KR100231790B1 - Transparent conductive coating composition and its applications - Google Patents

Abstract

The present invention is a composition for forming a conductive film,

a) antimony doped tin oxide (ATO), indium doped tin oxide (ITO), antimony

5 containing particles of this doped zinc oxide (AZO) alone or in combination

Conductivity with a particle distribution of from 400 nm and an average particle diameter of 80 nm or less

Fine particles; And

b) structurally stable zirconium eggs represented by the following general formula (2) or (3)

The coxide, zirconium alkoxy acetyl acetonate alone or under mixing

Dispersion stabilizer

Zr ₄ O (OPr ⁿ ) ₁₀ (acac) (2) ₄ (2)

Zr ₁₀ O ₆ (OH) ₄ (OPr ⁿ ) ₁₈ (AA) (3) ₆ (3)

It provides a composition comprising a.

Description

Preparation and application of a composition for forming a transparent conductive film

The present invention provides a coating composition, a method for manufacturing the same, a method for producing the same, and a method for manufacturing the same, and a method for preparing the transparent coating film which is coated on a non-conductive substrate such as glass, plastic, and fiber to form a conductive coating. Relates to a device.

In particular, the composition for forming a transparent conductive film of the present invention is applied to a front panel of a CRT or CDT using a transparent substrate such as glass or plastic, or to a front panel such as a plasma display panel (PDP) or a liquid crystal display (LCD). It has a protective effect.

Since the front panel of a video device made of glass or plastic is an insulator, static electricity is generated on the surface of the video device during operation. Due to the surface charging phenomenon, this substance such as dust around is easily adsorbed and contaminates the surface, resulting in deterioration of image quality. In addition, when the viewer unconsciously touches the front panel, an electric shock is felt, and sometimes such static electricity may cause loss or malfunction of IC circuits in the device. In order to solve the above problems, a method of removing a charge charged on a panel by coating a transparent conductive coating on the front surface of the imaging device is widely used.

Examples of the method of coating such a transparent antistatic coating film include the following examples. First, there is a method of forming a transparent conductive film composed of a metal or an inorganic oxide on the surface of the substrate using a method such as CVD, PVD, vacuum deposition, and sputtering. This dry process is mainly made of a batchwise method (Batchwise Method) is low productivity, and the equipment is expensive, the surface area or shape of the plate is limited by the size of the vacuum equipment has the disadvantage.

Second, a method of forming a conductive film by spraying conductive fine particles such as indium oxide (In ₂ O ₃ ) or tin oxide (SnO ₂ ) or fine metal powder on the front of the panel has been introduced. The film is not uniform in thickness, there is a phenomenon that a hole is formed in the antistatic film due to the bubbles generated during the spray, and there is a disadvantage that the adhesive strength between the substrate and the film is poor.

Third, in order to form such a conductive film, fine particles having excellent conductivity, such as tin oxide (SnO ₂ ) or indium oxide (In ₂ O ₃ ), are dispersed in an acrylate or an epoxy resin and spray-coated or coated on a substrate. After coating through spin coating or the like, a method of completing a coating by curing with heat or ultraviolet rays has been introduced. However, such a transparent conductive film has a disadvantage in that wear resistance is poor and the surface is easily damaged by a solvent such as alcohol or acetone.

Fourth, recently, U.S. Patent No. 5,256,484, U.S. Patent No. 5,382,383, Japanese Patent Publication No. 54613/1989, PCT Publication WO89 / 03114, WO90 / 02157 and the like have been disclosed in antimony doped tin oxide (ATO) or indium doped tin (ITO). Nanoparticles having excellent conductivity such as Odide) and general formula 1

<Formula 1>

A method of forming a conductive film having excellent conductivity and chemical resistance by introducing an organic silicon compound or a partial hydrolyzate thereof as a matrix material and mixing the same to form a coating solution and then applying it to a substrate has been introduced. In such a film-forming mixed solution, bisacetylacetonato alkoxyzirconium or acetylacetonato chelate may be used as part of the matrix material.

