KR20200009773A - A conductive film comprising crystal violet and silver nano wire and a composition for forming conductive film comprising crystal violet and silver nano wire ink - Google Patents

Abstract

The present invention relates to a conductive film including crystal violet and a silver nanowire and a conductive film forming composition including crystal violet and a silver nanowire ink. The conductive film forming composition further includes crystal violet to improve a yellowing phenomenon of the conductive film when manufacturing the conductive film or a transparent conductive film including a silver nanowire. In addition, the conductive film forming composition is excellent in optical properties, sheet resistance, UV light resistance and heat resistance so as to be usefully used in electrodes such as a liquid crystal display device, a plasma display device, a touch panel, an electroluminescent device, a thin film solar cell, a dye-sensitized solar cell, and an inorganic crystalline solar cell.

Description

A conductive film comprising crystal violet and silver nano wire and a composition for forming conductive film comprising crystal violet and silver nano wire ink}

A conductive film comprising a crystal violet and silver nanowires, and a composition for forming a conductive film comprising crystal violet and silver nanowire inks.

The transparent conductive substrate refers to a substrate that is transparent in the visible region by forming a transparent conductive thin film such as ITO on one surface of a glass substrate or a plastic film, and has conductivity, and is widely used in touch panels and the like.

In such a transparent conductive substrate, important performances are conductivity and transparency, and when the conductivity drops, smooth driving is difficult, and when the transparency decreases, the display performance decreases. However, when the thickness of the conductive thin film is increased to improve the conductivity of the conductive substrate, it is very difficult to improve both the conductivity and the transparency because the transmittance is decreased while the surface reflectance and the absorption rate of the conductive thin film increase.

Silver nanowire, one of the next generation transparent electrode materials that can replace ITO, is a metal material in the form of an elongated wire that is tens of micrometers in length and tens of nanometers in diameter. Silver, a material of nanowires, is a material with high electrical conductivity among various metals, and its reserves are not concentrated in some countries. In addition, silver nanowires have a great competitiveness among materials replacing ITO due to their simple manufacturing process and low manufacturing cost. In addition, when silver is manufactured in the form of nanowire, which is a one-dimensional structure, electrodes can be formed on a film having a curvature, so that it can be applied to a flexible display product, which is one of the disadvantages of ITO, and has high design freedom.

However, despite many advantages of the silver nanowire electrode, the silver nanowire electrode has a phenomenon that the surface of the electrode is changed to yellow by the silver nanowire when the electrode is manufactured, which is a major disadvantage in the high transmittance required for the transparent electrode. Furthermore, the yellow color of the electrode surface is less visible because of the problem of the electrode pattern is visible when introduced to the pattern electrode, such as a touch screen [15]. In addition, the silver nanowire has a property of returning to silver oxide, which is a state before the silver nanowire, as a characteristic of a metal material, and when the electrode is oxidized, electrical conductivity is lost and resistance increases.

S. Ye, et al. “Metal Nanowire Networks: The Next Generation of Transparent Conductors” Adv. Mater. 1-18 (2014) E. H. Cho, et al. "Low-visibility patterning of transparent conductive silver-nanowire films" Electro-optical materials 26095-26103 (2015)

One object of the present invention is to provide a conductive film with improved yellowing including silver nanowires.

Another object of the present invention is to provide a composition for forming a conductive film containing silver nanowire ink.

It is another object of the present invention to provide a transparent conductive film having improved yellowing including silver nanowires.

Another object of the present invention is to provide a method for producing the transparent conductive film.

In order to achieve the above object,

According to an aspect of the present invention, as a conductive film comprising silver nanowires,

A conductive film is provided, wherein the conductive film comprises crystal violet.

According to another aspect of the invention, the composition for forming a conductive film comprising a silver nanowire ink,

Provided is a composition for forming a conductive film, wherein the composition comprises crystal violet dispersed in a solvent, wherein the composition comprises crystal violet.

According to another aspect of the invention, a transparent substrate; And

On one side of the transparent substrate is provided a transparent conductive film comprising silver nanowires and crystal violet.

According to another aspect of the invention, preparing a transparent substrate (step 1);

A method of manufacturing a transparent conductive film is provided, comprising: depositing a conductive film including silver nanowires and crystal violet on one surface of the transparent substrate (step 2).

The composition for forming a conductive film including the silver nanowires of the present invention further includes crystal violet, so that yellowing of the conductive film is improved when the conductive film or the transparent conductive film including the silver nanowires is manufactured, thereby providing excellent optical properties. In addition, it is excellent in sheet resistance, UV light resistance and heat resistance, and can be usefully used for electrodes such as liquid crystal displays, plasma displays, touch panels, electroluminescent devices, thin film solar cells, dye-sensitized solar cells, and inorganic crystalline solar cells. have.

