KR20010051016A - Composition for transparent conductive layer and display device having transparent conductive layer formed therefrom - Google Patents

Abstract

The present invention provides a composition for forming a transparent conductive film and a display device having a transparent conductive film formed therefrom. The composition for forming a transparent conductive film is to form a transparent conductive film obtained by sequentially stacking a first layer and a second layer, and the first layer forming composition includes metal (M) fine particles and a solvent for dispersing it. Wherein the composition for forming the second layer contains silicon alkoxide Si (OR) ₄ (where R is an alkyl group having 1 to 4 carbon atoms) and a solvent and / or the metal (M) fine particles and the metal (M) fine particles It characterized in that it comprises one selected from metal salts. However, the metal fine particles are silver (Ag), gold (Au), copper (Cu), aluminum (Al), platinum (Pt), nickel (Ni), lead (Pb), cobalt (Co), rhodium (Rh) And ruthenium (Ru), tin (Sn), iridium (Ir), palladium (Pd) and titanium (Ti). The transparent conductive film formed by using the composition for forming a transparent conductive film of the present invention has a low surface resistance value. Therefore, if the transparent conductive film is formed on the cathode ray tube glass panel, the electromagnetic wave shielding effect is excellent by the coating of the conductive film without any additional measures such as supplementation of the circuit, and the light spot phenomenon does not appear, thus providing high quality film quality and image quality. Can be. In addition, when the transparent conductive film is formed on the optical filter support substrate of the plasma display device, it is possible to prevent external light reflection, improve contrast, prevent static electricity, and shield the electron shield without using a large-area filter film without sputtering, chemical vapor deposition, or the like. Excellent optical filters can be manufactured in large quantities.

Description

A composition for forming a transparent conductive film and a display device having a transparent conductive film formed therefrom {Composition for transparent conductive layer and display device having transparent conductive layer formed therefrom}

The present invention relates to a composition for forming a transparent conductive film and a display device having a transparent conductive film formed therefrom. More particularly, the present invention relates to a display device having excellent conductivity and no light spot generation, and to preventing external light reflection, improving contrast, preventing static electricity, and shielding electromagnetic waves. The present invention relates to a composition for forming a transparent conductive film for the purpose and a display device having a transparent conductive film formed therefrom.

Cathode ray tube drives the image using the phenomenon that the electron beam from the electron gun collides with the phosphor on the inner surface of the cathode ray tube, and when the surface of the cathode ray tube is charged by the electrons emitted from the electron gun, it causes shock when the human body is touched. Dust particles easily adhere to the surface. In addition, the reflection of external light on the surface of the cathode ray tube causes the viewer to experience visual discomfort or adversely affect image quality. In order to overcome this problem, a transparent conductive film is formed on the surface of the cathode ray tube panel using a conductive material. Here, as the conductive material, a metal oxide such as tin-doped indium tin oxide (ITO), antimony tin oxide (ATO), zinc tin oxide (ZTO), or a conductive polymer is used. do.

Recently, according to the trend of planarization of cathode ray tube, a transparent-tint panel or a semi-tint panel with a transmittance of about 80% is preferred as a glass panel. A method of lowering to a predetermined value range has emerged. In this case, a carbon material such as carbon black is generally used as the transparent conductive film forming material.

However, when the transparent conductive film is formed using a metal oxide, a conductive polymer, a carbon material, or the like as described above, since the conductivity of the coating film is not low enough to meet the electromagnetic shielding standard according to the TCO standard, the panel surface treatment of the cathode ray tube This alone is limited and requires additional processing, such as circuit enhancement.

A method of using metal fine particles as a conductive material which can be preferably used has been proposed. By the way, the transparent conductive film containing these metal microparticles | fine-particles will have a remarkably high reflectance even if the thickness of a coating film is a little thick by the characteristic of the raw material itself. Therefore, when the thickness of the coating film is formed as thin as possible, there is a problem in that a portion in which the metal fine particles are not applied during coating is generated and light is emitted to the outside through the uncoated portion so that light spots such as the milky way appear. This light spot generation phenomenon results in deterioration of image quality.

