JP2010143802A - Silicon oxide gel film, transparent conductive film and substrate in which transparent conductive film is laid and method for producing those - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a transparent conductive film having high transmittance, high conductivity, surface flatness and excellent heat resistance and containing a network structure composed of metal fine particles, a substrate in which the transparent conductive film is laid, and to provide a method for producing the transparent conductive film. <P>SOLUTION: The transparent conductive film is based on a silicon oxide gel film obtained by firing by heating and contains a network structure composed of metal fine particles, wherein the metal fine particles are made of a metal selected from Au, Ag, Cu, Pt, Pd, Fe, Co, Ni, Al, In and Sn or an alloy containing two or more of the metals. The substrate in which the transparent conductive film is laid is also provided. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

The present invention provides a transparent conductive film, a transparent conductive film laminated substrate, and a manufacturing method thereof, in which an oxide film mainly composed of silicon oxide containing a network structure composed of metal fine particles is laminated.

  Transparent conductive films for electrodes such as display devices such as plasma displays and organic EL, input sensors such as touch panels, solar cells such as thin-film amorphous Si solar cells and dye-sensitized solar cells Is used.

In particular, thin films mainly composed of ITO (In and Sn oxides) and ZnO, which are transparent oxides, are mainly used and may be produced by a coating method of a fine particle dispersion solution. In order to obtain high conductivity, it is generally produced by a vapor phase method using a sputtering apparatus or a vapor deposition apparatus.

  On the other hand, instead of the continuous transparent conductive film by the vapor phase method as described above, the metal film is formed in a lattice shape or a mesh shape, the metal film portion is responsible for conductivity, and the pore portion is light transmissive. A transparent conductive film in a form to bear is disclosed. For example, an EMI shield film for plasma displays in which a Cu film is etched after being formed into a lattice after forming a continuous film of Cu film is actually employed, and a metal fine particle dispersion solution is applied or printed for the same purpose. Thus, a method of forming a conductive portion having a network structure and performing plating has been studied. Any of these methods does not require a vacuum apparatus necessary for the vapor phase method, and can improve conductivity while maintaining transparency as compared with a transparent oxide.

2. Description of the Related Art Conventionally, a transparent conductive film laminated substrate having a network structure by screen printing a metal fine particle paste on a substrate in a mesh shape and heating and firing is known (Patent Document 1). Also known is a method in which a W / O type emulsion is prepared from a metal fine particle dispersion solution, and the fine metal particles form a network structure by coating and drying on the substrate, thereby forming a transparent conductive film on the substrate. (Patent Documents 2 and 3).

JP 2007-227906 A JP 2005-530005 Gazette JP 2007-234299 A

Transparent conductive films and transparent conductive film laminated substrates composed of materials having high transmittance, high conductivity, flatness, and excellent heat resistance and weather resistance are currently most demanded. Although it is, it has not been obtained yet.

  That is, any of the above-described methods can obtain a transparent conductive film laminated substrate having high transmittance and high conductivity which are important as a transparent conductive film. Therefore, the upper surface of the transparent conductive film inevitably has a convex conductive portion, and the flatness is not sufficient. Therefore, when another functional thin film is laminated on the upper part, for example, when used for an electrode for organic EL or an electrode of a thin film type solar cell, there is a concern that the light emission efficiency and the power generation efficiency are lowered.

  In addition, when laminating functional thin films, there are many places where it is currently necessary to rely on a vapor phase process, and it is necessary to heat a substrate or a functional thin film laminated substrate before or after film formation. Sufficient heat resistance is required for the transparent conductive film laminated substrate.

  Furthermore, in transparent conductive film laminated substrates used in solar cells that require sufficient weather resistance and performance maintenance for long-term outdoor use, organic substances contained inside decompose and precipitate over time. Then, since there exists a possibility of causing the fall of electric power generation efficiency, the transparent conductive film comprised with the material stable for a long period of time is desired.

  Accordingly, the present invention provides a transparent conductive film and a transparent conductive film laminated substrate that are made of a material having high transmittance, high conductivity, improved flatness, and excellent heat resistance and weather resistance. And

  The technical problem can be achieved by the present invention as follows.

  That is, the present invention is a silicon oxide gel film containing a network structure composed of metal fine particles and containing polysilazane as a main component (Invention 1).