Fifth, Korean Patent Publication No. 96-2743 proposes a coating solution which improves the smoothness and durability of a film by optimizing the degree of polymerization of a silica polymer used as a matrix in the transparent conductive film forming composition prepared as described above.

Of the matrix of a solution for forming a transparent conductive film shown in U.S. Patent No. 5,256,484, U.S. Patent No. 5,382,383, Japanese Patent Application Publication No. 54613/1989, PCT Publications WO89 / 03114 and WO90 / 02157, and Korean Patent Publication No. 96-2743 Zirconium oxy salts, alkoxybisacetylacetonato zirconium or acetylacetonato metal chelate materials used in part are not only used as part of the matrix, but more importantly, conductive particulates by reacting with the conductive particulates in solution to modify the surface of the conductive particulates. It stabilizes in solution and prevents agglomeration between each other during various manufacturing processes, and plays an important role in improving the storage stability of the solution. However, these zirconium oxy salts, alkoxybisacetylacetonato zirconium or acetylacetonato metal chelate materials have a low molecular weight and high reactivity, and thus react rapidly with the conductive fine particles to form a dense insulating film on the surface of the fine particles. It may also result in a decrease in conductivity.

The present invention solves these problems, and the composition and method for producing a transparent coating having excellent alkali resistance, water resistance, solvent resistance and smoothness, adhesion, especially conductivity on the surface of a substrate such as glass or plastic, and the composition It aims at providing the base material which carried out the coating by using.

1 is a structure of Zr ₄ O (OPr ⁿ ) ₁₀ (acac) ₄ by X-ray single crystal diffraction method.

2 is a structure of Zr ₁₀ O ₆ (OH) ₄ (OPrn) ₁₈ (AA) ₆ by X-ray single crystal diffraction method.

The transparent conductive film-forming composition of the present invention is characterized by containing the following composition components for improving physical properties.

(1) conductive fine particles:

As a component that shows the conductivity of the composition for forming a transparent conductive film of the present invention, fine powders of metal oxides having excellent conductivity such as antimony doped tin oxide (ATO), indium doped tin oxide (ITO), and antimony doped zinc oxide (AZO) are used. It became. The particle diameter of the metal fine particles dispersed in the composition has a size between 5 nm and 400 nm and preferably has an average particle diameter of 80 nm or less, and at least 60% of the total particles have a particle diameter of 100 nm or less. The branches have a distribution. These small particles do not cause light scattering to maintain film transparency. The transparent conductive film-forming composition developed in the present invention used AZO (Antimonuy doped Zine Oxide) in addition to the conductive particles such as ATO or ITO which are widely known. ATO and ITO conductive fine particles were 17.2% and 15.3% solids of Mitsubishi Metal Corp. in Japan, respectively, and Nissan Chemical Co., Japan. Used in sol state.

(2) dispersion stabilizer:

The transparent conductive film-forming composition of the present invention is a compound of the general formula (II), (III) below to stabilize the conductive fine particles to prevent agglomeration between each other during the manufacturing process of the composition

<Formula 2>

Zr ₄ O (OPr ⁿ ) ₁₀ (acac) (2) ₄

<Formula 3>

Zr ₁₀ O ₆ (OH) ₄ (OPr ⁿ ) ₁₈ (AA) (3) ₆

Partial condensates of zirconium alkoxides or zirconium alkoxyacetylacetonates, which are represented by and have a stable structure, were used. FIG. 1 shows the molecular structures identified by X-ray single crystal diffraction of Zr ₄ O (OPr ⁿ ) ₁₀ (acac) ₄ and Zr ₁₀ O ₆ (OH) ₄ (OPr ⁿ ) ₁₈ (AA) ₆ . CR Academ Sci., Paris, vol. 311, pp. 1161 (1990) and Mater. Res. Soc. Symp. Proc., Vol. 272, p. 3 (1992).

