone was used instead of 6 parts of titanium acetylate.

[Reference Example 3]

The amount of 100 parts of tin oxide, 10 parts of titanium ethoxide, 600 parts of 2-butanol, and 800 parts of glass beads was added in a total amount in a container, and kneaded in a hand mixer for 7 hours. After the kneading, the glass beads were taken out to prepare a dispersion. To the dispersion, 150 parts of DPHA, 5 parts of IRGACURE 184 and 100 parts of 2-butanol were added to prepare a photocurable composition. Then, a transparent conductive film having a thickness of 3 μm was produced by the same method as in Example 6.

[Reference Example 4]

The whole ingredients were added in an amount of 100 parts of zirconia, 10 parts of zirconium ethoxide, 270 parts of 2-butanol, and 400 parts of glass beads in a container, and kneaded in a hand mixer for 7 hours. After the kneading, the glass beads were taken out to prepare a dispersion. To the dispersion, 43 parts of DPHA, 2.2 parts of IRGACURE 184 and 60 parts of 2-butanol were added to prepare a photocurable composition. Then, a transparent conductive film having a thickness of 3 μm was produced by the same method as in Example 6.

[Reference Example 5]

A transparent conductive film having a thickness of 3 μm was produced by the same treatment as in Example 6 except that 40 parts of zirconium monobutoxyacetate was added in place of 40 parts of zirconium ethoxide.

[Reference Example 6]

In addition to adding 40 parts of zirconium monobutoxyacetate to replace 40 parts of zirconium ethoxide, by adding 90 parts of water and 410 parts of 2-butanol in place of 500 parts of 2-butanol, The same treatment as in Example 6 was carried out to prepare a transparent conductive film having a thickness of 3 μm.

<Evaluation method>

Further, the diameter of the inorganic fine particles and the high refractive index fine particles, the transmittance of the transparent conductive film, the twist, the surface resistance value, the refractive index, and the corrosion state of the metal container were carried out in the same manner as in Examples 1 to 6.

The above measurement results, evaluation results, and composition of each composition are shown in Table 2.

As is clear from the data shown in Table 2, when the metal complex is contained (Examples 6 to 11), regardless of whether or not the dispersing aid is contained, a dispersion having excellent storage stability can be obtained, even when stored in a metal container. There is still no state in which the metal container is corroded. Further, the transparent conductive film obtained by applying the photocurable composition of the dispersion liquids obtained in Examples 6 to 11 had a refractive index of 1.55 to 1.90, a transmittance of 85% or more, a twist of 1.5% or less, and a surface resistance value. It is 10 ¹² Ω/□ or less, has high refractive index, high transparency, and is excellent in electrical conductivity. When no metal complex was added (Reference Example 1), dispersion was difficult and a uniform dispersion could not be obtained. Further, when the ethyl isopropyl acetal and the dispersed dispersion (Reference Example 2) were added to a metal container, it was confirmed that there was a significant container corrosion state. When the high refractive index fine particles were not added (Reference Example 3), it was not possible to obtain a film satisfying all the characteristics such as high refractive index, high transparency, and electrical conductivity. When no conductive fine particles were added (Reference Example 4), it was confirmed that the film was not electrically conductive. When an alkoxide is contained as a metal complex (Reference Examples 5 and 6), the particle diameter becomes large with time, and the film characteristics also largely change. Further, when a large amount of water was contained (Reference Example 6), it was confirmed that the particle diameter was remarkably increased.

Claims (28)

