JP5607482B2 - Transparent conductive material and method for producing the same - Google Patents

Description

  The present invention relates to a transparent conductive material and a method for producing the same. More specifically, the present invention relates to a transparent conductor having excellent heat stability, high conductivity, and excellent permeability, and a simple manufacturing method thereof.

  The carbon nanotubes have a substantially cylindrical shape formed by winding one surface of graphite. A single-walled carbon nanotube is a single-walled carbon nanotube, a multi-walled carbon nanotube is a multi-walled carbon nanotube. What is wound in a layer is called a double-walled carbon nanotube. Carbon nanotubes have excellent intrinsic conductivity and are expected to be used as conductive materials.

  Transparent conductive films using carbon nanotubes are known. In order to produce a transparent conductive film using carbon nanotubes, when the carbon nanotubes are uniformly dispersed in a solvent, an ionic dispersant having excellent dispersibility is generally used. A uniform transparent conductor can be produced by obtaining a carbon nanotube aggregate that can provide a dispersion of a high concentration of carbon nanotube aggregates excellent in dispersibility.

  However, in general, the ionic dispersant is an insulating material, and decreases the conductivity of the carbon nanotube. Furthermore, since it has an ionic functional group, it is easily affected by environmental changes such as high temperature and high humidity, and resistance value stability is poor. From the above, when producing a transparent conductor having high conductivity and excellent permeability, it is necessary to remove the ionic dispersant used for dispersion from the transparent conductor.

  After applying the carbon nanotube dispersion liquid on the film, the excess ionic dispersant is removed by rinsing with water, so that the transparent conductive film having high conductivity and excellent permeability without damaging the characteristics of the carbon nanotube, The manufacturing method has been reported (for example, refer to Patent Document 1).

  In addition, a uniform carbon nanotube-containing polymer resin from which excess dispersant is removed by ultrafiltration has been reported (for example, see Patent Document 2).

  With respect to Patent Document 1, there is no description regarding heat resistance stability, and the rinsing process with water can be a major issue in mass productivity and mass production stabilization.

  In addition, Patent Document 2 relates to a carbon nanotube-containing polymer resin, and is not related to the transparent conductor and the method for producing the same, and there is no description regarding heat stability.

JP 2009-149516 A JP 2009-196877 A

  The present invention has been made in view of the above-mentioned problems and situations, and a solution to the problem is a transparent conductive material excellent in heat stability, high conductivity and excellent permeability, and a simple manufacturing method thereof. Is to provide.

  The inventors of the present application have found that the transparent conductivity and heat resistance stability are improved by removing the dispersant in advance by an ultrafiltration method in the course of intensive studies to solve the above-described problems, and the present invention has been achieved. It is a thing.

  That is, this invention consists of the following structures.

(I) The carbon nanotube [A], the dispersant [B], and the dispersion medium [C] have a mass ratio ([B] / [A]) of the dispersant [B] to the carbon nanotube [A] of 1 to 9. The dispersion liquid to be treated containing the carbon nanotube [A] content ratio {[A] / ([A] + [B] + [C])} in the range of 0.0003 to 0.015 mass% is dispersed. The dispersion liquid for coating is prepared by concentrating the concentration of carbon nanotubes of the treated dispersion liquid 10 to 500 times using an ultrafiltration membrane having a molecular weight cut off from the molecular weight of the agent [B]. After applying the liquid on the transparent substrate,
A method for producing a transparent conductor, comprising drying.

(II) The method for producing a transparent conductor according to claim 1, wherein the dispersant [B] is an ionic dispersant.

(III) The method for producing a transparent conductor according to claim 1 or 2, wherein the carbon nanotube [A] has a length of 1.0 µm or more.

(IV) The method for producing a transparent conductor according to any one of claims 1 to 3, wherein the carbon nanotube [A] dispersion contained in the dispersion to be treated has a diameter of 2.0 nm or less.

(V) On at least one surface of the transparent substrate, the carbon nanotube [A] and the dispersing agent [B] are added, and the mass ratio ([B] / [A]) of the dispersing agent [B] to the carbon nanotube [A] is 0. The conductive layer included in a range of 1 to 1.0 , and the increase in the resistance value of the conductive layer after heat treatment at 150 ° C. for 1 hour is 1.2 to 1.3 times that before the heat treatment. A transparent conductor.

(VI) The transparent conductor according to claim 5, wherein the dispersant [B] is an ionic dispersant.

(VII) The transparent conductor according to claim 5 or 6, wherein the carbon nanotube [A] has a length of 1.0 μm or more.

(VIII) The ratio of [550 nm light transmittance of transparent conductor] / [550 nm light transmittance of transparent substrate] is 50% or more, and the surface resistance value is 10 ⁰ to 10 ⁴ Ω / □. The transparent conductor according to any one of claims 5 to 7.

  According to the present invention, in a transparent conductor having carbon nanotubes on a base material and a base material, a liquid in which carbon nanotubes are dispersed in a solvent with a dispersant is removed in advance by an ultrafiltration method, A transparent conductor characterized by improving the transparent conductivity and heat resistance can be obtained by coating and drying on a substrate.

