JP2003151363A - Conductive film and manufacturing method of conductive film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a conductive film showing high conductivity and its manufacturing method with a low temperature process in regard to a wet conductive film, having high conductivity, transparency and superior visibility by improving poorness of visibility of a conductive film of a metal mesh which is prior art. SOLUTION: The conductive film and its manufacturing method are characterized by that a metal particulate holding layer is provided having at least a metal particulate holding part formed with a pattern, a metal particulate layer including held metal particulates is provided in the metal particulate holding part, and adjacent metal particulates of the metal particulates forming the metal particulate layer are crosslinked via a metal cross linking agent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a conductive film and its manufacturing method. Especially EL, PDP, LC
The present invention relates to a transparent conductive film useful as an electromagnetic wave shielding film and a transparent electrode of various display devices such as D and CRTs, or a transparent electrode of a solar cell, and a manufacturing method thereof. Furthermore, the present invention relates to a transparent conductive film having high conductivity and transparency and excellent visibility, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, a thin film made of a conductive oxide or a metal is generally used as a transparent conductive film.
Among them, the conductive oxide is excellent in transparency, but has a relatively large volume resistivity, and it is necessary to increase the film thickness in order to obtain a sufficiently low surface resistance. For this reason, especially in a large-area application where a low surface resistance is required, not only the film forming cost becomes very high, but also it is difficult to obtain a surface resistance that is sufficiently low in practical use. On the other hand, although metals have excellent conductivity, they are inherently small in transparency, and their practical use is currently limited to a very narrow range of applications.

On the other hand, it has been attempted to provide a mesh-shaped conductive structure formed of a metal wire or a carbon wire on the surface of a transparent substrate so as to achieve both high transparency and high conductivity. However, since the mesh structure has a limit in reducing the line width and the wire can be visually observed, when used in the above various display devices,
A significant reduction in visibility is inevitable.

Further, in a patterned conductive film such as a printed wiring body, due to the wetting characteristics of the conductive coating liquid and the base material, the line width becomes thicker when attempting to provide sufficient conductivity, When the line width is made narrow, it is difficult to secure sufficient conductivity.

[0005]

The present invention has been made in view of the above problems in the prior art, and an object thereof is to provide a conductive film exhibiting high conductivity in a low temperature process and a method for manufacturing the same. To do. Another object is to provide a transparent conductive film having high transparency and excellent visibility, and a method for manufacturing the same.

[0006]

The invention according to claim 1 has a metal fine particle holding layer in which at least a metal fine particle holding portion is patterned, and a metal fine particle layer containing metal fine particles held in the metal fine particle holding portion. And adjacent ones of the metal fine particles are cross-linked through a metal cross-linking agent.

According to a second aspect of the present invention, the pattern of the metal fine particle holding portion is a mesh having a line width of 5 μm or less, and the area of the metal fine particle holding portion is 40% of the area of the metal fine particle holding layer. It is below, and the light transmittance of the visible light region of the whole conductive film is 50% or more, It is a conductive film of Claim 1 characterized by the above-mentioned.

According to a third aspect of the present invention, a mercapto group, an amino group, a cyano group, a 2-pyridyl group, or a diphenylphosphino group is formed on the surface of the metal fine particle holding portion that is in contact with the metal fine particles. The transparent conductive film according to claim 1, which has one or more functional groups selected from the group consisting of:

According to a fourth aspect of the invention, the metal fine particles are A
g and / or Au are included.
The conductive film according to any one of 3 above.

A fifth aspect of the present invention is the conductive film according to the fourth aspect, wherein the fine metal particles have a primary particle diameter of 100 nm or less.

The invention of claim 6 is characterized in that the metal cross-linking agent has two or more functional groups selected from a mercapto group, an amino group, a cyano group, a 2-pyridyl group, a diphenylphosphino group and a hydroxyl group. The conductive film according to any one of claims 1 to 5.

According to a seventh aspect of the present invention, the metal cross-linking agent has a linear group having a functional group selected from a mercapto group, an amino group, a cyano group, a 2-pyridyl group, a diphenylphosphino group and a hydroxyl group at both ends. The conductive film according to any one of claims 1 to 5, which is an alkyl compound.