Examples of methods for the synthesis of structurally stable partial condensates of metal alkoxides or metal alkoxyacetylacetonates and their particular application to the sol-gel process show different properties from those of non-condensed metal alkoxides or metal alkoxyacetylacetonates. of the American Chemical Society (1991) Vol. 113, pp. 8190 (1991) and 115, pp. 8469 (1993), Mater. Res. Soc. Symp. Proc. 271, page 57 (1992), Polymer preprint, 34 (1), page 250 (1993).

On the other hand, as part of the matrix of the transparent conductive film-forming solution shown in U.S. Patent 5,256,484, U.S. Patent 5,382,383, Japanese Patent Publication No. 54613/1989, WO89 / 03114, WO90 / 02157, or Korean Patent Publication No. 96-2743 The zirconium oxy salts, bisacetylacetonato alkoxyzirconium or acetylnacetonate chelate materials used are not only used as part of the matrix, but more importantly, the conductive fine particles are reacted with the conductive fine particles in the solution to modify the surface of the conductive fine particles. It is used for the purpose of stabilizing within and improving the storage stability of the solution by preventing aggregation between each other during the manufacturing process.

Since these zirconium oxy salts, bisacetylacetonato alkoxy zirconium or acetylacetonatochelate materials have low molecular weight and high reactivity, they react rapidly with the conductive fine particles to form an insulating film that is dense on the surface of the fine particles. Problems that result in detriment have already been pointed out above. However, the partial condensates of structurally stable metal alkoxides or metal alkoxyacetylacetonates used in the present invention have a high molecular weight, have a cluster-type structure, and have a position showing selective reactivity at specific sites in the structure. It is difficult to form a dense zirconium oxide (ZrO ₂ ) insulating layer by reacting with the surface of, thus improving the dispersibility of the fine particles but not causing a decrease in conductivity.

(3) Binder:

In the composition for forming a transparent conductive film of the present invention, a silane, a metal alkoxide or a metal alkoxyacetyl as necessary in order to increase the adhesion between the film and the substrate and to increase the strength, smoothness, wear resistance, durability, chemical resistance and water resistance of the film. A binder such as acetonate or the like is used as part of the composition. As the silane used as the binder in the transparent conductive film-forming composition developed in the present invention, an organosilicon compound represented by Formula (I) or a partial hydrolyzate thereof was used. The metal alkoxides, metal alkoxyacetylacetonates or their partial hydrolyzates represented by the general formula (3) used in the present invention improve conductivity as compared to binders made of highly insulating silica materials when used alone or together with silane as a binder.

<Formula 4>

Meanwhile, in the inventions disclosed in U.S. Patent No. 5,256,484, U.S. Patent 5,382,383, Japanese Patent Publication No. 54613/1989, PCT Publication WO89 / 03114, WO90 / 02157, etc. The metal alkoxide having was used as a binder.

<Formula 5>

In this case, due to its high reactivity, the storage stability is poor and the quenching phenomenon frequently occurs in the obtained coating film. 113, pp. 8190 (1991), and 115, pp. 8469 (1993), Mater. Res. Soc. Symp. As described in Proc., Vol. Due to the linear growth of the polymer occurs whitening phenomenon is reduced or disappears. Such partial condensates of metal alkoxy acetylacetonates were synthesized by partial hydrolysis of metal alkoxy acetylacetonates at room temperature or high temperature with controlled amounts of water.

The transparent conductive film-forming composition of the present invention contains the above two components (1) conductive fine particles and (2) dispersion stabilizer as common components and, if necessary, uses a substance capable of forming silane or other metal oxide as a binder. And solvents and other additives can be prepared. The composition prepared in this way can be divided into the following five types.

Composition 1: Stable Dispersion of Particles Conductive Particles and Zirconium Compounds

Agent, a composition containing a solvent and a stabilizer for inhibiting polymerization.

Composition 2: Particulate Dispersion Stabilization Consisting of Conductive Particles and Zirconium Compounds

The composition containing the agent, the silane binder, a solvent, and the stabilizer for polymerization inhibition.

Composition 3: Stable Dispersion of Particles Conductive Particles and Zirconium Compounds

Agent, metal alkoxide or metal alkoxyacetylacetonate or

Binders, Solvents, and Polymerization Stability Using Partial Hydrolysates

A composition containing an agent.

