JP5363125B2 - Transparent conductive film laminated substrate and manufacturing method thereof - Google Patents

Description

Provided are a transparent conductive film and a transparent conductive film laminated substrate in which an oxide film containing silicon oxide as a main component encapsulating a network structure composed of fine metal particles of the present invention, and a method for producing the same.

  A transparent conductive film is used for electrodes such as a display device such as a plasma display and an organic EL, an input sensor such as a touch panel, a thin film amorphous Si solar cell, and a dye-sensitized solar cell.

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, as a method for forming a transparent conductive film, a metal film is formed in a lattice shape or a mesh shape in place of the continuous transparent conductive film by the vapor phase method as described above, and the metal film portion is A discontinuous transparent conductive film having a conductivity and a hole having a light transmission property is disclosed. For example, an EMI shield film for a plasma display in which Cu is etched in 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 ensuring transparency.

Conventionally, a transparent conductive film laminated substrate having a network structure by screen-printing a metal fine particle paste onto a substrate in a mesh form and heating and firing is known (Patent Document 1). Also known is a method of forming a transparent conductive film on a substrate by preparing a W / O type emulsion from a metal fine particle dispersion solution, forming a network structure on the substrate by applying and drying on a 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, the above-mentioned discontinuous transparent conductive film can obtain a transparent conductive film laminated substrate having high transmittance and high conductivity which are important as a transparent conductive film. In the laminated substrate, the conductive part inevitably becomes convex on the upper surface of the transparent conductive film laminated substrate due to the manufacturing method, 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

  That is, the present invention is a transparent conductive film characterized by being an oxide film mainly composed of silicon oxide containing a network structure composed of metal fine particles (Invention 1).

  Further, the present invention provides an oxide that is 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 in the metal fine particles. A transparent conductive film characterized by being an oxide film containing silicon as a main component (Invention 2).

  Further, the present invention provides the transparent conductive film characterized in that the silicon oxide is an oxide film mainly composed of silicon oxide formed using one or more of silica fine particles, silica-based compounds, and polysilazane. There is (Invention 3).

  Moreover, this invention is a transparent conductive film laminated substrate which laminated | stacked the said transparent conductive film on the glass substrate or the ceramic substrate (this invention 4).

  In the present invention, after forming a network structure composed of metal fine particles on a base material, a glass substrate or an adhesive layer containing silica fine particles, one or more types of silica-based compounds, and an organic binder is used. This is a method for producing a transparent conductive film laminated substrate, wherein the adhesive layer is transferred onto the ceramic substrate together with the network structure and then heated and fired (Invention 5).

  The present invention also provides a method for producing a transparent conductive film laminated substrate, comprising: applying a solution containing polysilazane as a main component to the surface of the transparent conductive film laminated substrate, followed by heating and baking and / or humidification. There is (Invention 6).

  The present invention is also a method for producing a transparent conductive film laminated substrate, wherein the surface of the transparent conductive film laminated substrate is subjected to chemical wet etching and / or physical polishing (etching or polishing) ( Invention 7).

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

  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 the substrate (10), and then a conductive portion having a network structure is formed by heating and / or chemical treatment (see FIG. 1). (A)).

  Next, using the adhesive layer coating agent (2) containing silica fine particles and / or a silica-based compound and an organic binder, the conductive part having the network structure is applied on the substrate (10), dried and bonded. Form a layer. ((B) of FIG. 1). Further, it is bonded to a glass substrate (11) or a ceramic substrate having excellent optical transparency and heat resistance ((C) in FIG. 1). After confirming that it is sufficiently adhered, the substrate (10) is removed and the network structure is transferred together with the adhesive layer ((D) of FIG. 1).

  Next, it is heated and fired at a temperature of 600 ° C. or less, and the organic binder and organic solvent in the adhesive layer are decomposed and scattered, so that it has high transmittance, high conductivity, improved flatness, and heat resistance. A transparent conductive film and a transparent conductive film laminated substrate (5) composed of a material excellent in weather resistance can be obtained ((E) in FIG. 1).