It is the figure which represented typically the ultrafiltration method in this invention.

  In the method for producing a transparent conductive material of the present invention, the carbon nanotube [A], the dispersant [B], and the dispersion medium [C] are mixed with a mass ratio of the dispersant [B] to the carbon nanotube [A] ([B] / [A]) is 1 to 9, and the content of carbon nanotube [A] {[A] / ([A] + [B] + [C])} is included in the range of 0.0003 to 0.015 mass%. A dispersion for coating is prepared by concentrating the concentration of carbon nanotubes in the dispersion to be treated 10 to 500 times using an ultrafiltration membrane having a molecular weight cut off larger than that of the dispersant [B]. The coating dispersion is coated on a transparent substrate and then dried.

  By manufacturing the transparent conductor through such steps, the heat resistance of the conductive layer containing the carbon nanotube [A] formed on the transparent substrate can be improved. That is, by adopting such a manufacturing method, it is possible to limit the dispersant [B] which is easily affected by environmental changes such as high temperature and high humidity and deteriorates resistance value stability before forming a conductive layer containing carbon nanotubes. By removing by the outer filtration method, it is possible to improve the conductivity of the conductive layer including the carbon nanotubes to be formed.

[carbon nanotube]
The carbon nanotube [A] used in the present invention is not particularly limited as long as it has a shape obtained by substantially winding one surface of graphite into a cylindrical shape. One surface of graphite is made into one layer. Both single-walled carbon nanotubes wound and multi-walled carbon nanotubes wound in multiple layers can be applied, and in particular, carbon having two or more double-walled carbon nanotubes in which one surface of graphite is wound in two layers is more than 50 out of 100 carbon nanotubes. It is preferable because the conductivity of the nanotube and the dispersibility of the carbon nanotube in the dispersion become extremely high. More preferably, 75 or more of 100 are double-walled carbon nanotubes, and most preferably 80 or more of 100 are double-walled carbon nanotubes. In addition, the double-walled carbon nanotube is preferable because the original function such as conductivity is not impaired even if the surface is functionalized by acid treatment or the like.

  A carbon nanotube is manufactured as follows, for example. A powdery catalyst in which iron is supported on magnesia is present in the entire horizontal cross-sectional direction of the reactor in a vertical reactor, methane is circulated in the vertical direction in the reactor, and methane and the catalyst are mixed in 500 to 1200. It is obtained by oxidizing the carbon nanotubes after contacting them at 0 ° C. to produce the carbon nanotubes. That is, carbon nanotubes containing single-walled to five-walled carbon nanotubes can be obtained by the carbon nanotube synthesis method. Carbon nanotubes can be oxidized and then subjected to an oxidation treatment to increase the ratio of single to 5 layers, particularly the ratio of 2 to 5 layers. The oxidation treatment is performed, for example, by a nitric acid treatment method. The nitric acid treatment method is not particularly limited as long as the carbon nanotube of the present invention can be obtained, but is usually performed in an oil bath at 140 ° C. The nitric acid treatment time is not particularly limited, but is preferably in the range of 5 hours to 50 hours.

  The length of the carbon nanotube is preferably 1.0 μm or more in order to produce a transparent conductor having high conductivity and high transmittance. More preferably, it is preferably 2.0 μm or more.

[Dispersant]
The dispersant [B] used in the present invention is a polymer or a low molecular weight anionic surfactant having a polysaccharide or an aromatic structure in the skeleton. Hereinafter, a polymer having a polysaccharide structure in the skeleton is referred to as a polysaccharide polymer, a polymer having an aromatic structure in the skeleton is referred to as an aromatic polymer, and a low molecular weight anionic surfactant is referred to as an anionic surfactant. The reason why such a dispersant [B] disperses the carbon nanotubes uniformly in the dispersion medium is considered as follows. Since carbon nanotubes are entangled with each other to form a strong aggregate, it is very difficult to disperse them in a solvent. In order to disperse and disperse carbon nanotubes in a solvent, it is necessary to interact with graphite of carbon nanotubes by π-electrons to break bundles and aggregates, or to dissolve bundles and aggregates by hydrophobic interactions with carbon nanotubes. . In the present invention, from the viewpoint of obtaining an isolated carbon nanotube dispersion from the above, it is presumed that the polysaccharide polymer and the aromatic polymer are effectively acting.

  Examples of the polysaccharide polymer preferably used for the dispersant [B] used in the present invention include carboxymethylcellulose and derivatives thereof, hydroxypropylcellulose and derivatives thereof, xylan and derivatives thereof. Among these, from the viewpoint of dispersibility, carboxymethyl cellulose or a derivative thereof is preferable, and further, use of an ionic salt of carboxymethyl cellulose or a derivative thereof is preferable. When a salt of the above carboxymethyl cellulose or a derivative thereof is used as the dispersant [B], examples of the cationic substance constituting the salt include alkali metal cations such as lithium, sodium and potassium, calcium, magnesium, barium and the like. Of alkaline earth metal cations, ammonium ions, or organic amines such as monoethanolamine, diethanolamine, triethanolamine, morpholine, ethylamine, butylamine, coconut oil amine, tallow amine, ethylenediamine, hexamethylenediamine, diethylenetriamine, polyethyleneimine Onium ions or these polyethylene oxide adducts can be used, but are not limited thereto.