According to an eighth aspect of the present invention, the metal fine particle holding layer includes an alkoxy gel layer formed from a starting material containing at least one kind selected from various alkoxides of Si, Al, Ti and Zr. It is a conductive film in any one of Claims 1-7 characterized by the above-mentioned.

According to a ninth aspect of the present invention, one of the hydrolyzable silane compounds wherein the metal fine particle holding portion has a functional group selected from a mercapto group, an amino group, a cyano group, a 2-pyridyl group and a diphenylphosphino group. 9. The conductive film according to claim 8, which is formed by bonding at least one kind to the surface of the alkoxy gel layer.

According to a tenth aspect of the present invention, the metal fine particle holding layer comprises one or more kinds selected from various alkoxides of Si, Al, Ti and Zr, a mercapto group, an amino group, a cyano group, a 2-pyridyl group and diphenyl. A metal-retaining alkoxy gel layer capable of holding metal fine particles on the entire surface, which is formed from a starting material containing at least one kind selected from hydrolyzable silane compounds having a functional group selected from a phosphino group. The conductive film according to any one of claims 1 to 7.

According to the invention of claim 11, in the method for producing a conductive film having at least a transparent conductive layer, the step of forming a metal fine particle holding layer having a metal fine particle holding portion patterned, wherein the metal fine particle holding layer is provided with metal fine particles. A method for producing a conductive film, comprising a step of holding, a step of holding a metal cross-linking agent on the held metal fine particles, and a step of holding the metal fine particles on the metal cross-linking agent.

In a twelfth aspect of the present invention, the metal fine particle holding layer, the step of forming a metal cross-linking agent on the held metal fine particles, and the step of holding the metal fine particles on the metal fine particles on which the metal cross-linking agent is formed are performed a plurality of times. The method for manufacturing a conductive film according to claim 11, wherein the method is repeated.

According to a thirteenth aspect of the present invention, the pattern of the metal fine particle holding portion is a mesh having a line width of 5 μm or less, and the area of the metal fine particle holding portion is 40% of the area of the metal fine particle holding layer. 13. The method for producing a conductive film according to claim 11, wherein the light transmittance in the visible light region of the entire conductive film is 50% or more.

According to a fourteenth aspect of the present invention, the metal fine particle holding portion has at least one functional group selected from a mercapto group, an amino group, a cyano group, a 2-pyridyl group and a diphenylphosphino group. The method for producing a conductive film according to any one of claims 11 to 13, wherein the conductive film is provided on the surface of the.

According to a fifteenth aspect of the present invention, the metal fine particles are
2. Ag and / or Au is included, It is characterized by the above-mentioned.
The method for producing a conductive film according to any one of 1 to 14.

The invention of claim 16 is characterized in that the fine metal particles have a primary particle diameter of 100 nm or less.
5 is a method for manufacturing a conductive film according to item 5.

According to a seventeenth aspect of the present invention, in the step of forming a metal fine particle holding layer, an alkoxy gel layer formed from a starting material containing at least one or more kinds selected from various alkoxides of Si, Al, Ti and Zr is formed. After patterning a non-retaining portion that inactivates the alkoxy gel layer with respect to the following hydrolyzable silane compound, a mercapto group, an amino group, a cyano group, 2- Forming one or more kinds of hydrolyzable silane compounds having a functional group selected from a pyridyl group and a diphenylphosphino group as a metal fine particle holding part, according to any one of claims 11 to 16. It is a manufacturing method of the conductive film described.

According to the eighteenth aspect of the present invention, in the step of forming the metal fine particle holding layer, one or more kinds selected from various alkoxides of Si, Al, Ti and Zr and a mercapto group, an amino group, a cyano group and a 2-pyridyl group are used. On a metal-retaining alkoxy gel layer capable of retaining metal fine particles on the entire surface, which is formed from a starting material containing at least one kind selected from hydrolyzable silane compounds having a functional group selected from diphenylphosphino groups. The method for producing a conductive film according to claim 11, further comprising patterning the non-holding portion.