A conductive fine particle dispersion liquid characterized by comprising conductive fine particles, a metal complex, and a dispersion medium, wherein the content of the metal complex is 2 to 45 parts by mass per 100 parts by mass of the conductive fine particles, and is dispersed. The content of the medium is 40 to 1000 parts by mass. The conductive fine particle dispersion according to claim 1, wherein the metal complex does not contain an alkoxide. The conductive fine particle dispersion according to claim 1 or 2, wherein the conductive fine particles are at least one selected from the group consisting of ITO, ATO, tin oxide, zinc oxide, indium oxide, zinc antimonate, and antimony pentoxide. Metal oxides. The conductive fine particle dispersion according to claim 1 or 2, wherein the metal complex is selected from the group consisting of zirconium, titanium, chromium, manganese, iron, cobalt, nickel, copper, vanadium, aluminum, zinc, indium, and tin. And a group of metals in which platinum is formed, and a ligand selected from the group consisting of β-diketones. The conductive fine particle dispersion according to claim 1 or 2, wherein the metal complex is a metal selected from the group consisting of zirconium, titanium, aluminum, zinc, indium, and tin, and is selected from the group consisting of trimethyl ethane. A ligand composed of a group of trifluoroacetic acid acetone, ethyl acetonylacetone, ethylene acetonide fluoride, and hexamethylene hexafluoroacetone. A photocurable composition containing conductive fine particles, which is characterized in that it is composed of conductive fine particles, a metal complex, an active energy ray-curable compound, a photopolymerization initiator, and a dispersion medium, and is electrically conductive per 100 parts by mass. The content of the fine particles and the metal complex is 2 to 45 parts by mass. The content of the dispersing medium is 40 to 1000 parts by mass, the content of the active energy ray-curable compound is 10 to 1000 parts by mass, and the content of the photopolymerization initiator is 0.1 to 20 per 100 parts by mass of the active energy ray-curable compound. Parts by mass. The photocurable composition containing conductive fine particles according to claim 6, wherein the metal complex does not contain an alkoxide. The photocurable composition containing conductive fine particles according to claim 6 or 7, wherein the conductive fine particles are selected from the group consisting of ITO, ATO, tin oxide, zinc oxide, indium oxide, zinc antimonate and antimony pentoxide. At least one metal oxide in the group. The photocurable composition containing conductive fine particles according to claim 6 or 7, wherein the metal complex is selected from the group consisting of zirconium, titanium, chromium, manganese, iron, cobalt, nickel, copper, vanadium, aluminum, A group of metals in which zinc, indium, tin, and platinum are grouped with a ligand selected from the group consisting of β-diketones. The photocurable composition containing conductive fine particles according to claim 6 or 7, wherein the metal complex is a metal selected from the group consisting of zirconium, titanium, aluminum, zinc, indium and tin, and is selected from the group consisting of A group of ligands consisting of trimethylacetamidofluoride, acetone, etidylacetone, etidylacetone trifluoride and etidinyl hexafluoride. A cured film containing conductive fine particles, which is characterized in that a photocurable composition containing conductive fine particles according to claim 6 or 7 of the patent application is applied or printed on a substrate and cured. A cured film containing conductive fine particles according to claim 11 in which the refractive index is 1.45 to 1.90, the light transmittance is 75% or more, the twist is 2.0% or less, and the surface resistance is 10 ¹² Ω/□ or less. . A conductive anti-reflection material characterized by having a cured film containing conductive fine particles as in the eleventh or twelfth aspect of the patent application. A display device characterized by having a cured film containing conductive fine particles as in the eleventh or twelfth aspect of the patent application. A conductive fine particle dispersion liquid characterized by comprising high refractive index fine particles having a refractive index of 1.8 or more, conductive fine particles, a metal complex containing no alkoxide, and a dispersion medium, wherein the content is high per 100 parts by mass. The content of the refractive index fine particles, the conductive fine particles is 30 to 900 parts by mass, the content of the metal complex containing no alkoxide is 3 to 450 parts by mass, and the content of the dispersion medium is 60 to 9000 parts by mass, and the moisture is 3 Below mass%. The conductive fine particle dispersion according to the fifteenth aspect of the invention, wherein the high refractive index fine particles are at least one metal oxide selected from the group consisting of zirconia, titanium oxide and cerium oxide. The conductive fine particle dispersion according to claim 15 or 16, wherein the conductive fine particles are at least one selected from the group consisting of ITO, ATO, tin oxide, zinc oxide, indium oxide, zinc antimonate, and antimony pentoxide. Metal oxides. The conductive fine particle dispersion according to claim 15 or 16, wherein the metal complex is selected from the group consisting of zirconium, titanium, chromium, manganese, iron, cobalt, nickel, copper, vanadium, aluminum, zinc, indium, and tin. And a group of metals in which platinum is formed, and a ligand selected from the group consisting of β-diketones. The conductive fine particle dispersion according to claim 15 or 16, wherein the metal complex is a metal selected from the group consisting of zirconium, titanium, aluminum, zinc, indium, and tin, and is selected from the group consisting of trimethyl ethane. A ligand composed of a group of trifluoroacetic acid acetone, ethyl acetonylacetone, ethylene acetonide fluoride, and hexamethylene hexafluoroacetone. A photocurable composition containing conductive fine particles for forming a transparent conductive film, characterized by high refractive index fine particles having a refractive index of 1.8 or more, conductive fine particles, a metal complex containing no alkoxide, and active energy a linear curable compound, a photopolymerization initiator, and a dispersion medium, wherein the content of the conductive fine particles is from 30 to 900 parts by mass per 100 parts by mass of the high refractive index fine particles, and the metal complex containing no alkoxide The content is 3 to 450 parts by mass, the content of the dispersion medium is 60 to 70,000 parts by mass, and the content of the active energy ray-curable compound is 14 to 10,000 parts by mass, and the light is hardened per 100 parts by mass of the active energy ray-curable compound. The content of the polymerization initiator is 0.1 to 20 parts by mass, and the water content is 3% by mass or less. The photocurable composition containing conductive fine particles for forming a transparent conductive film according to claim 20, wherein the high refractive index fine particles are at least one selected from the group consisting of zirconia, titanium oxide, and cerium oxide. Oxide. The photocurable composition containing conductive fine particles for forming a transparent conductive film according to claim 20 or 21, wherein the conductive fine particles are selected from the group consisting of ITO, ATO, tin oxide, zinc oxide, indium oxide, and zinc antimonate. And at least one metal oxide in the group of pentoxide. The photocurable composition containing conductive fine particles for forming a transparent conductive film according to claim 20 or 21, wherein the metal complex is selected from the group consisting of zirconium, titanium, chromium, manganese, iron, cobalt, nickel, A metal group of copper, vanadium, aluminum, zinc, indium, tin, and platinum, and a ligand selected from the group consisting of β-diketones. The photocurable composition containing conductive fine particles for forming a transparent conductive film according to claim 20 or 21, wherein the metal complex is grouped from zirconium, titanium, aluminum, zinc, indium and tin. The metal is formed with a ligand selected from the group consisting of trimethylacetamidofluoride, acetone, acetonylacetone, etidylacetate and hexafluoroacetone. A transparent conductive film characterized in that a photocurable composition containing conductive fine particles for forming a transparent conductive film according to any one of claims 20 to 24 is coated or printed on a substrate, and is cured. By. The transparent conductive film of claim 25, wherein the refractive index is 1.55 to 1.90, the light transmittance is 85% or more, the twist is 1.5% or less, and the surface resistance is 10 ¹² Ω/□ or less. A conductive anti-reflective material characterized by having a transparent conductive film as disclosed in claim 25 or 26 on a transparent resin substrate. A display device characterized by having a transparent conductive film as disclosed in claim 25 or 26 on the display surface.