  Further, the present invention provides a metal fine particle of the silicon oxide gel body film, a metal selected from Au, Ag, Cu, Pt, Pd, Fe, Co, Ni, Al, In, Sn, or two or more of the above metals. It is a silicon oxide gel body film which is an alloy containing (Invention 2).

  Moreover, this invention is a silicon oxide gel body film | membrane produced | generated using the perhydro polysilazane for the polysilazane of a main component in the said silicon oxide gel body film | membrane (this invention 3).

  Further, the present invention is a transparent conductive film obtained by heating and / or humidifying the silicon oxide gel body film according to any one of the above, wherein the transparent conductive film is an oxide mainly composed of silicon oxide. A transparent conductive film characterized in that a network structure composed of metal fine particles is encapsulated therein (Invention 4).

  Moreover, this invention is a transparent conductive film laminated substrate which laminated | stacked the said transparent conductive film on the glass substrate (this invention 5).

  Further, in the present invention, after a network structure composed of the metal fine particles described above is formed on a substrate, a solution containing polysilazane as a main component is applied to the network structure, A method for producing a silicon oxide gel film, comprising drying to prepare a silicon oxide gel film (Invention 6).

  Further, in the present invention, after a network structure composed of the metal fine particles described above is formed on a substrate, a solution containing polysilazane as a main component is applied to the network structure, A method for producing a transparent conductive film, wherein the silicon oxide gel body film is dried and heated and / or humidified (Invention 7).

  Further, in the present invention, after a network structure composed of the metal fine particles described above is formed on a substrate, a solution containing polysilazane as a main component is applied to the network structure, After preparing a silicon oxide gel body film by drying, the silicon oxide gel body film is adhered to a glass substrate as an adhesive layer, and then the substrate is removed, followed by heating and / or humidification treatment. This is a method for producing a conductive film (Invention 8).

  The transparent conductive substrate in which the oxide film mainly composed of silicon oxide containing the network structure composed of the metal fine particles according to the present invention is laminated has high transmittance, high conductivity, and flatness of the surface. Can be used as a transparent conductive film laminated substrate such as an organic EL or a thin film solar cell.

  The configuration of the present invention will be described in detail according to the manufacturing process shown in FIG.

  First, a metal fine particle dispersion solution or ink containing metal fine particles is applied or printed on a substrate (10), and then a conductive portion having a network structure is formed by heating and / or chemical treatment ((( A)).

  Next, the solution (2) containing polysilazane as a main component is adjusted so that the oxide finally formed as a main component has a film thickness covering the conductive portion having the network structure. It is applied ((B) in FIG. 1). Thereafter, a silicon oxide gel body film (3) including a conductive portion having a network structure composed of fine metal particles is produced on a substrate ((C) in FIG. 1).

  Next, after applying the above-mentioned solution (2) containing polysilazane as a main component to the upper surface of the glass substrate (11) or the upper surface of the silicon oxide gel body film, the upper surface of the glass substrate and the upper surface of the silicon oxide gel body are made to face each other. The glass substrate and the silicon oxide gel body film are adhered to each other (FIG. 1D).

  A silicon oxide gel body film (3) including a conductive portion having a network structure composed of metal fine particles is adhered to a glass substrate ((E) of FIG. 1). After that, the substrate is removed ((F) in FIG. 1). Furthermore, the transparent conductive film laminated substrate (5) having a network structure composed of the metal fine particles of the present invention is obtained by performing heating and / or humidification treatment to convert the silicon oxide gel body film into vitrification. (G in FIG. 1).

  The method of adhering the silicon oxide gel body film containing a conductive portion having a network structure composed of metal fine particles and the glass substrate may be other than the method described above. For example, in the case of simultaneously generating a silicon oxide gel body film containing a conductive portion having a network structure composed of metal fine particles and adhering to a glass substrate, a mesh composed of metal fine particles on the substrate is used. After forming a conductive portion having a shape structure, facing a glass substrate, inserting a solution containing polysilazane as a main component between the substrate and the glass substrate, and then drying to produce a silicon oxide gel film The substrate may be removed.

  The transparent conductive substrate obtained by the above-described method has high conductivity due to the conductive part having a network structure composed of metal fine particles, and an oxide mainly composed of silicon oxide is a network of the conductive part. Since the structure is filled with a portion, the transparent conductive film laminated substrate is improved in flatness on the upper surface, has high transmittance, and is excellent in heat resistance and weather resistance.