  Furthermore, for the purpose of improving surface flatness, after applying a solution containing polysilazane as a main component on the surface ((F) in FIG. 1), heating and / or humidification is performed to vitrify the polysilazane, thereby increasing the transmittance. It is possible to obtain a transparent conductive film (4) and a transparent conductive film laminated substrate (5) composed of a material having a high rate, high conductivity, improved flatness, and excellent heat resistance and weather resistance ( (G) of FIG.

  The surface may be subjected to chemical wet etching and / or physical polishing (etching or polishing) for the purpose of further improving the flatness and conductivity of the transparent conductive film with improved surface flatness ( (H) of FIG.

  The adhesive layer may be formed on the glass substrate or the ceramic substrate side, and the network structure may be transferred by aligning the network structure with the substrate and removing the base material.

Au, Ag, Cu, Pt, Pd, Fe, Co, Ni, Al, In, Sn, etc. can be used as the metal species of the metal fine particles of the present invention. Alternatively, an alloy containing two or more of the above 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 of electronic circuits.

The metal fine particles can be prepared using a gas phase method, a liquid phase method, a metal salt thermal decomposition method, or the like, which has been conventionally disclosed. Alternatively, a method in which a network structure is formed using the metal salt or organometallic compound of the metal and then chemically or physically reduced can be used.

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

  A substrate for applying or printing a metal fine particle dispersion solution or printing ink containing metal fine particles can withstand the formation of a conductive part having a network structure with the metal fine particle dispersion solution or printing ink containing metal fine particles. And heat resistance. Moreover, from the ease of transfer of a network structure composed of metal fine particles to a glass substrate or a ceramic substrate, as a base material that meets the above conditions, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, polyimide resins, A polyamide resin or the like is preferable.

  Next, when forming a conductive portion having a network structure containing metal fine particles, a method of applying a metal fine particle dispersion solution described in Patent Document 2 or a method of screen printing a metal fine particle dispersed ink described in Patent Document 1 May be used.

  After forming the conductive portion having a network structure containing 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 containing metal fine particles is preferably 0.4 to 10 μm. When it is thinner than 0.4 μm, sufficient conductivity cannot be obtained. This is because when the thickness exceeds 10 μm, the line width of the mesh portion tends to be increased at the same time, resulting in a decrease in transmittance.

Next, as shown in FIG. 1B, the entire surface of the base material on which the conductive portion having a network structure is formed is covered with a highly transparent adhesive to form the adhesive layer 2.
The adhesive used in the adhesive layer of the present invention is mainly composed of silica fine particles, one or more types of silica compounds, and an organic binder.

Organic binders include polyvinyl chloride, polycarbonate, polystyrene, polymethyl methacrylate, polybutyl methacrylate, polyester, polysulfone, polyvinyl butyral, polyvinyl acetal, polyphenylene oxide, polybutadiene, poly (N-vinyl carbazole), polyvinyl pyrrolidone, hydrocarbon resin , Ketone resin, phenoxy resin, polyamide, chlorinated polypropylene, polyimide, urea, cellulose, vinyl acetate, ABS resin, polyurethane, phenol resin, melamine resin, unsaturated polyester resin, alkyd resin, epoxy resin, silicone resin Examples include at least one of the group consisting of polymers, and / or any mixture thereof.

As the silica fine particles and the silica-based compound, colloidal silica in which colloidal silica fine particles are dispersed in water or an organic solvent, an alkyl silicate, a silane coupling agent, or a mixture thereof can be used.
The colloidal silica is preferably ultrafine particles having a particle diameter (diameter) of about 1 to 50 nm. The particle diameter of the colloidal silica in the present invention is an average particle diameter according to the BET method (a surface area is measured by the BET method, and the average particle diameter is calculated by converting the particles to be true spheres).

The colloidal silica is a known one, and commercially available ones include, for example, “methanol silica sol”, “MA-ST-M”, “IPA-ST”, “EG-ST”, “EG-ST-ZL”. "," NPC-ST "," DMAC-ST "," MEK-ST "," XBA-ST "," MIBK-ST "(all products of Nissan Chemical Industries, Ltd., all trade names)," OSCAL1132 ”,“ OSCAL1232 ”,“ OSCAL1332 ”,“ OSCAL1432 ”,“ OSCAL1532 ”,“ OSCAL1632 ”,“ OSCAL1132 ”(above, products of Catalyst Chemical Industry Co., Ltd., all trade names). be able to.