  Examples of the aromatic polymer preferably used for the dispersant [B] used in the present invention include, for example, an aromatic polyamide resin, an aromatic vinyl resin, a styrene resin, an aromatic polyimide resin, a conductive polymer such as polyaniline, polystyrene sulfone. Examples thereof include acid and polystyrene sulfonic acid derivatives such as poly-α-methylstyrene sulfonic acid. Among these, from the viewpoint of dispersibility, use of polystyrene sulfonic acid or a derivative thereof is preferable, and further, use of an ionic salt of polystyrene sulfonic acid or a derivative thereof is preferable.

  Examples of the anionic surfactant preferably used for the dispersant [B] used in the present invention include octylbenzenesulfonate, nonylbenzenesulfonate, dodecylbenzenesulfonate, dodecyldiphenyletherdisulfonate, monoisopropylnaphthalene. Sulfonate, diisopropylnaphthalenesulfonate, triisopropylnaphthalenesulfonate, dibutylnaphthalenesulfonate, naphthalenesulfonate formalin condensate, sodium cholate, sodium deoxycholate, sodium glycocholate, cetyltrimethylammonium bromide, etc. Is mentioned. Of these, sodium cholate or dodecylbenzene sulfonate is preferably used from the viewpoint of dispersibility.

[Molecular weight of dispersant]
The molecular weight of the dispersant used in the present invention is preferably 1000 to 300,000 weight average molecular weight in consideration of an increase in the viscosity of the dispersion liquid soluble in the dispersion medium.

[Dispersion medium]
As the dispersion medium [C] used in the present invention, an aqueous or non-aqueous dispersion medium capable of dissolving the dispersant can be used. Water is preferable from the viewpoint of waste liquid treatment, environment and disaster prevention.

  Non-aqueous solvents include hydrocarbons (toluene, xylene, etc.), chlorine-containing hydrocarbons (methylene chloride, chloroform, chlorobenzene, etc.), ethers (dioxane, tetrahydrofuran, methyl cellosolve, etc.), ether alcohols (ethoxyethanol, methoxy) Ethoxyethanol, etc.), esters (methyl acetate, ethyl acetate, etc.), ketones (cyclohexanone, methyl ethyl ketone, etc.), alcohols (ethanol, isopropanol, phenol, etc.), lower carboxylic acids (acetic acid, etc.), amines (triethylamine, triethylamine, etc.) Methanolamine, etc.), nitrogen-containing polar solvents (N, N-dimethylformamide, nitromethane, N-methylpyrrolidone, etc.), sulfur compounds (dimethyl sulfoxide, etc.) and the like can be used.

[Processed dispersion]
The dispersion to be treated used in the present invention refers to a dispersion in which carbon nanotubes [A] are isolatedly dispersed using the above-mentioned dispersant [B] and dispersion medium [C]. This is because if the dispersion of the dispersion to be treated is insufficient, it may aggregate on the filtration membrane during the ultrafiltration. In the present invention, as the dispersibility index, the diameter of the carbon nanotube dispersion representing isolated dispersion in the dispersion is used as the index. The diameter of the carbon nanotube dispersion is an apparent diameter of the carbon nanotube dispersion, which is large in an aggregated bundle and is the diameter of the carbon nanotube itself at the time of isolated dispersion, and is an index indicating the dispersion state of the carbon nanotube. Usually, carbon nanotubes exist stably as a bundle in a solution. However, by increasing the dispersibility of the solution to be treated by adding a dispersant or the like, it is possible to loosen the bundle and make the carbon nanotubes isolated. “Dispersed in isolation” means that the diameter of the carbon nanotube dispersion is 3.0 nm or less. The method for measuring the diameter of the carbon nanotube dispersion is shown below. The concentration of carbon nanotubes in the measurement liquid in which carbon nanotubes are dispersed is adjusted to 0.003 wt%, and spin coating is performed on a mica substrate. Then, it calculates | requires as an average of the diameter of about 100 carbon nanotube dispersion | distribution at random by AFM (Shimadzu, SPM9600M).

  The treated dispersion used in the present invention has a mass ratio ([B] / [A]) of the dispersant [B] to the carbon nanotube [A] of 1 to 9. When the mass ratio ([B] / [A]) is less than 1, it is difficult to uniformly disperse, which is not suitable. On the other hand, when the mass ratio ([B] / [A]) of the dispersant [B] to the carbon nanotube [A] is more than 9, the number of filtrations for improving the heat stability is increased, and the number of processes is simplified. It is not suitable because the merit is lost.