In the invention of claim 19, the non-retaining portion contains at least one selected from various long-chain alkylsilane compounds containing a hydrolyzable group and various long-chain fluoroalkylsilane compounds containing a hydrolyzable group. The method for producing a conductive film according to claim 17 or 18, wherein:

The invention of claim 20 is the method for producing a conductive film according to any one of claims 17 to 19, characterized in that the non-holding portion is formed by microcontact printing.

The invention of claim 21 is characterized in that the step of holding the metal fine particles includes an operation of immersing the metal fine particle holding layer in a dispersion liquid in which the metal fine particles are dispersed. It is a method for manufacturing a conductive film according to any of the above.

The invention of claim 22 is characterized in that the step of holding the metal fine particles includes an operation of applying a coating liquid containing the metal fine particles on the metal fine particle holding layer. It is a method for manufacturing a conductive film according to any of the above.

In a twenty-third aspect of the invention, the step of holding the metal cross-linking agent in the held metal fine particles includes an operation of immersing the metal fine-particle holding layer holding the metal in a solution containing the metal cross-linking agent. The method for producing a conductive film according to any one of claims 11 to 22, characterized in that.

According to a twenty-fourth aspect of the present invention, the step of holding the metal cross-linking agent on the held metal fine particles comprises the step of applying a coating solution containing the metal cross-linking agent onto the metal fine particle holding layer holding the metal. 11. The method according to claim 11, further comprising:
The method for producing a conductive film according to any one of 2 above.

[0030]

BEST MODE FOR CARRYING OUT THE INVENTION An example of an embodiment of the present invention will be described in detail below with reference to FIG. The conductive film 2 in the invention is formed on the transparent substrate 1 and includes at least the conductive layer 3, and the conductive layer 3 includes the metal fine particle holding layer 4. Further, the metal fine particle holding layer 4 includes the alkoxy gel layer 41 in which the metal fine particle holding portion 4a and the metal fine particle non-holding portion 4b are patterned, and holds the metal fine particle layer 7 in the metal fine particle holding portion 4a. Further, the metal fine particle layer 7 includes the metal fine particles 5
And the adjacent metal fine particles 5 are cross-linked by the metal cross-linking agent 6.

The method for producing the conductive film 2 is as follows. The metal fine particle holding layer 4 in which the metal fine particle holding portion 4a and the metal fine particle non-holding portion 4b are patterned is formed on the base material 1 [metal fine particle holding layer forming step], The metal fine particles 5 are held in the metal fine particle holding portion 4a [metal fine particle holding step], and the metal cross-linking agent 6 is held in the metal fine particles 5 [metal cross-linking agent holding step on the metal fine particles]. Agent 6
The step of holding the metal fine particles 5 is included in [a step of holding the metal fine particles on the metal crosslinking agent]. A detailed description will be given below for each step.

[Metal fine particle holding layer forming step] The metal fine particle holding layer 4 is the alkoxy gel layer 4 formed on the transparent substrate 1.
After patterning the metal fine particle non-holding portion 4b on the substrate 1,
It is formed by fixing a hydrolyzable silane compound having a metal-affinity functional group as the metal fine particle holding portion 4a to a portion where the metal fine particle non-holding portion 4b is not formed, if necessary. Further, although it is possible to directly pattern the metal fine particle holding portion 4a, the manufacturing method by the former method will be described here.

The substrate 1 is not particularly limited, but when it is a transparent conductive film, it is preferable to use a transparent substrate. It can be appropriately selected from various known plastic films or sheets having suitable mechanical rigidity including glass substrates. Specific examples include films of polyester, polyethylene, polypropylene, triacetyl cellulose, diacetyl cellulose and the like.