Examples of the alkyl silicate include methyl silicate, ethyl silicate, butyl silicate, or a hydrolysis polymerization reaction product obtained by mixing these together with a solvent, water, and a hydrolysis polymerization catalyst, followed by hydrolysis and polymerization.

Examples of the silane coupling agent include methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, isobutyltrimethoxysilane, Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, 3,3,3-trifluoropropyltrimethoxysilane, methyl-3,3,3-trifluoropropyldimethoxysilane, β- (3 , 4-Epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxymethyltrimethoxysilane, γ-glycidoxymethyltriexisilane, γ-glycidoxyethyltrimethoxysilane, γ-glycid Cyethyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ- (β -Glycidoxyethoxy) propyltrimethoxysilane, γ- (meth) acrylooxymethyltrimethoxysilane, γ- (meth) acrylooxymethyltriethoxysilane, γ- (meth) acrylooxyethyltrimethoxysilane, γ- (meth) acrylooxyethyltriethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane Silane, γ- (meth) acrylooxypropyltriethoxysilane, butylto Limethoxysilane, isobutyltriethoxysilane, hexyltriethoxysilaoctyltriethoxysilane, decyltriethoxysilane, butyltriethoxysilane, isobutyltriethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltriethoxysilane, 3- Ureidoisopropylpropyltriethoxysilane, perfluorooctylethyltrimethoxysilane, perfluorooctylethyltriethoxysilane, perfluorooctylethyltriisopropoxysilane, trifluoropropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyl Methyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, - mercaptopropyltrimethoxysilane, trimethylsilanol, methyl trichlorosilane and the like.

The content of the silica fine particles and the silica-based compound contained in the adhesive layer in the present invention is preferably in the range of 10% by weight to 80% by weight in the adhesive layer. When the content of the silica fine particles and the silica-based compound is outside the above range, the flatness of the finally obtained transparent conductive film laminated substrate is inferior, which is not preferable.

Moreover, an ultraviolet absorber, a color pigment, an antistatic agent, an antioxidant, a silane coupling agent, and the like can be appropriately used as necessary for the adhesive layer.

The adhesive layer may be provided on one surface of the transfer substrate (glass substrate or ceramic substrate) instead of being provided on the substrate side.

As a method for forming the adhesive layer, a coating agent in which the above-mentioned adhesive material is dissolved in an organic solvent or water or dispersed in water to adjust the viscosity is prepared, and applied and dried by a conventionally known coating method such as gravure coating or spin coating. The method can be used.

The thickness of the adhesive layer is preferably 0.5 to 50 μm, more preferably 1.0 to 30 μm. If the thickness of the adhesive layer is less than 0.5 μm, sufficient adhesion to the substrate may not be obtained. In addition, if the thickness of the adhesive layer is greater than 50 μm, it is not preferable because the firing time becomes longer when performing the heat firing in the next step.

Next, as shown in FIG. 1C, after the base material and the glass substrate 11 are bonded together, heat treatment and pressure treatment are performed as necessary, the base material is peeled off, and the transparent conductive film is formed. Transfer to the glass substrate 11. As the transfer method, a known transfer method can be used, and it may be appropriately selected according to the base material to be used, the material of the substrate to be transferred, and the adhesive layer. For example, a transfer method using a laminator, a transfer method using a press, a thermal transfer method using a thermal head, and the like can be used.

Next, the substrate on which the transparent conductive film is transferred is heated and baked using a commonly used heating and baking furnace to decompose and scatter the organic binder. Here, it is preferable to perform the heating and baking temperature in a temperature range of 300 ° C to 600 ° C. If the heating and baking temperature is less than 300 ° C., not only will the baking process take a long time and the productivity will decrease, but also the organic binder will remain in the transparent conductive film without being decomposed or scattered and the transmittance will decrease. This is not preferable because of the possibility. On the other hand, when the heating and baking temperature is higher than 600 ° C., the glass substrate may be warped, which is not preferable.

The heating and baking time may be adjusted as appropriate together with the baking temperature according to the organic binder used for the adhesive layer, and it may be usually treated for about 5 minutes to 10 hours, but is not particularly limited.