On the other hand, the plasma display device is for displaying an image by using a gas discharge phenomenon, and has been spotlighted as a display device that can replace a cathode ray tube with excellent display capability such as display capacity, brightness, contrast, afterimage, and viewing angle. have. Such a plasma display device is discharged from a gas between the electrodes by a direct current or an alternating voltage applied to the electrode, and excites the phosphor by the radiation of ultraviolet rays accompanying the light, thereby emitting light.

In the plasma display device, the current in the driving circuit and the alternating current (AC) electrode and the high voltage for the plasma discharge are the main causes of the electromagnetic wave generation. The frequency range of these main electromagnetic waves is 30-200 MHz, and a transparent conductive thin film or a conductive mesh is mainly used as a filter for blocking such electromagnetic waves while maintaining high transmittance and low reflectance characteristics. In this case, a conductive film made by sputtering silver, copper, or ITO is mainly used as the transparent conductive thin film, and as the conductive mesh, a special resin treatment is performed after electroless plating of metals such as copper, copper and nickel on a mesh fabric such as polyester. A fine conductive mesh or a fine metal mesh formed by a photolithography process is mainly used.

However, in the case of using the above-described conductive mesh, it is possible to deposit a metal material thickly and increase the electromagnetic shielding efficiency, but the transmittance is lowered by partially covering the display light emitting part, and the image quality is deteriorated due to the moiré phenomenon and the manufacturing cost is increased. There is a high disadvantage. When the above-mentioned transparent conductive thin film is used, the transmittance is excellent, but there is a problem in that the manufacturing cost is increased due to the need for additional expensive equipment because sputtering or chemical vapor deposition is used in forming the thin film.

The technical problem to be achieved by the present invention is to provide a composition for forming a transparent conductive film for the purpose of solving the above problems, excellent conductivity and no light spot generation phenomenon, anti-reflective light, contrast enhancement, anti-static and electromagnetic shielding purposes.

Another object of the present invention is achieved by a display device having a transparent conductive film formed from the composition for forming a transparent conductive film.

1 is a cross-sectional view of a transparent conductive film according to an embodiment of the present invention.

<Explanation of symbols for main parts of drawing>

10 ... substrate 20 ... first layer

30 ... 2nd floor 40 ... 3rd floor

21, 31 ... metal particulate 32 ... hydrolyzate of silicon alkoxide

In order to achieve the above technical problem, in the present invention, as a composition for forming a transparent conductive film in which the first layer and the second layer are sequentially laminated,

The first layer-forming composition comprises a metal (M) fine particles and a solvent for dispersing it,

The second layer-forming composition comprises a silicon alkoxide Si (OR) ₄ (where R is an alkyl group having 1 to 4 carbon atoms) and a solvent and / or a metal salt containing the metal (M) fine particles and the metal (M) fine particles A composition for forming a transparent conductive film, characterized in that it comprises one selected from (However, the fine metal particles are silver (Ag), gold (Au), copper (Cu), aluminum (Al), platinum (Pt), nickel ( At least one selected from the group consisting of Ni, lead (Pb), cobalt (Co), rhodium (Rh), ruthenium (Ru), tin (Sn), iridium (Ir), palladium (Pd), and titanium (Ti) Is provided).

The average particle diameter of the metal fine particles is 5 to 120nm, the content of the metal fine particles in the composition for forming the first layer is 0.1 to 1.5 parts by weight based on 100 parts by weight of the total weight of the composition, the metal fine particles in the composition for forming the second layer The content of is preferably 0.005 to 0.5 parts by weight based on 100 parts by weight of the total weight of the composition. In addition, a third layer may be formed on the second layer to protect them, and the composition for forming the third layer may include silicon alkoxide Si (OR) ₄ , provided that R is an alkyl group having 1 to 4 carbon atoms. And one selected from a solvent and / or metal (M) fine particles and a metal salt containing the metal (M) fine particles. At this time, the average particle diameter of the metal (M) fine particles is 5 to 120nm, the content thereof is 0.005 to 0.5 parts by weight based on 100 parts by weight of the total weight of the composition for third formation.

On the other hand, the composition for forming the second layer further includes a catalyst for assisting hydrolysis of the silicon alkoxide, wherein the catalyst is used at least one selected from the group consisting of hydrochloric acid and nitric acid.