As the material for forming the alkoxy gel layer 41, for example, the following two systems can be used. A) one or more selected from various metal alkoxides of Si, Al, Ti, Zr and hydrolysates thereof, B) in addition to A), a mercapto group, an amino group, a cyano group, a 2-pyridyl group, Specific examples of one or more metal alkoxides selected from hydrolyzable silane compounds having a metal-affinity functional group selected from diphenylphosphino groups include tetraethoxysilane, methyltriethoxysilane, phenyltriethoxysilane, and chloro. Trimethoxysilane, vinyltriethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltri Ethoxysilane, Aluminum triisopropoxide, Al Examples include aluminum tributoxide, aluminum diisopropoxide ethyl acetoacetate, titanium tetraisopropoxide, titanium diisopropoxy (bis-2,4-pentanedionate) and zirconium tetrabutoxide, but they are versatile and hydrolyzable. From the viewpoint of compatibility with silane compounds, Si
Alkoxides are preferably used.

Specific examples of the metal-affinity hydrolyzable silane compound include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane,
Mercaptomethyldimethylethoxysilane, mercaptomethylmethyldiethoxysilane, mercaptomethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyldimethylethoxy Silane, 3-cyanopropyldimethylmethoxysilane, 3-cyanopropylmethyldimethoxysilane, 3-cyanopropyltrimethoxysilane, 3
-Cyanopropyltriethoxysilane, 3-cyanopropyltrichlorosilane, 2-pyridylethyltrimethoxysilane, diphenylphosphinoethyldimethylethoxysilane, 2-diphenylphosphinoethyltriethoxysilane, and the like, but metal affinity is particularly A hydrolyzable silane compound having a strong mercapto group or amino group is preferably used.

The alkoxy gel layer 41 is formed by applying the composition containing A) or B) to a transparent substrate and curing it. Examples of the coating method include spin coating, knife coating, spray coating, dip coating, and a method using a slit coater, a microgravure coater, and the like, which is appropriately selected and used according to various conditions such as the coating area.

The metal fine particle non-holding portion 4b is appropriately selected from one or more kinds selected from various long-chain alkylsilane compounds containing a hydrolyzable group and various long-chain fluoroalkylsilane compounds containing a hydrolyzable group as its forming substance. Used. As specific examples, n-octadecylmethoxydichlorosilane, n-octadecylmethyldichlorosilane, n-octadecylmethyldiethoxysilane, n-octadecyltrichlorosilane, n-octadecyltrimethoxysilane, n-octadecyltriethoxysilane,
n-hexadecyltrichlorosilane, n-hexadecyltrimethoxysilane, n-tetradecyltrichlorosilane, dodecyltrimethoxysilane, dodecyltrichlorosilane, heptadecafluoro-1,1,2,2-tetrahydrodecyltrichlorosilane, heptadeca Fluoro-
Examples include 1,1,2,2-tetrahydrodecyltriethoxysilane.

The pattern of the metal fine particle non-holding portion 4b can be a desired pattern according to the purpose. For example, in the case of a printed wiring board, it can be formed to have a desired wiring pattern. In the case of using a transparent conductive film, the area occupancy of the pattern of the metal fine particle non-holding portion 4b needs to be 60% or more with respect to the entire area of the metal fine particle holding layer 4, and Holding part 4a
It is necessary that the pattern shape is a mesh shape having a line width of 5 μm, preferably 1 μm or less. If the area occupancy rate is 60% or less, sufficient transparency cannot be ensured because the metal fine particle holding portion, that is, the portion that becomes a light shielding portion later is too large. Also, the line width is 5
When it is more than μm, the visibility is remarkably reduced.

As a method for forming the metal fine particle non-holding portion 4b, microcontact printing is preferably used.
It is possible to form the metal fine particle non-holding portion 4b on the alkoxy gel layer 41 by using a silicone resin stamp having the convex pattern of the metal fine particle non-holding portion 4b.

When B) is used as the alkoxy gel layer-forming material, the metal fine particle holding portion 4a is formed by patterning the metal fine particle non-holding portion 4b so that the metal fine particle non-holding portion 4b non-forming portion is the metal fine particle. The holding portion 4a is automatically patterned. On the other hand, when A) is used as the alkoxy gel layer forming substance, it is necessary to form the metal fine particle holding portion 4a in the metal fine particle non-holding portion 4b non-forming portion. As a forming method, by immersing the transparent substrate 1 on which the alkoxy gel layer 4 having the metal fine particle non-holding portion 4b is formed, in a solution containing the hydrolyzable silane compound having a metal affinity functional group. As an example, an operation of chemically reacting the hydrolyzable silane compound having a metal-affinity functional group with the metal fine particle non-holding portion 4b non-forming portion can be given.