Hereinafter, the present invention will be described in detail.

One aspect of the present invention is to provide a conductive film comprising silver nanowires with improved yellowing,

Specifically, it provides a conductive film comprising silver nanowires, the conductive film comprises a crystal violet.

In the conductive film, the crystal violet may be dispersed in the conductive film.

In addition, the conductive film may further include KOH, and KOH may be dispersed in the conductive film.

The conductive film including silver nanowires according to the present invention exhibits the best optical properties when considering both haze, b * and a * values by including crystal violet instead of other dyes (Experimental Example 1 and Table 2). Reference).

In addition, the conductive film including silver nanowires according to the present invention includes crystal violet, and further includes KOH, thereby exhibiting optical properties and sheet resistance, UV light resistance, and heat resistance, which are improved when the crystal violet is included alone. (See Experimental Example 4 and Table 5)

The conductive film including the silver nanowires according to the present invention includes a crystal violet, so that the sheet resistance is 40 kW / sq or less, the b * value is 1.0 or less, the light transmittance is 85% or more, and the haze value is 0.8% or less. As a conductive film, in particular, it can be usefully used as a transparent conductive film.

In addition, since it is possible to implement a wide range of transparent conductive film by adjusting the concentration, it can be usefully used in electrical or optical devices. Specific examples thereof may be usefully used in electrodes such as liquid crystal displays, plasma displays, touch panels, electroluminescent devices, thin film solar cells, dye-sensitized solar cells, and inorganic crystalline solar cells.

Another aspect of the present invention is a composition for forming a conductive film containing silver nanowire ink,

Provided is a composition for forming a conductive film, wherein the composition comprises crystal violet dispersed in a solvent, wherein the composition comprises crystal violet.

Specifically, the composition is obtained by incorporating crystal violet dispersed in a solvent into a silver nanowire ink, and crystal violet dispersed in a solvent represents a crystal violet solution in which crystal violet is dispersed in a solvent.

In the composition for forming a conductive film,

The solvent may be any one selected from the group consisting of water, ethanol, dimethylsulfoxide (DMSO), acetonitrile, diacetone alcohol and tetrahydrofuran, and may be acetonitrile.

When acetonitrile is used as a solvent, the b * value decreases the most, and other solvents do not exhibit UV light resistance. Therefore, the use of acetonitrile as a solvent may be used to transmit permeability, Haze, b *, sheet resistance, and UV light resistance. Given all the values, they may be suitable (see Experimental Example 2 and Table 3).

Crystal violet may be included in an amount of 1 to 1.7 wt% based on 100 wt% of the solvent. When the crystal violet is added in less than 1 wt%, the decrease in b * value is small, and when it exceeds 1.7 wt%, the sheet resistance value rises rapidly and there is a problem that the solubility is poor.

In addition, the crystal violet may be included in an amount of 1.2 to 1.5 wt% with respect to 100 wt% of the solvent. When the crystal violet is included in an amount of 1.2 to 1.5 wt% based on 100 wt% of the solvent, optical properties, sheet resistance, and solubility may all be excellent.

The composition may further comprise KOH. KOH is contained in crystal violet dispersed in a solvent and mixed in silver nanowire ink.

KOH may be included in an amount of 0.5 to 1.0 wt% based on 100 wt% of the solvent. When KOH is included in less than 0.5 wt%, the heat resistance is not improved, when included in more than 1.0 wt%, the sheet resistance value is rapidly increased, the solubility is lowered, b * value may be rather increased.

In addition, when KOH is included in 1.0 wt% with respect to 100 wt% of the solvent, the optical properties, sheet resistance, solubility. Both light resistance and heat resistance can exhibit excellent effects.

On the other hand, the crystal violet, that is, the crystal violet solution dispersed in the solvent may include 0.3 to 0.7 wt% with respect to 100 wt% of the silver nanowire ink. When included in less than 0.3 wt%, the decrease in b * value is small, can not be expected to improve the yellowing phenomenon, if included in more than 0.7 wt%, there may be a problem that the sheet resistance value rises sharply.

Another aspect of the invention, a transparent substrate; And

Provided is a transparent conductive film comprising silver nanowires and crystal violet on one surface of the transparent substrate.