  The metal fine particles of the conductive part having a network structure composed of metal fine particles may be a gas phase method such as a gas evaporation method or a liquid phase reduction method in which a metal salt is reduced in a solution, or a metal complex. It can be prepared using a method of preparing metal fine particles by thermal decomposition of

  Au, Ag, Cu, Pt, Pd, Fe, Co, Ni, Al, In, Sn, etc. can be used as the metal raw material for the metal fine particles. Alternatively, an alloy containing two or more kinds of the metals may be used. In recent years, it is more preferable to use Au, Ag, Cu, Pt, Pd, or an alloy containing two or more kinds of Au, Ag, Cu, Pt, Pd, which has been used for forming fine wiring in electronic circuits.

  The metal fine particles are prepared in a dispersion solution or printing ink and applied or printed on the substrate. Therefore, the surface of the metal fine particles is preferably treated with an appropriate surface treatment agent or dispersant. As the surface treating agent or dispersing agent, it is preferable to use a surface treating agent or dispersing agent that is optimally dispersed in each dispersion solution or each printing ink.

The substrate (10) for applying or printing the metal fine particle dispersion solution or the printing ink containing the metal fine particles has chemical resistance to the solution containing polysilazane as a main component, and has a mesh shape with the metal fine particle dispersion solution or the printing ink containing the metal fine particles. It is necessary to have chemical resistance and heat resistance that can withstand the formation of a conductive portion having a structure. As the substrate meeting the above conditions, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, polyimide resins, polyamide resins and the like are preferable.
Moreover, after forming a silicon oxide gel body film from polysilazane, the substrate surface may be coated with a coating that weakens the affinity with silicon oxide so that the substrate can be easily peeled off.

  Next, when forming a conductive portion having a network structure composed of metal fine particles, a method of applying a metal fine particle dispersion solution described in Patent Document 2 or a screen printing of a metal fine particle dispersed ink described in Patent Document 1 You may use the method to do.

  After forming a conductive portion having a network structure composed of metal fine particles, it is preferable to perform heating and / or chemical treatment within a range that the substrate can withstand for the purpose of improving conductivity.

  The thickness of the conductive portion having a network structure composed of metal fine particles is preferably 0.4 μm or more. When it is thinner than 0.4 μm, sufficient conductivity cannot be obtained. The upper limit film thickness is preferably 10 μm. This is because when the thickness exceeds 10 μm, the line width of the net portion tends to be widened at the same time, resulting in a decrease in transmittance.

  Next, a solution containing polysilazane as a main component is applied so as to enclose a conductive portion having a network structure composed of metal fine particles ((B) of FIG. 1).

Polysilazane is a linear or cyclic compound having a silazane bond represented by —SiR ¹ ₂ —NR ² —SiR ¹ ₂ — (wherein R ¹ and R ² each independently represents a hydrogen atom or a hydrocarbon group). is a generic term, ^Si-NR 2 -Si bond by reaction with heating or water is a material that form Si-O-Si network by decomposition.
In the present invention, perhydropolysilazane in which R ¹ and R ² in the above general formula are hydrogen, or partially organicized polysilazane in which R ² is a methyl group is preferably used.

The solution prepared with polysilazane as a main component may contain a metal fine particle catalyst (such as Pd) or an amine catalyst in order to improve the reactivity of the silazane bond of polysilazane.
Alternatively, an organic titanium compound may be included for the purpose of preventing cracks in silicon oxide when vitrifying. For example, as an organic titanium compound described in JP-A-2006-265344, there are a tetraalkoxytitanium compound, a titanium chelate compound, a titanium acylate compound, a titanate coupling agent, and the like.

JP 2006-265344 A

  The content of polysilazane in the solution containing polysilazane as a main component is preferably 40 wt% or less. More preferably, it is 20 wt% or less. If it is thicker than 40 wt%, it is not preferable because the viscosity increases when it is applied or there is a problem in storage stability. The lower limit of the concentration is not particularly limited, but if it is 1 wt% or less, it is not preferable because the productivity is poor because it is necessary to repeatedly apply the coating several times in order to obtain a desired thickness.