Another technical problem of the present invention is a first layer comprising metal fine particles by applying a composition for forming a first layer comprising metal (M) fine particles and a solvent for dispersing it; And

A silicon alkoxide Si (OR) ₄ (wherein R is an alkyl group having 1 to 4 carbon atoms) and a solvent and / or a metal salt containing the metal (M) fine particles and the metal (M) fine particles above the first layer A second conductive layer comprising a hydrolyzate of silicon alkoxide and / or metal fine particles by applying a composition for forming a second layer comprising one; a display element comprising a transparent conductive film formed by sequentially laminating However, the metal fine particles are silver (Ag), gold (Au), copper (Cu), aluminum (Al), platinum (Pt), nickel (Ni), lead (Pb), cobalt (Co), rhodium (Rh) , Ruthenium (Ru), tin (Sn), iridium (Ir), palladium (Pd) and titanium (Ti).

The third layer including the hydrolyzate of the silicon alkoxide and the metal fine particles may be formed by spray coating a composition for forming a third layer including the silicon alkoxide and the solvent and / or metal (M) fine particles on the second layer. have.

The transparent conductive film is particularly formed on the surface of the glass panel of the cathode ray tube or on the surface of the filter support substrate of the plasma display device.

The present invention provides a transparent conductive film having improved characteristics such as conductivity and electron shielding of a display device, wherein a dispersion of metal fine particles is applied to form a first layer including metal fine particles, and a silicon alkoxide and / or first layer thereon. It is characterized by using a coating film having a second layer containing a hydrolyzate of silicon alkoxide and / or metal fine particles by applying a coating liquid containing the same metal fine particles or salts thereof as used in formation. Here, it is also possible to further form a third layer containing the hydrolyzate of silicon alkoxide and / or the same metal fine particles as used in the first layer and the second layer on the second layer. At this time, the second layer serves to maintain the overall film strength of the transparent conductive film, and the third layer serves to protect the lower layer.

When the second layer and / or the third layer contains metal fine particles, the metal fine particles in the first layer cover the uncoated portion to prevent the occurrence of light spots, and in conjunction with the metal fine particles in the conductive layer. By lowering the contact resistance between the fine particles it serves to significantly reduce the surface resistance of the transparent conductive film itself.

Referring to each component constituting the composition for forming a transparent conductive film according to the present invention.

The composition for transparent conductive film formation of this invention mixes the composition for 1st layer formation and the composition for 2nd layer formation. In the case where the third layer is further formed on the second layer, the composition for forming the third layer is also mixed with the composition for forming the first layer and the second layer.

The composition for forming the first layer is prepared by mixing metal (M) fine particles and a solvent for dispersing it. At this time, the metal fine particles are silver (Ag), gold (Au), copper (Cu), aluminum (Al), platinum (Pt), nickel (Ni), lead (Pb), cobalt (Co), rhodium (Rh), At least one selected from the group consisting of ruthenium (Ru), tin (Sn), iridium (Ir), palladium (Pd) and titanium (Ti) is used. Of these, metal (M) fine particles are preferably not easily oxidized and stable silver (Ag), gold (Au), or platinum (Pt), and particularly silver (Ag) / gold (Au) alloys having excellent light transmittance lowering effects. Or silver (Ag) / palladium (Pd) alloy is more preferable. The particle diameter of the metal fine particles is more preferably 5 to 120 nm. If the particle diameter of the metal fine particles is less than 5 nm, the conductivity is lowered. If the particle size exceeds 120 nm, the film may become turbid, which is not preferable.

The content of the metal fine particles may be controlled in an arbitrary range according to the transmittance of the substrate itself coated with the composition, the surface resistance value of the desired transparent conductive film, etc., in particular 0.1 based on 100 parts by weight of the total weight of the first layer-forming composition It is preferably from 1.5 parts by weight. If the content of the metal fine particles is less than 0.1 part by weight, the contrast and the conductive properties are lowered, and if it exceeds 1.5 parts by weight, the transmittance is too low, which is not preferable.

As a solvent for dispersing the fine metal particles, alcohol solvents such as methanol, butanol, ethanol, methyl cellosolve, and the like, water or a mixed solvent thereof are used. And the content of this solvent is preferably 98.5 to 99.9 parts by weight based on 100 parts by weight of the total weight of the first layer-forming composition.