  In addition, the dispersion liquid to be treated used in the present invention has a carbon nanotube [A] content {[A] / (carbon nanotube [A] + dispersant [B] + dispersion medium [C])} of 0.0003 to The range is 0.015% by mass. When the content of carbon nanotube [A] {[A] / (carbon nanotube [A] + dispersant [B] + dispersion medium [C])} is less than 0.0003, the amount of the solution to be filtered is very large. This is unsuitable because the benefits of simplification of processes are lost. On the other hand, when the content {[A] / (carbon nanotube [A] + dispersant [B] + dispersion medium [C])} of the carbon nanotube [A] is more than 0.015, an aggregate due to an increase in concentration It is not suitable because there is concern about the occurrence of

  The preparation method of the dispersion to be treated used in the present invention is not particularly limited as long as the dispersion state described above can be obtained. For example, the following procedure can be used. In other words, it is possible to prepare a dispersion to be treated by dispersing at the above concentration from the time of dispersion, or to disperse in a deeper concentration range at the time of dispersion and to dilute with a dispersion medium after dispersion to adjust to the predetermined concentration. . Among them, since the treatment time at the time of dispersion can be shortened, once a dispersion solution containing carbon nanotubes in a concentration range of 0.003 to 0.15 mass% in the dispersion medium is prepared, dilution is performed to obtain a predetermined value. The concentration is preferably used. Dispersion means during the preparation include mixing and dispersing machines commonly used for coating production of carbon nanotubes and a dispersant in a dispersion medium (for example, a ball mill, a bead mill, a sand mill, a roll mill, a homogenizer, an ultrasonic homogenizer, a high-pressure homogenizer, an ultrasonic device, an atomizer. A lighter, a dissolver, a paint shaker, etc.). Among them, the method of dispersing using an ultrasonic device is preferable because the dispersibility of the carbon nanotubes in the obtained dispersion is good.

  The diameter of the carbon nanotube dispersion in the dispersion to be treated thus prepared is preferably 2.0 nm or less, and more preferably 1.5 nm or less.

[Ultrafiltration membrane]
In the present invention, the dispersion to be treated is ultrafiltered using an ultrafiltration membrane, and the concentration of the carbon nanotube dispersion is concentrated 10 to 500 times to prepare a coating dispersion.

  The ultrafiltration membrane is a filtration membrane intended for a liquid, and the size of the pore is not clearly defined, but is usually 0.01 μm or less. As shown in FIG. 1, ultrafiltration is a separation technique in which particles in a solution are removed using an ultrafiltration membrane 1 to obtain a filtrate 2. Regarding the pores 3 of the ultrafiltration membrane 1, since it may be difficult to see the pores of the membrane with an electron microscope or the like, an index indicating the size of the pores 3 is used as a standard substance having a known molecular weight. A method is adopted in which the molecular weight corresponding to a blocking rate of 90% is determined by permeation. This molecular weight is called fractionated molecular weight. Usually, the molecular weight cutoff of the ultrafiltration membrane is about 1,000 to 300,000. Ultrafiltration membranes are roughly classified into organic membranes using polymer materials and inorganic membranes such as ceramic membranes from the viewpoint of materials. Examples of the polymer membrane include cellulose acetate, polyacrylonitrile, and polysulfone.

  The ultrafiltration membrane 1 used in the present invention has a molecular weight cut off larger than that of the dispersant [B]. As a result, it is possible to concentrate the concentration of carbon nanotubes contained in the carbon nanotube-treated dispersion liquid 4 by removing the dispersant having a weight average molecular weight equal to or lower than the molecular weight cutoff of the ultrafiltration membrane together with the dispersion medium. It becomes.

  Examples of the material of the filtration membrane include polymer materials such as polysulfone, polyacrylonitrile, polyolefin polymer electrolyte complex, cellulose acetate derivative, polyacrylonitrile, polyolefin, polyvinyl alcohol, polyethersulfone, polyamide, polioimide, aromatic polyamide, and polyimide. Inorganic ceramics such as alumina and porous ceramics are preferred. In particular, polysulfone is preferable in that the molecular weight cut off is large.

[Dispersant amount after ultrafiltration]
In the present invention, in the ultrafiltration step, the concentration of carbon nanotubes in the dispersion is concentrated 10 to 500 times (that is, 90 to 99.8% by volume of the dispersion to be treated is removed) for coating. A dispersion is obtained. Regarding the amount ratio of the dispersing agent in the coating dispersion, the carbon nanotube [A] and the dispersing agent [B are used in order to improve the heat resistance stability (the decrease in the resistance value change rate after heating at 150 ° C. for 1 hour is small). The mass ratio of [B] to [A] ([B] / [A]) is preferably in the range of 0.1 to 1.0. More preferably, the mass ratio of [B] to [A] ([B] / [A]) is in the range of 0.1 to 0.8. When the mass ratio of [B] to [A] ([B] / [A]) is 1.0 or less, the change in the resistance value of the conductive layer after heat treatment at 150 ° C. for 1 hour is Can be suppressed to 1.0 to 1.3 times. Regarding the lower limit of the mass ratio of [B] to [A] ([B] / [A]), the lower the better, the better. However, from the viewpoint of dispersibility of the coating dispersion after ultrafiltration Therefore, it is preferably 0.1 or more.

  In order to quantify the amount of the dispersant removed by filtration, an analysis method corresponding to the type of the dispersant may be applied as appropriate. In the case of carboxymethylcellulose or a derivative thereof, or a salt thereof that can be preferably used in the present invention as the dispersant, anthrone sulfate method, which is one of the methods for quantifying saccharides, can be mentioned. In this analysis method, the glycosidic bond of a polysaccharide is hydrolyzed with concentrated sulfuric acid, and further dehydrated to furfural and its derivatives, then reacted with anthrone to form a blue-green complex, and the absorbance of the saccharide is determined by absorbance measurement. Perform quantification.