Composition 4: Stable Dispersion of Particulates Conductive Particles and Zirconium Compounds

Agent, silane binder, metal alkoxide or metal alkoxyacetylacetone

Binders, Solvents, Polymerizations Using Yite or Their Partial Hydrolysates

A composition containing a stabilizer for blocking.

Composition 5: The composition which added silica to the compositions 1-4.

The preferred manufacturing process of the transparent conductive film-forming compositions developed in the present invention and the physical properties of the substrate coated with the prepared composition are as follows.

Composition 1

As a component that shows the conductivity of the transparent conductive film-forming composition developed in the present invention, a metal oxide having excellent conductivity such as antimony doped tin oxide (ATO), indium doped tin oxide (ITO), and antimony doped zinc oxide (AZO) Fine powder was used. The metal oxide fine particles dispersed in the composition have a particle diameter of between 5 nm and 400 nm and preferably have an average particle diameter of 80 nm or less, and at least 60% of the total particles have a particle diameter of 100 nm or less. Has a distribution. These small particles do not cause light scattering to maintain film transparency.

Partial condensates of zirconium alkoxides or zirconium alkoxyacetylacetonates have been used as the fine particle dispersion stabilizers composed of zirconium compounds used to stabilize these conductive fine particles to prevent agglomeration of one another during the preparation of the composition.

This dispersion stabilizer is dissolved in an alcoholic solvent and then added with stirring the conductive particulate sol. The concentration of the dispersion stabilizer is less than 1 to 80% by weight, preferably diluted to 2 to 50% by weight. The ratio of the conductive particles in the solid content present in the composition to the dispersion stabilizer converted into zirconium oxide (ZrO ₂ ) is preferably 1 to 5. If the ratio is less than 1, the conductivity of the film is deteriorated due to aggregation of the conductive fine particles, and if it is 5 or more, the adhesion of the film is inferior. The solid content in the composition is preferably 0.1 to 10% by weight. If the solid content is less than 0.1%, the conductivity of the film is bad, and if it is more than 10%, the storage stability of the solution is poor. The ratio of the dispersion stabilizer in terms of the water present in the composition and the zirconium oxide (ZrO ₂₎ is 0.1 to 40 are suitable. If this ratio is less than 0.1, the conductivity of the conductive fine particles is reduced, and if it is more than 40, the storage stability of the solution is poor. In order to prevent the partially hydrolyzable substance of zirconium alkoxyacetylacetonate present in the composition from growing at room temperature to form a polymer, the storage stability of the composition is deteriorated, organic materials capable of coordinating growth with these zirconium center metal atoms can be prevented. Used as storage stabilizer. The materials used are glycol, N-methylpyrrolidone, morpholine, ethyl cellulsolve, dimethyl formamide, diacetone alcohol and the like. The ratio of dispersion stabilizer and storage stabilizer in terms of zirconium oxide (ZrO ₂ ) is expressed by weight. 1-25 are suitable. If the ratio is 25 or more, the storage stability of the solution deteriorates. If the ratio is less than 1, the uniformity of the coating layer is lowered.

Composition 2

Composition 2 is prepared by adding silane or partial hydrolyzate of silane represented by formula (A) as a binder to composition 1. The molar ratio of the amount of water used in the partial hydrolysis of the silane and the silane monomer is 1 to 4, and preferably 2 to 4 is used. If this ratio is less than 1, unhydrolyzed monomers or oligomers with too low molecular weight can be present and evaporate during the coating process. When growing the silane, the pH is preferably 2 to 5, and preferably, the pH is 2 to 3, and the acid used is hydrochloric acid, nitric acid, acetic acid, or the like. When growing the silane, the temperature is suitably 0 to 200 캜, preferably 25 to 80 캜. As for the weight ratio of the zirconium dispersion stabilizer converted into the zirconium oxide which exists in a composition, and the silane converted into silica, 0.05-2.0 are suitable. If this ratio is less than 0.05, the conductivity of the conductive fine particles is inferior, and if it is 2.0 or more, the transparency of the film is inferior. The ratio of the weight of the conductive fine particles present in the composition and the sum of the zirconium dispersion stabilizer in terms of zirconium oxide and silane in terms of silica is preferably 0.5 to 5.0. If the ratio is less than 0.5, the conductivity of the film is lowered. If the ratio is larger than 5.0, the adhesion of the film is deteriorated. The solid content in the composition is preferably from 0.1 to 20% by weight. If the solid content is less than 0.1% and the conductivity of the film is poor and more than 20%, the storage stability of the solution is poor.