The composition for forming a second layer of the present invention contains silicon alkoxide Si (OR) ₄ (where R is an alkyl group having 1 to 4 carbon atoms), a solvent and / or the metal (M) fine particles and the metal (M) fine particles It is prepared by mixing one or more selected from metal salts. In this case, the same metal fine particles as those of the metal fine particles of the first layer-forming composition are used.

As the metal salt containing the metal fine particles, chlorides, nitrates, sulfonates and the like of the corresponding metals are used. The content of the metal fine particles is 0.005 to 0.5 parts by weight based on 100 parts by weight of the total weight of the composition for forming the second layer. If the content of the metal fine particles or salts thereof is more than 0.5 parts by weight, the film may become cloudy and less than 0.005 parts by weight, which is not preferable because the conductivity is lowered.

Specific examples of the silicon alkoxide include tetraethyl orthosilicate (ES28), methyl silicate oligomer (MS51) and the like, and the content thereof is 1.0 to 10.0 parts by weight based on 100 parts by weight of the total weight of the composition for forming a second layer. . At this time, if the silicon alkoxide content is less than 1.0 part by weight, the film is weak and easily scratched. If the silicon alkoxide content is more than 10.0 parts by weight, it is difficult to form the film or the film may crack during heat treatment. There is a problem that the efficiency is poor. As a solvent for dissolving this silicon alkoxide, ethanol, methanol, butanol, water, a mixture thereof and the like are used. The content of this solvent is 96 to 99 parts by weight based on 100 parts by weight of the total weight of the composition for forming the second layer.

In some cases, an acid catalyst such as hydrochloric acid, nitric acid, or the like is used as the material for promoting hydrolysis of the silicon alkoxide in the composition for forming the second layer. At this time, the content of the catalyst is a normal level.

The composition for forming a third layer is selected from silicon alkoxide Si (OR) ₄ (where R is an alkyl group having 1 to 4 carbon atoms) and a solvent and / or metal (M) fine particles and a metal salt containing the metal (M) fine particles. It is prepared by mixing one or more selected. In this case, the silicon alkoxide and the solvent may be used in the same kind and content as in the preparation of the composition for forming the second layer.

When the metal fine particles are added to the composition for forming a third layer, the kind and particle diameter thereof are the same as those used for producing the composition for forming the first layer and the second layer. And the content of the metal fine particles or salts thereof is 0.005 to 0.5 parts by weight based on 100 parts by weight of the third layer-forming composition. If the content of metal fine particles or salts thereof is less than 0.005 parts by weight, the effect of improving conductivity is insignificant, and if it exceeds 0.5 parts by weight, the film may become turbid, which is not preferable.

Hereinafter, a method of manufacturing a transparent conductive film using the composition for forming a transparent conductive film according to the present invention will be described in more detail.

First, metal (M) fine particles having a particle diameter of 5 to 120 nm are dispersed in a solvent to prepare a composition for forming a first layer.

Subsequently, the silicon alkoxide is dissolved in a solvent to prepare a composition for forming a second layer. In some cases, when preparing the composition for forming the second layer, a colloidal solution of metal (M) fine particles having a particle size of 5 to 120 nm or a salt thereof is added, and a catalyst for assisting hydrolysis of silicon alkoxide may be added.

The first layer-forming composition prepared as described above is applied onto a substrate, and then the second layer-forming composition is applied on the resultant. Subsequently, a transparent conductive film is obtained by heat-processing the said resultant at 150-300 degreeC. At this time, when the heat treatment temperature is less than 150 ° C, the film is not dense and easily scratched. When the heat treatment temperature exceeds 300 ° C, the film is deteriorated, which is not preferable.

In the process of manufacturing the transparent conductive film, it is also possible to separately or not perform the drying process after applying the composition for forming the first layer. The method of applying the composition for forming the first layer and the composition for forming the second layer is not particularly limited. It is preferable to use the spin doping method in the production method of the composition for forming the second layer, but since the stain may be formed on the coating film by the rotational air during the spin process of the large screen, in this case, dip coating, roll coating or capillary It is preferable to use a coating method using a head of the type.

On the other hand, after applying the composition for forming the second layer, it is also possible to form a third layer by spray coating the composition for forming the third layer. In the case of forming the third layer as described above, the heat treatment at 150 to 300 ° C. is performed after spray coating of the composition for forming the three layers.