  The coating dispersion prepared by such a method has a carbon nanotube dispersion having a diameter of 2.0 nm or less, and has good dispersibility like the dispersion to be treated.

[Transparent substrate]
In this invention, after apply | coating the dispersion liquid for coating obtained as mentioned above on a transparent base material, it is made to dry and a transparent conductive body is manufactured. A transparent substrate means what has the performance which permeate | transmits 50% or more of light with a wavelength of 550 nm at least. As long as these characteristics are satisfied, the form is not particularly limited. For example, even a transparent film that can be wound up to a thickness of 250 μm or less, a transparent substrate exceeding 250 μm in thickness can be applied.

  Examples of the transparent base material used in the present invention include resin and glass. Examples of the resin include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polycarbonate (PC), polymethyl methacrylate (PMMA), polyimide, polyphenylene sulfide, aramid, polypropylene, polyethylene, polylactic acid, polyvinyl chloride, Examples include polymethyl methacrylate, alicyclic acrylic resin, cycloolefin resin, and triacetyl cellulose. As the glass, ordinary soda glass can be used. Moreover, these several base materials can also be used in combination. For example, a composite substrate such as a substrate in which a resin and glass are combined and a substrate in which two or more kinds of resins are laminated may be used. The resin film may be provided with a hard coat. The kind of transparent substrate is not limited to the above, and an optimal one can be selected from transparency, durability, cost, etc. according to the application.

[Application of dispersion liquid for coating to transparent substrate]
In the method for producing a transparent conductive body of the present invention, the coating dispersion obtained above is applied to a transparent base material, and then the solvent is dried to fix the carbon nanotubes on the transparent base material. obtain.

  In the present invention, the method for applying the coating dispersion on the transparent substrate is not particularly limited. Known application methods such as spray coating, dip coating, spin coating, knife coating, kiss coating, gravure coating, slot die coating, screen printing, inkjet printing, pad printing, other types of printing, or roll coating can be used . The application may be performed in a plurality of times, or two different application methods may be combined. The most preferred application method is roll coating.

[Adjustment of coating thickness]
Since the coating thickness (wet thickness) when coating the coating dispersion on the transparent substrate also depends on the concentration of the coating dispersion, it may be adjusted as appropriate so that the desired light transmittance and surface resistance can be obtained. . The coating amount of the carbon nanotubes in the present invention can be easily adjusted to achieve various uses requiring transparent conductivity. For example, by increasing the film thickness, the surface resistance is lowered, and the film thickness is decreased. to have a higher tendency by the coating amount be ^1mg / ^{m 2 ~40mg} / m 2 in the case when a transparent conductive film 550nm light transmittance of / the 550nm light transmittance of the substrate more than 50% Can do.

If the coating amount is 40 mg / m ² or less, it can be 50% or more. Furthermore, if the coating amount is 30 mg / m ² or less, it can be 60% or more. Furthermore, if the coating amount is 20 mg / m ² or less, it can be 70% or more, and if the coating amount is 10 mg / m ² or less, it can be 80% or more.

The light transmittance at 550 nm of the substrate means the light transmittance including the surface resin layer when the substrate has a surface resin layer. The surface resistance of the film by the coating amount is also readily adjustable, it coating weight surface resistance of the film if ^1mg / ^{m 2 ~40mg} / m 2 is to be ¹⁰ 0 ^{~10 4 Ω} / □ This is preferable. Furthermore, although depending on the content of the aromatic polymer and various additives, the surface resistance of the film can be 10 ¹ Ω / □ or less if the coating amount is 40 mg / m ² or less. If the coating amount is 30 mg / m ² or less, the surface resistance value of the film can be 10 ² Ω / □ or less. Furthermore, if the application amount is 20 mg / m ² or less, it can be 10 ³ Ω / □ or less, and if the application amount is 10 mg / m ² or less, it can be 10 ⁴ Ω / □ or less.

[Wetting agent]
When applying the coating dispersion on the transparent substrate, a wetting agent may be added to the coating dispersion in order to suppress coating unevenness. When a water-based dispersion ratio is selected as the dispersion medium for the coating dispersion and coating is performed on a transparent substrate having a non-hydrophilic surface, a wetting agent such as a surfactant or alcohol is added to the coating dispersion. Thus, the coating dispersion liquid can be applied on the transparent substrate without being repelled. As the wetting agent, alcohol is preferable, and methanol, ethanol, propanol, and isopropanol are preferable among alcohols. Lower alcohols such as methanol, ethanol and isopropanol are highly volatile and can be easily removed when the substrate is dried after coating. In some cases, a mixture of alcohol and water may be used.