The solvent used in the solution containing polysilazane as a main component is not particularly limited as long as it dissolves polysilazane and does not react rapidly with polysilazane. Specific examples include aliphatic hydrocarbons, aromatic hydrocarbons, ketones, esters, ethers, and halogenated hydrocarbons. These solvents may be used alone or in combination.
In view of the solubility of polysilazane and low reactivity with polysilazane, aliphatic hydrocarbons such as octane, nonane, decane, undecane, dodecane, tridecane and tetradecane, and aromatic hydrocarbons such as benzene, toluene and xylene are preferred.

The method for applying a solution containing polysilazane as a main component is not particularly limited. For example, dip coating, spin coating, spray coating, flexographic printing, screen printing, gravure printing, roll coating, meniscus coating And die coating method.

In the case of applying the above-described solution containing polysilazane as a main component, it is preferable that the silicon oxide gel film be prepared so as to have a film thickness sufficient to cover the network structure composed of the metal fine particles. Although the thickness varies depending on the film thickness of the network structure composed of metal fine particles, it is preferably prepared to be 0.5 μm to 10 μm. If the thickness is 0.5 μm or less, the conductive part cannot be sufficiently covered, and if it is 10 μm or more, cracks and voids are generated in the process of further vitrification by heating and / or humidifying the silicon oxide gel body film. It is easy to generate and is not preferable. Cracks and voids are not preferable because they cause a decrease in transmittance.

In order to obtain a desired thickness of the silicon oxide gel body film, the number of times of coating may be divided into several times. Alternatively, the coating thickness may be changed each time coating is performed.

After applying a solution containing polysilazane as a main component, the coating film is dried at 200 ° C. or lower. The drying time is preferably about 30 seconds to 2 hours. By this drying step, a part of the silazane bond of polysilazane reacts to produce a silicon oxide gel film containing a network structure composed of metal fine particles ((C) in FIG. 1).
It is preferable to select optimum conditions for the drying temperature and drying time depending on the concentration of the solution containing polysilazane as a main component, the type of catalyst, and the like.

Next, a solution containing polysilazane as a main component is applied to the upper surface of the glass substrate or the surface of the silicon oxide gel body film described above, and then dried to form a silicon oxide gel. It is made to adhere ((D) of FIG. 1).
The film thickness of the silicon oxide gel, which is the adhesive layer, is not particularly limited, but may be appropriately selected so that sufficient adhesion can be obtained between the silicon oxide gel body film containing the network structure composed of metal fine particles and the glass substrate. It ’s fine.
Preferably it is 10 micrometers or less. More preferably, it is 5 micrometers or less, More preferably, it is 1 micrometer or less. When it is thicker than 10 μm, there is a high possibility of cracks and voids when vitrified, which is not preferable.

A transparent conductive film substrate in which a silicon oxide gel film containing a network structure composed of metal fine particles is laminated on a glass substrate by removing the substrate (10) after confirming that it is sufficiently adhered Can be obtained.

Next, the glass substrate on which the silicon oxide gel body film has been laminated at 100 to 500 ° C. in the atmosphere is vitrified by heating for 10 minutes to 24 hours to oxidize the network structure composed of metal fine particles. A transparent conductive film laminated substrate (5) in which silicon gel is laminated on a glass substrate can be obtained ((G) in FIG. 1).

Alternatively, the glass substrate on which the silicon oxide gel body film is laminated at room temperature in the atmosphere is vitrified by standing for 1 to 4 weeks, and the silicon oxide containing the network structure composed of metal fine particles is glass. A transparent conductive film laminated substrate laminated on the substrate can be obtained.

  When heating at 100 ° C. or lower in the air, it is preferable to humidify. By humidifying, the reaction of the silazane bond is promoted, and the standing time for vitrification can be shortened.

    The surface resistance value in the transparent conductive laminated substrate according to the present invention is preferably 100Ω / □ or less, more preferably 50Ω / □ or less, and still more preferably 20Ω / □ or less. When it is 100Ω / □ or more, it is difficult to say that it is a highly conductive film, which is not preferable.

  The centerline surface roughness (Ra) in the transparent conductive laminated substrate according to the present invention is preferably 1.0 μm or less, more preferably 0.2 μm or less, and even more preferably 0.1 μm or less. When the thickness is 1.0 μm or more, the function is lowered when a functional thin film is laminated, which is not preferable.