Considering the various functions of the transparent conductive film such as antireflection, antifouling, control of transmittance, and improved conductivity, formation of the third layer may not be desirable, but it may improve surface texture and occur when forming the first and second layers. It is very useful in that it can compensate for the existing film defects.

The transparent conductive film obtained according to the manufacturing process as described above is 10 mW / ?, which is much smaller than 3000 mW /? That can achieve the TCO specification. The conductivity is very good inside and out. This is because the metal fine particles are much more excellent in conductivity than the metal oxide fine particles used as ordinary transparent conductive particles. In addition, the uncoated portion of the metal fine particles, which may be present in the first layer, is filled with the metal fine particles contained in the second layer and / or the third layer, thereby overcoming the light spot phenomenon which is usually pointed out as a problem in the conductive layer of the metal fine particles. can do.

The transparent conductive film prepared according to the present invention is applicable to various display devices. In particular, when applied to the glass panel of the cathode ray tube, it can be used as a conductive film having antistatic and electromagnetic shielding functions, and when applied to an optical filter support substrate of a plasma display device, it can be used as a filter having an anti-reflection function and excellent electromagnetic shielding function. Can be. Here, a transparent substrate formed of a transparent material is used as the support substrate for the optical filter. Specific examples thereof include a glass substrate and an acrylic resin substrate. As a method of applying the composition for forming a transparent conductive film of the present invention to an optical filter support substrate of a plasma display device and then heat-treating it, a method of baking by heating or heating using light such as ultraviolet rays is used. As described above, when the composition for forming a transparent conductive film of the present invention is used to manufacture an optical filter of a plasma display device, the sputtering method, the chemical vapor deposition method, etc. are used by using a wet coating method using the composition for forming a transparent conductive film containing metal fine particles. In comparison, manufacturing costs are reduced and mass production is possible.

1 is a cross-sectional view showing a transparent conductive film in a preferred embodiment of the present invention.

Referring to FIG. 1, the first layer 20, the second layer 30, and the third layer 40 are sequentially stacked on the substrate 10. As the substrate 10, a glass panel of a cathode ray tube, an optical filter supporting substrate of a plasma display device, or the like is used. Clear tint panels or semi-tint panels are used as glass panels, and glass substrates and acrylic resin substrates are used as optical filter support substrates.

The first layer 20 is a layer coated with the metal fine particles 21 to provide conductivity. The second layer 30 includes the metal fine particles 31 and the hydrolyzate 32 of the silicon alkoxide as the protective layer of the first layer 20.

On the second layer 20, a third layer 40 made of a hydrolyzate of silicon alkoxide is formed.

Hereinafter, the present invention will be described in detail with reference to the following examples, but the present invention is not limited to the following examples.

<Example 1>

12 g of 2% Ag aqueous dispersion was mixed with 25 g of ethanol, 38 g of methanol, and 25 g of methyl cellosolve to prepare a coating solution for forming a first layer.

Subsequently, 0.1 g of silver nitrate and 3 g of tetraethylorthosilicate were mixed with 9.5 g of water, 24 g of methanol, 30 g of ethanol, and 33 g of butanol, and 0.5 g of nitric acid was added thereto, stirred at 60 ° C. for about 4 hours to form a coating solution for forming a second layer. Was prepared.

After the glass panel of the cathode ray tube was washed with hydrofluoric acid and water, the coating liquid for forming the first layer was poured on the glass panel, and the rotation speed of the panel was raised to about 150 rpm. Then, the coating solution for forming the second was spin-coated in the same manner as the coating solution for forming the first layer. Subsequently, the panel was dried and calcined at 200 ° C. for about 30 minutes to obtain a transparent conductive film of a cathode ray tube.

<Example 2>

A transparent conductive film was obtained according to the same method as in Example 1 except that the coating solution for forming a third layer was prepared as follows, and then spray-coated after spin coating the coating solution for forming a second layer.

A coating solution for forming a third layer was prepared by mixing 3.5 g of tetraethylorthosilicate with 10 g of water, 50 g of methanol, 30 g of ethanol, and 6.5 g of butanol.