[Metal Fine Particle Holding Step] As the metal fine particles 5, it is possible to use Ag, Au, or a combination or alloy thereof, but it is preferable to include Au. The metal fine particles can be relatively easily manufactured by many known techniques. For example, fine particles of an alloy of Ag and Au are obtained by adding an aqueous solution of silver nitrate and chloroaurate to citric acid,
It can be obtained by reducing with a reducing agent such as ethylenediaminetetraacetic acid (EDTA).

In the case of forming a transparent conductive film, the particle size of the metal fine particles 5 is preferably 100 nm or less, and particularly preferably 50 nm or less, from the viewpoint of transparency. When the primary particle size is 100 nm or more, not only transparency is deteriorated but also haze is likely to occur, resulting in deterioration of visibility.

The metal fine particles 5 correspond to the metal fine particle holding layer 4 described above.
By immersing the transparent substrate 1 on which the metal fine particles 5 are dispersed in a dispersion liquid in which the metal fine particles 5 are dispersed, or by applying a coating liquid containing the metal fine particles 5 to the transparent substrate 1, the metal fine particle holding portion 4
held in a.

[Step of retaining metal cross-linking agent on metal fine particles] The metal cross-linking agent 6 is prepared by immersing the transparent base material on which the metal fine particles are retained in a solution prepared by dissolving the metal cross-linking agent 6 in an appropriate solvent. Alternatively, by applying a coating liquid containing a metal cross-linking agent to the metal fine particle holding layer 4, the metal fine particles 5 are held by the metal fine particles 5.

As the metal cross-linking agent 6, a known one such as a compound having two or more functional groups selected from a mercapto group, an amino group, a cyano group, a 2-pyridyl group, a diphenylphosphino group and a hydroxyl group is used. You can Further, it is preferable to use one containing a mercapto group or an amino group, which has a high affinity for metals. For example, 2-mercaptoethanol, 2-mercaptoethylamine, 1,
6-hexanediol and the like. In addition, compounds represented by the following chemical formulas (1) to (3) can also be used.

[0046]

[Chemical 1]

[Step of Retaining Metal Fine Particles on Metal Crosslinking Agent] The substrate on which the metal fine particles holding the metal crosslinking agent 6 are held in the above step is immersed in a dispersion liquid in which the metal fine particles 5 are dispersed, or By coating the transparent substrate 1 with a coating liquid containing the metal fine particles 5, the metal fine particles are held by the metal cross-linking agent. Here, in order to develop sufficient conductivity,
It is important to alternately repeat the [step of holding the metal crosslinking agent on the metal fine particles] and the [step of holding the metal fine particle on the metal crosslinking agent]. In this way, the metal fine particle layer 7 is formed. The repeated operation is preferably performed 5 times or more in order to exhibit sufficient conductivity, although it depends on the kinds of the fine metal particles and the metal crosslinking agent used.

[0048]

EXAMPLES The present invention will be specifically described below with reference to examples in which the present invention is applied to a transparent conductive film, but the present invention is not limited to these examples. First, a PDMS stamp forming method, a method for preparing various solutions, and various evaluation methods common to each example and comparative example will be described.