[Heat resistance stability]
Regarding the heat resistance stability of the transparent conductor of the present invention after heat treatment at 150 ° C. for 1 hour, the change in the resistance value of the conductive layer is preferably 1.2 to 1.3 times that before the heat treatment . By the range of this, a touch panel, liquid crystal display, it can be preferably used an organic electroluminescence, as a transparent conductive film-coated substrate, such as electronic paper. That is, if the change in resistance value after the treatment is 1.2 to 1.3 times or less, a stable operation with a small error can be realized as the base material.

[Transparent conductivity]
Regarding the transparent conductivity of the transparent conductor of the present invention, the ratio of the light transmittance of 550 nm of the transparent conductor / the light transmittance of 550 nm of the transparent substrate is 50% or more, and the surface resistance value is 10 ⁰ to 10 ⁴ Ω / □. Preferably there is.

More preferably, the ratio of the light transmittance of 550 nm of the transparent conductor / the light transmittance of 550 nm of the transparent substrate is 80% or more, and the surface resistance value is preferably 10 ⁰ to 10 ⁴ Ω / □. By being in this range, it can be preferably used as a substrate with a transparent conductive film such as a touch panel, a liquid crystal display, organic electroluminescence, and electronic paper. That is, if it is 1 × 10 ⁰ Ω / □ or more, the substrate can have high transmittance and low power consumption, and if it is 1 × 10 ⁴ Ω / □ or less, the above coordinates of the touch panel can be obtained. The influence of errors in reading can be reduced.

[Use of transparent conductive film of the present invention]
The transparent conductive film of the present invention is used as a display-related transparent electrode such as a touch panel, a liquid crystal display, organic electroluminescence, and electronic paper, which are mainly required to have a smooth surface.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by these Examples. The measurement method used in this example is shown below.
In addition, especially the thing which does not show n number is measuring by n number 2, and has shown the average value.

(1) Surface resistance value The probe shown below was brought into close contact with the conductive layer side at room temperature by the four-terminal method at the center of the conductive surface of the transparent conductive composite material sampled to 5 cm × 10 cm, and the resistance value was measured. The measuring instrument used was a resistivity meter MCP-T360 type manufactured by Dia Instruments Co., Ltd., and the MCP-TPO 3P manufactured by Dia Instruments Co., Ltd. was used as the 4-probe probe.

(2) 550 nm transmittance Based on JIS-K7361 (1997), the light transmittance was obtained by loading the film into a spectrophotometer (Hitachi U-2100) and measuring the light transmittance at a wavelength of 550 nm. .
Next, a method for producing a carbon nanotube transparent conductive composite material and an evaluation result will be described.

(3) Measurement of carbon nanotube length After spin coating a carbon nanotube dispersion liquid adjusted to a concentration of 0.003 wt% on a mica substrate, the diameter of the carbon nanotube dispersion is 1.5 nm or less by AFM (Shimadzu, SPM9600M). Only the carbon nanotube length was measured.

(4) Diameter measurement of carbon nanotube dispersion After adjusting the concentration of carbon nanotubes in the measurement liquid in which carbon nanotubes are dispersed to 0.003 wt% and spin-coating on a mica substrate, randomization is performed by AFM (Shimadzu, SPM9600M). The diameter of about 100 carbon nanotube dispersions was measured.

(5) Dispersant quantification method 100 ml of the filtrate obtained by ultrafiltration of the treated dispersion was concentrated under reduced pressure using an evaporator until water disappeared, and the concentrate was washed with water in a 25 ml volumetric flask. I was up. Anthrone sulfuric acid test solution (66 mL of sulfuric acid was added to 34 mL of water and dissolved by adding 50 mg of anthrone and then dissolved by adding 1 g of thiourea to the above sample) and heated in a boiling bath for 10 minutes. Thereafter, the sample was quenched in cold water, and the absorbance at 620 nm was measured. The CMC content of the specimen or the like was determined by plotting the absorbance on a calibration curve created from the absorbance of the standard diluent.

(6) Molecular weight measurement method for dispersant Using gel permeation chromatography (GPC, Shimadzu Corporation, 10A series (pump, injector, etc.) LC Solution, column used, Shodex / Asahi GF-7M HQ manufactured by Showa Denko KK The weight average molecular weight (Mw) of an aqueous lithium bromide solution (10 mmol / L) was measured at a sample concentration of 0.48 mg / ml, an injection amount of 100 μl, a flow rate of 1.0 ml / min, and a time of 30 min.

Example 1
[Catalyst preparation example]
About 24.6 g of iron (III) ammonium citrate (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 6.2 kg of ion-exchanged water. About 1000 g of magnesium oxide (MJ-30 manufactured by Iwatani Corporation) was added to this solution, and after vigorously stirring with a stirrer for 60 minutes, the suspension was introduced into a 10 L autoclave container. At this time, 0.5 kg of ion exchange water was used as a washing solution. In a sealed state, it was heated to 160 ° C. and held for 6 hours. Thereafter, the autoclave container was allowed to cool, the slurry-like cloudy substance was taken out from the container, excess water was filtered off by suction filtration, and a small amount of water contained in the filtered material was dried by heating in a 120 ° C. drier. The obtained solid content was collected on a sieve, and the particle size in the range of 20 to 32 mesh was collected while being finely divided in a mortar. The granular catalyst body shown on the left was introduced into an electric furnace and heated at 600 ° C. for 3 hours in the atmosphere. The bulk density was 0.32 g / mL. Further, when the filtrate was analyzed by an energy dispersive X-ray analyzer (EDX), iron was not detected. From this, it was confirmed that the added iron (III) ammonium citrate was supported on the entire amount of magnesium oxide. Furthermore, from the EDX analysis result of the catalyst body, the iron content contained in the catalyst body was 0.39 wt%.