Composition 3

Composition 3 is prepared by adding metal alkoxide, metal alkoxyacetylacetonate or partial hydrolyzate thereof represented by formula (b) as a binder to composition 1. Partial condensates of metal alkoxides or metal alkoxyacetylacetonates were synthesized by partial hydrolysis at room or high temperature with controlled amounts of water. In terms of molar ratio of the amount of water used, 0.1 to 2.0 of the metal alkoxide or metal alkoxyacetylacetonate is suitable, and preferably 0.5 to 1.5. In the case of partial hydrolysis, a temperature of 0 to 200 ° C is suitable, and preferably 25 to 150 ° C. The weight ratio of the zirconium dispersion stabilizer and the conductive fine particles in terms of the metal oxide present in the composition is preferably 0.001 to 1. If the ratio is less than 0.001, the weight ratio of the conductive fine particles is precipitated, and if the ratio is larger than 1, the conductivity of the film is deteriorated.

In addition, the weight ratio of the zirconium dispersion stabilizer converted to the metal oxide and the binder converted to the metal oxide is preferably 0.001 to 10. If the ratio is less than 0.001, the transparency of the film is lowered and the chemical resistance is lowered when the ratio is larger than 10. The solid content in the composition is preferably from 0.1 to 20% by weight. If the solid content is less than 0.1%, the conductivity of the film is poor, and if it is more than 20%, the storage stability of the solution is poor.

Composition 4

Composition 4 is prepared by adding, as a binder, a partial hydrolyzate of silane or silane represented by formula (1) and a metal alkoxide, metal alkoxyacetylacetonate or their partial hydrolyzate represented by formula (2) as a binder. The ratio of the zirconium dispersion stabilizer, the conductive fine particles and the weight ratio in terms of the metal oxide present in the composition is preferably 0.001 to 1. If this ratio is less than 0.001, precipitation of conductive fine particles occurs, and if it is greater than 1, the conductivity of the film is deteriorated. In addition, the weight ratio of the zirconium dispersion stabilizer in terms of metal oxide and the binder in terms of metal oxide is preferably 0.001 to 10. If the ratio is less than 0.001, the transparency of the film is lowered and the chemical resistance is lowered when the ratio is larger than 10.

The proportion of the metal alkoxide, metal alkoxy acetylacetonate, or partial hydrolyzate binder thereof in the total weight of the binder converted into the metal oxide present in the composition is 0.001 to 0.99. The ratio of the sum of the conductive fine particles and the metal oxide binder and the zirconium dispersion stabilizer is 0.5 to 5, and if the ratio is less than 0.5, the conductivity of the film is poor. The solid content in the composition is preferably from 0.1 to 20% by weight. If the solid content is less than 0.1%, the conductivity of the film is poor, and if it is more than 20%, the storage stability of the solution is poor.

Composition 5

Composition 5 is a mixed solution in which silica is added to compositions 1 to 4 in order to increase the matting effect of the coating. The silica is dispersed in an alcoholic solvent and has a colloidal sol (MA-ST-M) having an average particle size of 60 nm or an aqueous solution of Nissan Chemical Co., Japan having an average particle size of 40 nm. Colloidal sol (ST-033) is used. The weight of the silica colloid in the solids material in the solvent is suitably not more than 50% of the total solids weight. If the weight of the silica gel is more than 50% of the total weight of the solid, the transparency of the film is deteriorated and wear resistance, chemical resistance, durability and adhesion to the substrate are poor. The weight ratio of the conductive fine particles and other metal oxides is suitably 1 to 5, and if the ratio is less than 1, the conductivity of the coating is lowered. If the ratio is larger than 5, the wear resistance, chemical resistance, durability, and adhesion to the substrate are poor. The solid content in the composition is preferably from 0.1 to 20% by weight. If the solid content is less than 0.1%, the conductivity of the film is poor, and if it is more than 20%, the storage stability of the solution is poor.