[Preparation of Ag Fine Particle Dispersion] AgNO
₃ 0.18 g of distilled water dissolved in 1000 g of solution was stirred and boiled while sodium citrate dihydrate 1.5
A solution prepared by dissolving 0 g in 100 g of distilled water was added, and then the mixture was boiled for 30 minutes while stirring to obtain an Ag fine particle dispersion liquid. As a result of TEM observation, the average primary particle diameter was about 10 nm. [Preparation of Au Fine Particle Dispersion] HAuCl ₄ .4H ₂ O0.
A solution prepared by dissolving 0.50 g of sodium citrate dihydrate in 50 g of distilled water was added while stirring and boiling 21 g of a solution prepared by dissolving 500 g of distilled water, and then boiled for 15 minutes while stirring to give a deep red color. To obtain a dispersion liquid of Au fine particles.
As a result of TEM observation, the average primary particle diameter was about 13 nm. [Preparation of treatment liquid for forming fine metal particle holding portion] A 10% methanol solution of 3-mercaptopropyltrimethoxysilane was prepared to obtain a treatment liquid for forming fine metal particle adsorption portion. [Metal Crosslinking Agent Solution] 2-Mercaptoethylamine 5 m
A mol / L aqueous solution was prepared and used as a metal crosslinking agent solution. [PDMS Stamp Formation] Using a known method, a silicone resin stamp in which the grid pattern of the metal fine particle holding portion is formed in a concave shape was formed. The concave pattern shape has a line width of 1 μm and an area occupation ratio of 15
%.

[Evaluation of Transparent Conductive Film] (Surface Resistivity) Mitsubishi Chemical Corporation Loresta AP (MC
(P-T400) was measured by the 4-end needle method. (Transmittance) Measurement was performed using a reflection / transmittance meter (HR-100) manufactured by Murakami Color Research Laboratory Co., Ltd. (Visual evaluation) It was confirmed whether the grid pattern was visible. Table 1 shows all the evaluation results of Examples and Comparative Examples.

<Example 1> (Formation of alkoxy gel layer) Tetraethoxysilane 5.
To 21 g, 3.38 g of 0.1N hydrochloric acid was added and hydrolyzed, and then ethanol was added to prepare a solution having a concentration of 4% by weight in terms of silica. This solution was applied onto a glass substrate with a spin coater and dried, and then heat-treated at 100 ° C. for 1 minute to cure the solution, thereby forming an alkoxy gel layer. (Pattern formation of non-holding portion of metal fine particles) The PDMS stamp coated with a 0.2% hexane solution of octadecyltrichlorosilane was applied to the surface of the glass substrate on which the alkoxy gel layer was formed, on which the alkoxy gel layer was formed. By pressing for a few seconds, the metal fine particle non-holding portion was patterned.

(Pattern formation of metal fine particle holding portion) The glass base material on which the metal fine particle non-holding portion is formed is immersed in the treatment liquid for forming the metal fine particle holding portion at room temperature for 10 minutes,
The metal fine particle holder was patterned. (Holding of Metal Fine Particles on Metal Fine Particle Holding Portion) The glass base material on which the metal fine particle holding portion is pattern-formed is referred to as Ag
It was immersed in the fine particle solution at room temperature for 30 minutes to hold the Ag fine particles in the metal fine particle holding portion. (Retention of Metal Crosslinking Agent on Metal Fine Particles) The glass substrate on which the Ag fine particles were retained was immersed in the metal crosslinking agent solution at room temperature for 30 minutes.
After soaking for a minute, it was washed with water to hold the metal cross-linking agent on the Ag fine particles held in the metal fine particle holding portion.

(Holding of Metal Fine Particles to Metal Crosslinking Agent) The glass base material holding the metal crosslinking agent was immersed in the Ag fine particle solution at room temperature for 30 minutes and then thoroughly washed with water to remove silver fine particles from the metal crosslinking agent. Were held by the metal fine particles that were held. (Multilayering) By holding the metal cross-linking agent on the metal fine particles and holding the metal fine particles on the metal cross-linking agent alternately 10 times, a conductive film was obtained, and the transparent conductive film of Example 1 was obtained.

Example 2 The same procedure as in Example 1 was carried out except that the Au particles were used instead of the Ag particles instead of the Ag particles being held in the metal particle holding portion of Example 1.

Example 3 Ag was added to the metal cross-linking agent of Example 1.
Instead of Ag particles, the place where the particles are held is Au.
When the fine particles are used and the subsequent holding of the metal cross-linking agent on the metal fine particles and the holding of the metal cross-linking agent on the metal cross-linking agent are repeated alternately 10 times, the metal fine particles to be held are Ag fine particles, A
The same procedure as in Example 1 was repeated except that the u particles were repeated in this order.