<Comparative Example 1>

The first layer and the second layer forming coating liquid were prepared in the same manner as in Example 1 except that no silver nitrate was added at the time of preparing the coating liquid for forming the second layer, and then a transparent conductive film was formed therefrom.

<Comparative Example 2>

A coating liquid for forming a first layer and a second layer was prepared in the same manner as in Example 1, except that 12g of ITO fine particles having a particle size of about 80 nm instead of an Ag aqueous dispersion was used to obtain a transparent conductive film.

In the transparent conductive film of the cathode ray tube manufactured according to Example 1-2 and Comparative Example 1-2, the results of surface resistance and light spot development are shown in Table 1 below.

division Surface resistance (Ω /?) Light spot phenomenon Example 1 0.45 × 10 ³ Almost none Example 2 0.65 × 10 ³ Almost none Comparative Example 1 1.3 × 10 ³ Light spots appear in the form of Milky Way Comparative Example 2 7.5 × 10 ³ Almost none

From Table 1, it can be seen that the transparent conductive films according to Examples 1 and 2 have a significantly lower surface resistance value and almost no light spot phenomenon than those of Comparative Examples 1-2.

On the contrary, when the coating liquid for forming the second layer does not contain metal fine particles (Comparative Example 1), the surface resistance value is not only higher than that of the transparent conductive film according to Example 1, but also light spot phenomena in the form of the Milky Way appear. In the case of using the exclusive oxide fine particles (Comparative Example 2), there was no light spot phenomenon, but the surface resistance value was remarkably high, indicating poor electrical conductivity.

<Example 3>

4 g of a 5% Ag aqueous dispersion was mixed with 25 g of ethanol, 38 g of methanol, and 25 g of methyl cellosolve to prepare a coating solution for forming a first layer.

Subsequently, 0.15 g of silver nitrate and 3 g of tetraethylorthosilicate were mixed with 9.5 g of water, 24 g of methanol, 30 g of ethanol, and 33 g of butanol, and 0.5 g of nitric acid was added thereto and stirred at room temperature for about 24 hours to prepare a coating solution for forming a second layer. Prepared.

The first layer-forming coating liquid was applied onto a glass substrate and dried to form a first layer. Subsequently, the coating solution for forming the second layer was applied on the first layer, and then dried and baked at 200 ° C. for about 30 minutes to complete an optical filter for a plasma display device.

<Example 4>

An optical filter for a plasma display device was completed in the same manner as in Example 3, except that 0.3 g of silver nitrate was used instead of 0.15 g of nitric acid when preparing the coating solution for forming the second layer.

<Example 5>

The plasma display device was manufactured according to the same method as Example 3 except that 30 g of a 5% Ag aqueous dispersion was used in the preparation of the first layer forming coating and 0.4 g of nitrate was used in the preparation of the coating solution for forming the second layer. The optical filter was completed.

<Comparative Example 3>

An optical filter for a plasma display device was completed in the same manner as in Example 3 except that silver nitrate was not added to the coating liquid for forming the second layer.

In the optical filter for plasma display device manufactured according to Example 3-5 and Comparative Example 3, the surface resistance is measured and shown in Table 2 below.

division Surface resistance (Ω /?) Example 3 600 Example 4 300 Example 5 20 Comparative Example 3 10000

It can be seen that the optical filters manufactured according to Examples 3 to 5 from Table 2 have significantly reduced surface resistance compared to the case of Comparative Example 2, thereby improving conductivity.

The transparent conductive film formed by using the composition for forming a transparent conductive film of the present invention has a low surface resistance value. Therefore, when the transparent conductive film is formed on the cathode ray tube glass panel, the electromagnetic wave shielding effect is excellent only by coating the conductive film without any additional measures such as complementing the circuit. In addition, since the light spot phenomenon does not appear, it is possible to provide high quality film quality and image quality.

In addition, when the transparent conductive film is formed on the optical filter support substrate of the plasma display device, it is possible to prevent external light reflection, improve contrast, prevent static electricity, and shield the electron shield without using a large-area filter film without sputtering, chemical vapor deposition, or the like. Excellent optical filters can be manufactured in large quantities. In the case of manufacturing the optical filter by this method, the manufacturing cost can be significantly reduced as compared with the case of using the sputtering method, the chemical vapor deposition method and the like.