[Production Example 1 of carbon nanotube-containing composition]
132 g of the solid catalyst body prepared in the catalyst preparation example was taken and introduced onto the quartz sintered plate at the center of the reactor installed in the vertical direction. While heating the catalyst layer until the temperature in the reaction tube reaches about 860 ° C., nitrogen gas is supplied from the bottom of the reactor toward the top of the reactor using a mass flow controller at 16.5 L / min. Circulated to pass through. Thereafter, while supplying nitrogen gas, methane gas was further introduced at 0.78 L / min for 60 minutes using a mass flow controller, and the gas was passed through the catalyst body layer for reaction. The contact time (W / F) obtained by dividing the weight of the solid catalyst body by the flow rate of methane at this time was 169 min · g / L, and the linear velocity of the gas containing methane was 6.55 cm / sec. The quartz reaction tube was cooled to room temperature while the introduction of methane gas was stopped and nitrogen gas was passed through at 16.5 L / min.

  The heating was stopped and the mixture was allowed to stand at room temperature. After the temperature reached room temperature, the carbon nanotube-containing composition containing the catalyst body and the carbon nanotubes was taken out from the reactor.

[Production Example 2 of carbon nanotube-containing composition]
Using 115 g of the carbon nanotube composition with catalyst obtained in Production Example 1 containing carbon nanotubes, the catalyst metal, iron, and its carrier, MgO, are dissolved by stirring in 2000 mL of a 4.8N hydrochloric acid aqueous solution for 1 hour. did. The obtained black suspension was filtered, and the filtered product was again put into 400 mL of a 4.8N hydrochloric acid aqueous solution, treated with MgO, and collected by filtration. This operation was repeated three times to obtain a carbon nanotube composition from which the catalyst was removed. The above-mentioned carbon nanotube composition was added to concentrated nitric acid (first grade assay 60 to 61%, manufactured by Wako Pure Chemical Industries, Ltd.) having a weight of about 300 times. Thereafter, the mixture was heated to reflux with stirring in an oil bath at about 140 ° C. for 25 hours. After heating to reflux, a nitric acid solution containing the carbon nanotube-containing composition was diluted with ion-exchanged water three times and suction filtered. The carbon nanotube composition was stored in a wet state containing water after washing with ion-exchanged water until the suspension of the filtered material became neutral. The average outer diameter of the carbon nanotube composition was 1.7 nm. The proportion of the double-walled carbon nanotubes was 90%, the Raman G / D ratio measured at a wavelength of 633 nm was 79, and the combustion peak temperature was 725 ° C.

(Preparation of treated dispersion)
Wet water-containing carbon nanotube composition obtained in a 20 mL container, weigh 15 mg in terms of dryness, 1 wt% sodium carboxymethylcellulose solution (11 kDa, 50-200 cps manufactured by Daicel), and add ion-exchanged water. 10 g. Nitric acid was used to adjust the pH to 4.0, and an ultrasonic homogenizer output was 20 W, and dispersion treatment was performed under ice-cooling for 7.5 minutes to prepare a carbon nanotube solution. The liquid temperature during dispersion was adjusted to 10 ° C. or lower. The obtained liquid was centrifuged at 10,000 G for 15 minutes with a high-speed centrifuge to obtain 9 mL of the supernatant. Ion exchanged water was added to the supernatant, and the concentration was adjusted so that the carbon nanotubes would be 0.0015 wt% to obtain a treated dispersion.

  The above dispersion to be treated is ultrafiltered at 0.3 MPa with a compressor using an ultrafilter Q2000 (fractional molecular weight 200,000, manufactured by ADVANTEC) and a stirring type ultra holder UHP-76K, and further ultrafilter unit USY. Ultrafiltration was performed using -20 (ADVANTEC) and a syringe for pressurization. By this operation, the solution to be treated was concentrated to 0.15 wt% to prepare a coating dispersion.

  After adding ion-exchanged water and ethanol to the above dispersion for coating to adjust the dispersion concentration to 0.08 wt% and the ethanol concentration to 4 wt%, a wire bar is used on a PET film (Toray Co., Ltd. Lumirror U46). The carbon nanotube composition was fixed by drying for 1 minute in a 125 ° C. dryer.

  As a result of measuring the length of the carbon nanotube, it was 2.13 μm.

  As a result of measuring the diameter of the carbon nanotube dispersion, it was 1.44 nm.