Comparative Example 1 A transparent conductive film was formed in the same manner as in Example 1 except that a copper mesh having a line width of 50 μm and an opening of 300 × 300 μm was used instead of the PDMS stamp.

[0057]

[Table 1]

[Evaluation Result] As is clear from the results shown in Table 1, the conductive film obtained in the present invention has excellent transparency and conductivity and excellent visibility.

[0059]

The conductive film of the present invention can be a conductive film having high conductivity in a low temperature process. In addition, by forming fine metal particles in a fine mesh pattern and forming a transparent conductive layer in which the metal fine particles are cross-linked with each other through a metal cross-linking agent, high conductivity and transparency are exhibited and excellent visibility is obtained. Can be a conductive film. Further, by repeating the retention of the metal fine particles on the metal cross-linking agent and the retention of the metal cross-linking agent on the metal fine particles, the conductivity is further improved.

[0060]

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing an example of a transparent conductive film of the present invention.

FIG. 2 is an enlarged view of a transparent conductive layer of the present invention.

[Explanation of symbols]

1 base material 2 Conductive film 3 Conductive layer 4 Metal fine particle retention layer 4a Metal fine particle holder 4b Metal fine particle non-holding part 5 metal particles 6 Metal cross-linking agents 7 Metal fine particle layer

   ─────────────────────────────────────────────────── ─── Continued front page    F term (reference) 4M104 AA10 BB08 BB09 CC01 DD22                       DD28 DD51 DD71 DD78 GG20                       HH14 HH16 HH20                 5G307 FA01 FB02 FC09 FC10                 5G323 BA01 BA05 BB01 BC03 CA05

Claims (24)