  The total light transmittance in the transparent conductive laminated substrate according to the present invention is preferably 60% or more, more preferably 70% or more, and still more preferably 80% or more. If it is 60% or less, it is difficult to say that it is highly transparent, which is not preferable.

  A typical embodiment of the present invention is as follows.

  The thickness of the silicon oxide gel body film of the transparent conductive film can be determined by masking the substrate (using a polyimide masking tape) and forming the silicon oxide gel body film, and then removing the masking tape. Was measured with a stylus type surface roughness meter (manufactured by DEKTAK) and measured as the film thickness of the silicon oxide gel body film.

    For the surface roughness of the transparent conductive film laminated substrate, the centerline surface roughness (Ra) was measured using a stylus type surface roughness meter (manufactured by DEKTAK).

    For the surface resistance, three points of the sample were measured using MCP-T600 (manufactured by Mitsubishi Chemical Corporation), and the average value was defined as the surface resistance value.

    The total light transmittance was measured at three points using the haze meter NDH2000 (manufactured by Nippon Denshoku Industries Co., Ltd.), and the average value was defined as the transmittance.

<Preparation method of silver fine particles 1>
40 g of silver nitrate, 37.9 g of butylamine, and 200 mL of methanol were added and stirred for 1 hour to prepare solution A. Separately, 62.2 g of isoascorbic acid was taken, 400 mL of water was added and dissolved by stirring, and then 200 mL of methanol was added to prepare solution B. B liquid was stirred well and A liquid was dripped at B liquid over 1 hour and 20 minutes. After completion of the dropwise addition, stirring was continued for 3 hours and 30 minutes. After completion of stirring, the mixture was allowed to stand for 30 minutes to precipitate the solid. After removing the supernatant by decantation, 500 mL of water was newly added, and the supernatant was removed by stirring, standing, and decantation. This purification operation was repeated three times. The settled solid was dried in a dryer at 40 ° C. to remove moisture. Further, 20 g of the obtained silver fine particles and 0.2 g of Disperbyk-106 (manufactured by Big Chemie Japan) were mixed in a mixed solution of 100 mL of methanol and 5 mL of pure water, mixed for 1 hour, and then 100 mL of pure water was added, After filtering the slurry, the slurry was dried in a dryer at 40 ° C. to obtain silver fine particles 1. Silver fine particles 1 had an average primary particle diameter of 60 nm as observed with an electron microscope.

<Preparation method of silver fine particle dispersion solution 2>
4 g of silver fine particles 1, 30 g of toluene and 0.2 g of BYK-410 (manufactured by Big Chemie Japan) are mixed, dispersed for 1.5 minutes with an ultrasonic disperser with an output of 180 W, and 15 g of pure water is added. The obtained emulsion was subjected to a dispersion treatment for 30 seconds with an ultrasonic disperser with an output of 180 W to prepare a metal fine particle dispersion 2.

<Method for producing network structure containing silver fine particles>
A silver fine particle dispersion solution 2 was applied on a polyethylene terephthalate resin substrate (hereinafter referred to as a PET substrate) by a bar coater and then dried to prepare a transparent conductive film in which metal fine particles were connected in a network form on the PET substrate. Further, in order to improve the conductivity of the conductive portion, heat treatment is performed at 70 ° C. in the atmosphere for 30 seconds, and further heat treatment is performed at 70 ° C. for 30 minutes in an atmosphere containing formic acid vapor, thereby forming a network composed of silver fine particles A transparent conductive film laminated substrate having a cylindrical structure was produced.

Example 1
A silicon oxide gel after drying a perhydropolysilazane solution (manufactured by AZ-Electronic Materials, trade name: Aquamica NP-110) on a PET substrate on which a network structure containing silver fine particles produced by the method described above is laminated. It applied so that the thickness of a body film might be set to 2.0 micrometers. Next, it left still at 30 degreeC for 1 hour, and obtained the silicon oxide gel body film | membrane.
Next, the perhydropolysilazane solution was applied on a glass substrate so that the thickness of the silicon oxide gel body film was 0.5 μm, and then bonded at a position facing the silicon oxide gel body film side, at 30 ° C. The glass substrate and the silicon oxide gel body film were bonded by drying for 1 hour.
Next, the PET substrate was removed and baked at 250 ° C. for 3 hours to obtain a transparent conductive film laminated substrate having a network structure containing silver fine particles. The center line average roughness (Ra) was 0.08 μm, and the surface flatness was excellent as compared with the conventional transparent conductive film. The surface resistance value was 10Ω / □, and the total light transmittance was 81%. As a heat resistance test, the sample was heated at 250 ° C. for 1 hour as a heat resistance test, and had the same surface resistance and total light transmittance as before the heating.