By the above production method, a transparent conductive film and a transparent conductive film laminated substrate made of a material having high transmittance, high conductivity, flatness, and excellent heat resistance and weather resistance are obtained. I can do it.

  Further, the transparent conductive film laminated substrate may be a silica fine particle and / or a silica-based material depending on a metal type, a film thickness, a line width, a heating temperature at the time of heating and firing, and a time of the conductive portion having a network structure including metal fine particles. Surface flatness may deteriorate due to the difference in volume shrinkage between the compound and the metal fine particles. A method for further improving the surface flatness will be described below.

  First, a solution containing polysilazane as a main material is applied to the surface of the transparent conductive film laminated substrate obtained by the above-described production method.

Polysilazane is a general term for linear or cyclic compounds having -SiR ¹ ₂ -NR ² -SiR ¹ _2- (R1 and R2 each independently represents a hydrogen atom or a hydrocarbon gas) having a silazane bond, and heating Alternatively, the Si—NR ² —Si bond is decomposed by reaction with moisture to form a Si—O—Si network. 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 using polysilazane as a main raw material may contain a metal fine particle catalyst (such as Pd fine particle) or an amine catalyst in order to improve the reactivity of the silazane bond of polysilazane.

  The content of polysilazane in a solution containing polysilazane as a main raw material 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 repeatedly to obtain a desired thickness.

  The solvent used in the solution containing polysilazane as a main material is not particularly limited as long as it is a solvent that 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 of applying a solution containing polysilazane as a main raw material 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.

  After applying a solution containing polysilazane as a main raw material, the glass substrate on which the silicon oxide gel film is laminated at 100 to 500 ° C. in the air is heated for 10 minutes to 24 hours to be vitrified, so that the surface becomes flat. A transparent conductive film laminated substrate having improved properties can be obtained ((H) in FIG. 1).

Alternatively, a transparent conductive film laminated substrate with improved surface flatness can be obtained by allowing it to stand for 1 to 4 weeks in the atmosphere at room temperature for vitrification.

  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.

  Furthermore, it is preferable to perform a chemical wet etching method and / or a physical polishing method (etching or polishing) for the purpose of improving the surface property and conductivity of the transparent conductive film laminated substrate obtained by the above-described production method.

As a chemical wet etching method, a mixed acid such as hydrofluoric acid or ammonium fluoride used in general wet etching of glass, or a commercially available glass etching agent (for example, glass etching agent manufactured by Flosstec) is used. It is preferable to use it.

The etching conditions are preferably determined by appropriately determining optimum conditions while confirming the surface flatness and conductivity of the transparent conductive film substrate.

  As a physical polishing method, a general glass polisher cloth, a glass polisher apparatus, or the like can be used. When a large area and high-speed workability are required, polishing may be performed using a commercially available apparatus for polishing display glass.

  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 even more preferably 10Ω / □ 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 0.5 μm or less, and even more preferably 0.1 μm. When the thickness is larger than 1.0 μm, the function is deteriorated when the 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.

  In the examples, silver fine particles are exemplified as the metal fine particles, but the metal species is not limited.

    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 size of 60 nm as observed with an electron microscope.

<Preparation Method of Silver Fine Particle Dispersion Solution 2> (Preparation with reference to Special Table 2005-530005)
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 silver fine particle dispersion solution 2.

<Method for producing network structure containing silver fine particles>
A transparent conductive film in which metal fine particles are connected in a network form on a PET substrate by applying a silver fine particle dispersion solution on a polyethylene terephthalate resin substrate (hereinafter referred to as PET substrate) having a thickness of 100 μm using a bar coater and then drying. Was made. 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. The base material with which the structure was laminated | stacked was produced.