[Claims] 1. A metal fine particle holding layer having at least a patterned metal fine particle holding portion, and a metal fine particle layer containing the metal fine particles held in the metal fine particle holding portion, wherein the metal fine particles are provided. A conductive film, wherein adjacent ones of the metal fine particles forming a layer are crosslinked with each other via a metal crosslinking agent. 2. The pattern of the metal fine particle holding portion is a mesh having a line width of 5 μm or less, and the area of the metal fine particle holding portion is 40% or less with respect to the area of the metal fine particle holding layer, and The light transmittance of the entire conductive film in the visible light range is 5
It is 0% or more, The conductive film of Claim 1 characterized by the above-mentioned. 3. A mercapto group is provided on the surface of the metal fine particle holding portion on the side in contact with the metal fine particles of the metal fine particle holding portion.
The transparent conductive film according to claim 1, which has one or more functional groups selected from an amino group, a cyano group, a 2-pyridyl group, and a diphenylphosphino group. 4. The fine metal particles are Ag and / or Au.
The conductive film according to claim 1, comprising: 5. The conductive film according to claim 4, wherein the metal fine particles have a primary particle diameter of 100 nm or less. 6. The metal cross-linking agent has two or more functional groups selected from a mercapto group, an amino group, a cyano group, a 2-pyridyl group, a diphenylphosphino group and a hydroxyl group. The conductive film according to any one of to 5. 7. The metal cross-linking agent is a linear alkyl compound having a functional group selected from a mercapto group, an amino group, a cyano group, a 2-pyridyl group, a diphenylphosphino group and a hydroxyl group at both ends. Claim 1 characterized by the above-mentioned.
The conductive film according to any one of to 5. 8. The metal fine particle holding layer comprises Si, Al, T
The conductive film according to claim 1, further comprising an alkoxy gel layer formed from a starting material containing at least one selected from various alkoxides of i and Zr. 9. The hydrolyzable silane compound, wherein the metal fine particle holding portion has a functional group selected from a mercapto group, an amino group, a cyano group, a 2-pyridyl group, and a diphenylphosphino group, The conductive film according to claim 8, wherein the conductive film is formed by bonding to the surface of the alkoxy gel layer. 10. The metal fine particle holding layer comprises Si, Al,
One selected from at least one selected from various alkoxides of Ti and Zr and a hydrolyzable silane compound having a functional group selected from a mercapto group, an amino group, a cyano group, a 2-pyridyl group and a diphenylphosphino group. The conductive film according to claim 1, further comprising a metal-retaining alkoxy gel layer capable of retaining the metal fine particles on the entire surface, which is formed from a starting material containing at least one kind or more. 11. A method for producing a conductive film having at least a conductive layer, the step of forming a metal fine particle holding layer having a patterned metal fine particle holding portion, the step of holding the metal fine particle in the metal fine particle holding layer, and the step of holding the metal fine particle holding layer. A method for producing a conductive film, comprising: a step of holding the metal crosslinking agent on the metal fine particles; and a step of holding the metal fine particles on the metal crosslinking agent. 12. The method according to claim 11, wherein the step of holding the metal cross-linking agent on the held metal fine particles and the step of holding the metal fine particles on the metal fine particles holding the metal cross-linking agent are repeated a plurality of times. The method for manufacturing a conductive film of. 13. The pattern of the metal fine particle holding portion is a mesh having a line width of 5 μm or less, and the area of the metal fine particle holding portion is 40% of the area of the metal fine particle holding layer.
The light transmittance in the visible light region of the entire conductive film is 50% or more, which is below.
2. The method for producing a conductive film as described in 2. 14. The metal fine particle holding part comprises a mercapto group,
12. The surface of the metal fine particle holding part has one or more kinds of functional groups selected from an amino group, a cyano group, a 2-pyridyl group and a diphenylphosphino group.
14. The method for producing a conductive film according to any one of 13 to 13. 15. The metal fine particles are Ag and / or A.
The method for producing a conductive film according to claim 11, further comprising u. 16. The method for producing a conductive film according to claim 15, wherein the fine metal particles have a primary particle diameter of 100 nm or less. 17. The metal fine particle holding layer forming step comprises:
On the alkoxy gel layer formed from a starting material containing at least one selected from various alkoxides of i, Al, Ti and Zr, the alkoxy gel layer is inactivated by the following hydrolyzable silane compound. After patterning the non-holding portion, a hydrolyzable silane having a functional group selected from a mercapto group, an amino group, a cyano group, a 2-pyridyl group, and a diphenylphosphino group in a portion where the non-holding portion is not formed. The method for producing a conductive film according to any one of claims 11 to 16, comprising forming one or more kinds of compounds as a metal fine particle holding portion. 18. The step of forming a metal fine particle holding layer comprises:
One or more selected from various alkoxides of i, Al, Ti and Zr, and a mercapto group, amino group, cyano group, 2
-Pyridyl group, formed from a starting material containing at least one or more selected from hydrolyzable silane compounds having a functional group selected from diphenylphosphino group,
The method for producing a conductive film according to claim 11, further comprising patterning a non-holding portion on the metal-holding alkoxy gel layer capable of holding the metal fine particles on the entire surface. 19. The non-retaining portion contains one or more kinds selected from various long-chain alkylsilane compounds containing a hydrolyzable group and various long-chain fluoroalkylsilane compounds containing a hydrolyzable group. Item 19. A method for producing a conductive film according to item 17 or 18. 20. The method for producing a conductive film according to claim 17, wherein the non-holding portion is formed by microcontact printing. 21. The step of holding the metal fine particles comprises immersing the metal fine particle holding layer in a dispersion liquid in which the metal fine particles are dispersed.
0. The method for producing a conductive film as described in 0. 22. The steps of holding the metal fine particles include an operation of applying a coating liquid containing the metal fine particles on the metal fine particle holding layer.
The method for producing a conductive film according to any one of 1. 23. The step of holding the metal cross-linking agent on the held metal fine particles includes an operation of immersing the metal fine-particle holding layer holding the metal in a solution containing the metal cross-linking agent. A method of manufacturing a conductive film according to claim 11. 24. The step of retaining the metal crosslinking agent on the retained metal fine particles includes an operation of applying a coating solution containing the metal crosslinking agent onto the metal fine particle retaining layer on which the metal is retained. The method for producing a conductive film according to any one of claims 11 to 22.