(Example 2)
The water-containing wet carbon nanotube composition obtained in the 20 mL container was weighed in a dry conversion equivalent of 15 mg, 1 wt% sodium carboxymethylcellulose (11 kDa, 50 to 200 cps) aqueous solution, and ion-exchanged water was added. Added to 10 g. Nitric acid was used to adjust the pH to 4.0, and an ultrasonic homogenizer output was 20 W, and dispersion treatment was performed under ice-cooling for 7.5 minutes to prepare a carbon nanotube solution. The liquid temperature during dispersion was adjusted to 10 ° C. or lower. The obtained liquid was centrifuged at 10,000 G for 15 minutes with a high-speed centrifuge to obtain 9 mL of the supernatant. Ion exchanged water was added to the supernatant, and the concentration was adjusted so that the carbon nanotubes would be 0.0015 wt% to obtain a treated dispersion.

The treated dispersion was subjected to ultrafiltration using an ultra filter unit USY-20 (fractionated molecular weight 200,000, ADVANTEC) and a syringe for pressurization. By repeating this operation, the solution was concentrated to 0.15 wt% to prepare a coating dispersion.
The carbon nanotube dispersion was applied onto a PET film (Lumirror U46 manufactured by Toray Industries, Inc.) using a wire bar and dried in a 125 ° C. dryer for 1 minute to immobilize the carbon nanotube composition.

  As a result of measuring the length of the carbon nanotube, it was 2.28 μm.

  As a result of measuring the diameter of the carbon nanotube dispersion, it was 1.14 nm.

(Comparative Example 1)
The treated dispersion liquid of Example 1 was applied onto a PET film (Lumilar U46 manufactured by Toray Industries, Inc.) using a wire bar, and dried in a 125 ° C. dryer for 1 minute to immobilize the carbon nanotube composition.

  This film was rinsed with ion exchange water for 30 seconds to remove the dispersant. After rinsing, water droplets adhering to the film were removed with an air duster and then dried at room temperature.

(Comparative Example 2)
The treated dispersion liquid of Example 2 was applied onto a PET film (Lumilar U46 manufactured by Toray Industries, Inc.) using a wire bar and dried in a 125 ° C. dryer for 1 minute to immobilize the carbon nanotube composition.

  This film was rinsed with ion exchange water for 30 seconds to remove the dispersant. After rinsing, water droplets adhering to the film were removed with an air duster and then dried at room temperature.

(Comparative Example 3)
The treated dispersion liquid of Example 1 was applied onto a PET film (Lumilar U46 manufactured by Toray Industries, Inc.) using a wire bar, and dried in a 125 ° C. dryer for 1 minute to immobilize the carbon nanotube composition.

(Comparative Example 4)
The treated dispersion liquid of Example 2 was applied onto a PET film (Lumilar U46 manufactured by Toray Industries, Inc.) using a wire bar and dried in a 125 ° C. dryer for 1 minute to immobilize the carbon nanotube composition.

  The evaluation results of the above Examples and Comparative Examples are summarized in Table 1.

  As mentioned above, although the Example of invention was described, this invention is not limited to the said Example, A various change can be made within the range of the summary of this invention described in the claim. .

  The transparent conductive material and the method for producing the same according to the present invention can be widely used as a conductive material requiring heat stability, high transparency, and conductivity.

DESCRIPTION OF SYMBOLS 1 Ultrafiltration membrane 2 Filtrate 3 Pore 4 Dispersion A Carbon nanotube B Dispersant C Dispersion medium

Claims (8)

  The carbon nanotube [A], the dispersant [B], and the dispersion medium [C] have a mass ratio ([B] / [A]) of the dispersant [B] to the carbon nanotube [A] of 1 to 9, carbon nanotubes The dispersion liquid to be treated containing the content of [A] {[A] / ([A] + [B] + [C])} in the range of 0.0003 to 0.015% by mass is added to the dispersant [B The concentration of carbon nanotubes in the dispersion to be treated is concentrated 10 to 500 times using an ultrafiltration membrane having a fractional molecular weight greater than the molecular weight of A method for producing a transparent conductor, wherein the transparent conductor is dried after being applied onto a substrate.   The manufacturing method of the transparent conductor of Claim 1 whose said dispersing agent [B] is an ionic dispersing agent.   The manufacturing method of the transparent conductor of Claim 1 or 2 whose length of the said carbon nanotube [A] is 1.0 micrometer or more.   The manufacturing method of the transparent conductor in any one of Claims 1-3 whose diameter of the carbon nanotube [A] dispersion | distribution contained in the said to-be-processed dispersion liquid is 2.0 nm or less. On at least one side of the transparent substrate, the carbon nanotube [A] and the dispersant [B] are mixed at a mass ratio ([B] / [A]) of the dispersant [B] to the carbon nanotube [A] of 0.1 to 0.1. It has a conductive layer included in a range of 1.0, and the increase in the resistance value of the conductive layer after heat treatment at 150 ° C. for 1 hour is 1.2 to 1.3 times that before the heat treatment. Transparent conductor.   The transparent conductor according to claim 5, wherein the dispersant [B] is an ionic dispersant.   The transparent conductor according to claim 5 or 6, wherein the carbon nanotube [A] has a length of 1.0 µm or more. The ratio of [550 nm light transmittance of transparent conductor] / [550 nm light transmittance of transparent substrate] is 50% or more, and the surface resistance value is 10 ⁰ to 10 ⁴ Ω / □. The transparent conductor according to any one of 7.

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