Example 2
A silicon oxide gel after drying a perhydropolysilazane solution (manufactured by AZ-Electronic Materials, trade name: Aquamica NP-110) on a PET substrate on which a network structure containing silver fine particles produced by the method described above is laminated. It applied so that the thickness of a body film might be set to 1.5 micrometers. Next, it left still at 30 degreeC for 1 hour, and obtained the silicon oxide gel body film | membrane.
Next, the perhydropolysilazane solution was applied on a glass substrate so that the thickness of the silicon oxide gel body film was 1.0 μm, and then bonded at a position facing the silicon oxide gel body film side, at 30 ° C. The glass substrate and the silicon oxide gel body film were bonded by drying for 1 hour.
The center line average roughness (Ra) was 0.09 μm, and the surface flatness was improved. The surface resistance value was 15Ω / □, and the total light transmittance was 80%.

Comparative Example 1
The silver fine particle dispersion solution was applied and dried on the PET substrate by the above-described method, heat treatment and chemical treatment were performed, and a network structure containing silver fine particles was laminated. The surface resistance value was 6Ω / □, and the total light transmittance was 86%.
The center line average roughness (Ra) measured by a surface roughness meter was 1.2 μm, and the surface was poor in flatness. As a heat resistance test, when heated at 250 ° C. for 1 hour, the PET film shrunk, and at the same time it turned yellow and lost its function as a transparent conductive film.

The transparent conductive film and the transparent conductive film substrate according to the present invention have high conductivity (low resistance), high transmittance, excellent heat resistance and flatness, and the transparent conductive film and the transparent conductive according to the present invention. Since the manufacturing method of the conductive film laminated substrate can be easily manufactured without using a special apparatus, it is suitable for a thin-film solar cell or a transparent electrode for organic EL.

It is the flowchart which showed the manufacturing method of the transparent conductive film laminated substrate which concerns on this invention.

Explanation of symbols

1 Network structure composed of fine metal particles
2 Polysilazane solution
3 Silicon oxide gel (intermediate state between polysilazane and silica)
4 Transparent conductive film 5 Transparent conductive film laminated substrate
10 Substrate
11 Glass substrate

Claims (8)

A silicon oxide gel body film containing a network structure composed of metal fine particles and containing polysilazane as a main component. 2. A silicon oxide gel body in which the metal fine particles according to claim 1 are a metal selected from Au, Ag, Cu, Pt, Pd, Fe, Co, Ni, Al, In, and Sn, or an alloy containing two or more of the above metals. film. 3. The silicon oxide gel film according to claim 1, wherein the silicon oxide gel film is formed by using perhydropolysilazane as a main component polysilazane. A transparent conductive film obtained by heating and / or humidifying the silicon oxide gel body film according to any one of claims 1 to 3, wherein the transparent conductive film is an oxide mainly composed of silicon oxide. A transparent conductive film characterized in that a network structure composed of fine metal particles is contained therein. A transparent conductive film laminated substrate obtained by laminating the transparent conductive film according to claim 4 on a glass substrate. After forming a network structure composed of metal fine particles on a substrate, a solution containing polysilazane as a main component is applied to the network structure, and then dried to prepare a silicon oxide gel film The method for producing a silicon oxide gel body film according to any one of claims 1 to 3. After forming a network structure composed of metal fine particles on a substrate, applying a solution containing polysilazane as a main component to the network structure, and then drying to prepare a silicon oxide gel film The method for producing a transparent conductive film according to claim 4, wherein the silicon oxide gel body film is heated and / or humidified. After forming a network structure composed of metal fine particles on a substrate, applying a solution containing polysilazane as a main component to the network structure, and then drying to prepare a silicon oxide gel film 6. The method for producing a transparent conductive film according to claim 5, wherein after the silicon oxide gel body film is adhered to a glass substrate as an adhesive layer, the substrate is removed, followed by heating and / or humidification treatment.

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