Film properties

The transparent conductive film-forming composition prepared as described above is coated on a substrate by a general wet coating method such as dip coating, spin coating, and spray coating, and dried at room temperature. A film can be formed by hardening at the temperature more than degreeC. The film thus prepared has a surface resistance of 10 ³ to 10 ¹¹ Ω / □ depending on the kind of conductive fine particles and the thickness of the film, and has a pencil strength of 3H to 8H and excellent water resistance and chemical resistance. The present invention is described in more detail through the following examples, but is not limited to these examples only, and the scope thereof is defined by the claims.

<Manufacture example 1>

Conductive fine particles: 15% solids in methanol in a sol form of water-dispersed ATO (17.2% solids) manufactured by Mitsubishi Metal, Japan, 15.3% solids dispersed in methanol, and AZO (30% solids) manufactured by Nissan Chemical Co., Ltd. It was diluted with and used as conductive fine particles.

<Manufacture example 2>

ZA-M: Zr ₄ O (OPr ⁿ ) ₁₀ (acac) ₄ was synthesized according to CR Academ, Sci, Paris, pp. 311, page 1161 (1990), and used in a solvent of 3% solids in methanol.

<Manufacture example 3>

ZB-M: Zr ₁₀ O ₆ (OH) ₄ (OPr ⁿ ) ₁₈ (AA) ₆ was converted into Mater. Res. Soc. Symp. Proc., Vol. 3, p. 272 (1992) was used to dissolve in solid solvent with 3% solids.

<Manufacture example 4>

ZC-M: Zr (OBU) 4 and acetyl acetone were reacted in a molar ratio of 1: 4 to obtain a tetrakisacetylacetonato zirconium compound, which was then hydrolyzed by reacting with 3 equivalents of water in a methanol solvent, and again 3% solids. Diluted with methanol and used.

Production Example 5

Silane: After diluting tetramethoxy silane in methanol with 5% solids, water was added by 2 equivalents of tetramethoxy silane, adjusted to pH = 2 using nitric acid, and then boiled for 2 hours to complete the silane binder solution.

<Manufacture example 6>

Zn-M: A bisacetylacetonato zinc compound manufactured by Aldrich, USA was purchased, and 1 equivalent of water was added in methanol solvent, hydrolyzed at 60 ° C., and diluted with methanol to 3% solids.

<Manufacture example 7>

Silica: Silicazol MA-ST-M manufactured by Nissan Chemical Co., Ltd., Japan, was diluted to 5% solids in methanol, and passed through a filter having a pore size of 0.5 to remove particles of excessive size.

<Manufacture example 8-16>

Each component was mixed at a composition ratio as shown in Table 1 and Table 2, followed by stirring for 1 hour to prepare a composition for forming a transparent conductive film.

<Production Comparative Example 1>

BZ-M: Zr (OBU) 4 and acetyl acetone were reacted in a molar ratio of 1: 2 to obtain a dibutoxybisacetylacetonato zirconium compound, which was then diluted with methanol to a solid content of 3%.

<Production Comparative Example 2>

TZ-M: Zr (OBU) 4 and acetyl acetone were reacted in a molar ratio of 1: 4 to obtain a tetrakisacetalacetonato zirconium compound, which was diluted with methanol to a solid content of 3% and used.

<Production Comparative Examples 3 to 10>

Each component was mixed at a composition ratio as shown in Table 2 and then stirred for 1 hour to prepare a composition for forming a transparent conductive film.