Although the present invention has been described with reference to the above embodiments, it is merely illustrative, and those skilled in the art will understand that various modifications and equivalent other embodiments are possible therefrom. . Therefore, the true technical protection scope of the present invention will be defined by the technical spirit of the appended claims.

Claims (11)

As a composition for forming the transparent conductive film which the 1st layer and the 2nd layer were laminated sequentially, The first layer-forming composition comprises a metal (M) fine particles and a solvent for dispersing it, The second layer-forming composition comprises a silicon alkoxide Si (OR) ₄ (where R is an alkyl group having 1 to 4 carbon atoms) and a solvent and / or a metal salt containing the metal (M) fine particles and the metal (M) fine particles A composition for forming a transparent conductive film, characterized in that it comprises one selected from (However, the fine metal particles are silver (Ag), gold (Au), copper (Cu), aluminum (Al), platinum (Pt), nickel ( At least one selected from the group consisting of Ni, lead (Pb), cobalt (Co), rhodium (Rh), ruthenium (Ru), tin (Sn), iridium (Ir), palladium (Pd), and titanium (Ti) to be). The method of claim 1, wherein the average particle diameter of the metal fine particles is 5 to 120nm, The content of the metal fine particles in the composition for forming the first layer is 0.1 to 1.5 parts by weight based on 100 parts by weight of the total weight of the composition, The content of the metal fine particles in the composition for forming the second layer is 0.005 to 0.5 parts by weight based on 100 parts by weight of the total weight of the composition. The method of claim 1, wherein the composition for forming a third layer on the second layer, The composition for forming a third layer is selected from silicon alkoxide Si (OR) ₄ (where R is an alkyl group having 1 to 4 carbon atoms) and a solvent and / or metal (M) fine particles and metal salts containing the metal (M) fine particles. Transparent conductive film-forming composition comprising a selected one. The method of claim 3, wherein the average particle diameter of the metal (M) fine particles is 5 to 120nm, The composition for forming a transparent conductive film, characterized in that the content is 0.005 to 0.5 parts by weight based on 100 parts by weight of the total weight of the composition for third formation. The composition for forming a transparent conductive film of claim 1, further comprising a catalyst for assisting hydrolysis of the silicon alkoxide in the composition for forming the second layer. The composition of claim 1, wherein the catalyst is at least one selected from the group consisting of hydrochloric acid and nitric acid. A first layer containing metal fine particles by applying a composition for forming a first layer comprising metal (M) fine particles and a solvent for dispersing it; And A silicon alkoxide Si (OR) ₄ (wherein R is an alkyl group having 1 to 4 carbon atoms) and a solvent and / or a metal salt containing the metal (M) fine particles and the metal (M) fine particles above the first layer A second conductive layer comprising a hydrolyzate of silicon alkoxide and / or metal fine particles by applying a composition for forming a second layer comprising one; a display element comprising a transparent conductive film formed by sequentially laminating However, the metal fine particles are silver (Ag), gold (Au), copper (Cu), aluminum (Al), platinum (Pt), nickel (Ni), lead (Pb), cobalt (Co), rhodium (Rh) And ruthenium (Ru), tin (Sn), iridium (Ir), palladium (Pd) and titanium (Ti). The method of claim 7, wherein the average particle diameter of the metal fine particles is 5 to 120nm, The content of the metal fine particles in the composition for forming the first layer is 0.1 to 1.5 parts by weight based on 100 parts by weight of the total weight of the composition, The content of the metal fine particles in the composition for forming the second layer is 0.005 to 0.5 parts by weight based on 100 parts by weight of the total weight of the composition. The method of claim 7, wherein the third layer-forming composition comprising silicon alkoxide and a solvent and / or metal (M) fine particles is spray-coated on the second layer to include a hydrolyzate of silicon alkoxide and metal fine particles. A display element characterized in that three layers are stacked. 10. The method of claim 9, wherein the average particle diameter of the metal (M) fine particles is 5 to 120nm, A content of the display element is 0.005 to 0.5 parts by weight based on 100 parts by weight of the total weight of the third forming composition. The display element according to any one of claims 7 to 10, wherein the transparent conductive film is formed on the surface of the glass panel of the cathode ray tube or on the surface of the filter support substrate of the plasma display device.