Example 1
The following adhesive layer coating solution 1 is applied on a PET base material on which a network structure containing silver fine particles prepared by the above-described method is laminated so that the thickness after drying is 5 μm, and is 5 at a temperature of 100 ° C. The layer was dried to form an adhesive layer.
<Adhesive layer coating solution 1>
After dissolving 8 g of polyvinyl butyral resin (Sekisui Chemical Co., Ltd., ESREC BL-2) in 52 g of normal butanol, 40 g of methanol dispersion of silica sol (silica sol 30% by weight, average particle size 15 nm) is added and stirred to form an adhesive layer coating. Liquid 1 was produced.
<Transfer>
A hot laminator (manufactured by Taisei Laminator, Taisei First Laminator) is made to face a surface of a glass substrate having a thickness of 1 mm on which the adhesive layer of a PET substrate having a network structure containing silver fine particles and an adhesive layer is formed. VAII-700) was used for heat pressure welding at 180 ° C. and left to cool to room temperature, and then the PET base material was peeled off to transfer the network structure containing silver fine particles and the adhesive layer onto the glass substrate.
<Heating and firing>
The glass substrate on which the network structure containing silver fine particles and the adhesive layer are laminated is heated and fired for 30 minutes in a firing furnace heated to 500 ° C. (Electric Muffle Furnace KM-280, manufactured by Advantech Toyo Co., Ltd.). A glass substrate on which a conductive film was laminated was produced.
<Planarization>
A perhydropolysilazane solution (manufactured by AZ-Electronic Materials, trade name: Aquamica NP-110) was applied to the surface of the transparent conductive film laminated substrate using a spin coater.
Next, it is baked at 250 ° C. for 3 hours to vitrify perhydropolysilazane, and has a network structure composed of silver fine particles, and a transparent conductive film in which an oxide film mainly composed of silicon oxide is laminated. A conductive film laminated substrate was obtained.
The center line average roughness (Ra) was 0.3 μm, and the surface flatness was excellent as compared with the conventional transparent conductive film. The surface resistance value was 5Ω / □, and the total light transmittance was 81%. Although it heated at 300 degreeC as a heat resistance test for 1 hour as a heat resistance test, it was the same surface resistance value and total light transmittance as before heating.

Example 2
Similar to Example 1 described above, a transparent conductive film laminated substrate having a network structure composed of silver fine particles and laminated with an oxide film mainly composed of silicon oxide was prepared.
Next, the surface of the transparent conductive film laminated substrate was polished using a commercially available glass etchant to produce a transparent conductive film laminated substrate with improved surface properties.
The center line average roughness (Ra) was 0.1 μm, and the surface flatness was improved. The surface resistance value was 3Ω / □, and the total light transmittance was 81%.

Comparative Example 1
The silver fine particle dispersion solution was applied and dried on a PET substrate by the method described above, 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. When heated at 300 ° C. for 1 hour as a heat resistance test, the PET film contracted, 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 stack substrate according to the present invention have low resistance and high transmittance, excellent heat resistance and flatness, and the transparent conductive film and the transparent conductive film laminated substrate according to the present invention. Since the production method can be easily produced without using a special apparatus, it is suitable for a thin film solar cell or a transparent electrode for organic EL.

1 Network structure composed of fine metal particles
2 Silica filler mixed adhesive layer 3 Polysilazane solution 4 Transparent conductive film 5 Transparent conductive film laminated substrate
10 Base material 11 Glass substrate

Claims (3)

Reticulated structure oxide as a main component silicon oxide containing therein the film Der Ru translucent transparent conductive film manufacturing method of the transparent conductive film laminated substrate laminated on a glass substrate or a ceramic substrate made of a metal fine particle The metal fine particles are a metal selected from Au, Ag, Cu, Pt, Pd, Fe, Co, Ni, Al, In, Sn, or an alloy containing two or more of the metals, A silicon oxide formed using one or more of silica fine particles, silica-based compounds, and polysilazanes. After forming a network structure composed of metal fine particles on a substrate, silica fine particles, silica-based compounds 1 After transferring the adhesive layer together with the network structure onto the glass substrate or the ceramic substrate through the adhesive layer containing at least one kind and an organic binder, the transparent conductive film is further heated and fired. Was coated with a solution composed mainly of polysilazane on the surface of the layer substrate, firing and / or the transparent conductive film manufacturing method of a multilayer substrate, characterized in that the humidification. The method for producing a transparent conductive film laminated substrate according to claim 1, characterized by performing chemical wet etching and / or physical polishing the surface of the transparent conductive film laminated substrate (etching or polishing). A transparent conductive film laminated substrate manufactured by the manufacturing method according to claim 1.

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