10 cc each of the compositions prepared according to the composition ratios of Preparation Examples and Comparative Examples were applied by a spin method on 10 cm × 10 cm glass specimens whose surface temperature was preheated to 40 ° C., and then baked in a 180 ° C. oven for 30 minutes.

The storage stability of the solution prepared as described above was determined by whether the solution precipitated and whether the surface resistance value of the obtained transparent conductive film increased. The surface resistance obtained using the solution prepared as described above was measured by applying an applied voltage of 500 volts and 10 volts for 10 seconds using Hiresta and Loresta manufactured by Mitsubishi Chemical Corporation, Japan. The reflectivity of the transparent conductive film was measured by using BYK Gardner's micro-TRI-gloss, and the transparency was measured by using haze meter to measure the transmittance and blur. The film strength was determined by the pencil hardness measurement method shown in ASTM D3363, and the adhesion of the film was determined by the tape test method shown in ASTM D3359.

The durability of the film was determined by measuring the change in conductivity, adhesion, transparency, reflectance, and pencil hardness of the film after the following method.

○: less than 10% of the initial physical properties, △: less than 20% of the initial physical properties, ×: 20% or more of the initial physical properties.

Alkali resistance: 120 deposits in 15% by weight aqueous ammonia solution.

Salt water resistance: 120 hours immersion in 10 wt% brine solution.

Hot water resistance: Soak for 30 minutes in boiling water.

Solvent resistance: Soak for 1 week in acetone, ethanol, normal propanol at room temperature.

The physical properties of the film prepared by the above method are shown in Tables 3 and 4.

TABLE 1

TABLE 2

TABLE 3

TABLE 4

Claims (8)

In the composition for forming a conductive film, a) antimony doped tin oxide (ATO), indium doped tin oxide (ITO), antimony 5 containing particles of this doped zinc oxide (AZO) alone or in combination Conductivity with a particle distribution of from 400 nm and an average particle diameter of 80 nm or less Fine particles; And b) structurally stable zirconium eggs represented by the following general formula (2) or (3) The coxide, zirconium alkoxy acetyl acetonate alone or under mixing Dispersion stabilizer Zr ₄ O (OPr ⁿ ) ₁₀ (acac) (2) ₄ (2) Zr ₁₀ O ₆ (OH) ₄ (OPr ⁿ ) ₁₈ (AA) (3) ₆ (3) Where Dr ⁿ is the normal profile, acac is an acetyl acetonate ligand, AA is an arylacetonate ligand) Composition comprising a. The method of claim 1, A composition further comprising a binder containing an organosilicon compound represented by the general formula (1), a partial hydrolyzate thereof and a metal alkoxide represented by the general formula (4), a metal alkoxyacetylacetonate or a partial hydrolyzate thereof. The method of claim 1, A composition further comprising a binder containing a metal alkoxide, metal alkoxyacetylacetonate represented by the general formula (4) or a partial hydrolyzate thereof.

The method of claim 1, A composition further comprising a binder containing a metal alkoxide, metal alkoxyacetylacetonate represented by the general formula (5) or a partial hydrolyzate thereof.

The method of claim 1, The composition further comprises a binder containing silane.

The composition of claim 1 further comprising colloidal silica. On the conductive substrate, a) antimony doped tin oxide (ATO), indium doped tin oxide (ITO), antimony 5 containing particles of this doped zinc oxide (AZO) alone or in combination Conductivity with a particle distribution of from 400 nm and an average particle diameter of 80 nm or less Fine particles; And b) structurally stable zirconium eggs represented by the following general formula (2) or (3) The coxide, zirconium alkoxy acetyl acetonate alone or under mixing Dispersion stabilizer Zr ₄ O (OPr ⁿ ) ₁₀ (acac) (2) ₄ (2) Zr ₁₀ O ₆ (OH) ₄ (OPr ⁿ ) ₁₈ (AA) (3) ₆ (3) An imaging device panel having a conductive coating coated with a composition. The method of claim 7, wherein An imaging device panel characterized by having a surface conductivity of 10 ³ to 10 ¹⁵ Ω / □ and a haze of 3% or less.

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