The transparent substrate may be hard or flexible. For example, silicon substrate, glass substrate, poly methyl methacrylate (PMMA) substrate, poly vinyl pirrolidone (PVP) substrate, polystyrene (PS) substrate, polycarbonate , PC) Substrate, Polyethersulfone (PES) Substrate, Cyclic olefin copolymer (COC) Substrate, Triacetylcellulose (TAC) Substrate, Polyvinyl Alcohol Substrate, Polyimide (PI) Substrate Substrates, polyethylene terephthalate (PET) substrates, polyether sulfone (PES) substrates, polyethylenenaphthalate (PEN) substrates, and the like may be used.

The transparent conductive film includes a crystal violet, has a sheet resistance of 40 kW / sq or less, a b * value of 1.0 or less, a light transmittance of 85% or more, and a haze value of 0.8% or less, and may be usefully used as a transparent conductive film. It is possible to implement a wide range of transparent conductive film by adjusting the concentration, it can be usefully used in electronic devices, electrical devices or optical devices. Specific examples thereof may be usefully used in electrodes such as liquid crystal displays, plasma displays, touch panels, electroluminescent devices, thin film solar cells, dye-sensitized solar cells, and inorganic crystalline solar cells.

Moreover, as a specific example of an electronic device, a liquid crystal display, a plasma display, display devices, such as an organic electroluminescence display or an electronic paper, input sensors, such as a touch panel, a thin film type amorphous Si solar cell and a dye-sensitized solar cell Solar cells using sunlight, and the like.

Another aspect of the invention, the step of preparing a transparent substrate (step 1);

It provides a method for producing a transparent conductive film comprising a; depositing a conductive film comprising a silver nanowire and a crystal violet on one surface of the transparent substrate (step 2).

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

Step 1 is a step of preparing a transparent substrate, the transparent substrate is a silicon substrate, a glass substrate, a poly methyl methacrylate (PMMA) substrate, a poly vinyl pirrolidone (PVP) substrate , Polystyrene (PS) substrate, Polycarbonate (PC) substrate, Polyethersulfone (PES) substrate, Cyclic olefin copolymer (COC) substrate, Triacetylcellulose (TAC) substrate A polyvinyl alcohol substrate, a polyimide (PI) substrate, a polyethylene terephthalate (PET) substrate, and a polyethylenenaphthalate (PEN) substrate may be prepared.

Step 2 is a step of depositing a conductive film including silver nanowires and crystal violet on one surface of the transparent substrate, specifically, applying a composition for forming a conductive film according to the invention on a transparent substrate, and drying to deposit a conductive film Step.

The step of depositing a composition for forming a conductive film on the transparent substrate may use various methods such as, for example, bar coating, slot-die coating, dip coating, knife coating, screen coating, gravure coating, or air-knife coating. have. Depending on the thickness of the conductive film, the drying time is 1 to 3 minutes, the temperature may be adjusted in the range of 50 to 150 ℃, but is not limited thereto.

In one embodiment according to the present invention, the composition for forming a conductive film was applied to a transparent substrate, dried for 3 minutes in a 50 ° C. oven, and dried for 2 minutes in a 120 ° C. oven, but this is only an example. no.

Hereinafter, the present invention will be described in detail by Examples and Experimental Examples.

However, the following Examples and Experimental Examples are only illustrative of the present invention, and the content of the present invention is not limited to the following Examples and Experimental Examples.

<Production of Conductive Film Formation Composition>

Preparation Example Preparation of Silver Nanowire Ink

Silver nanowire ink was prepared by calculating the weight fraction of silver nanowire to 0.23 wt% in deionized water to prepare a silver nanowire ink, which was used in Example A below.

<Example A-1> Preparation of the composition for conductive film formation

Step 1: A crystal violet solution was prepared by adding acetonitrile in a weight fraction of 1.0% by weight of Crystal Violet to prepare a crystal violet solution.

Step 2: The composition for forming a conductive film was prepared by adding a silver nanowire ink obtained in the preparation example in a weight fraction such that the crystal violet solution was 0.5 wt%.

<Example A-2> Preparation of the composition for conductive film formation

A conductive film-forming composition was prepared in the same manner as in Example A-1, except that deionized water was used instead of acetonitrile.

<Example A-2> Preparation of the composition for conductive film formation

A conductive film-forming composition was prepared in the same manner as in Example A-1, except that ethanol was used instead of acetonitrile.

Example A-4 Preparation of a Conductive Film Formation Composition

A conductive film-forming composition was prepared in the same manner as in Example A-1, except that DMSO (dimethyl sulfoxide) was used instead of acetonitrile.

Example A-5 Preparation of a Composition for Forming a Conductive Film

A composition for forming a conductive film was prepared in the same manner as in Example A-1, except that diacetone alcohol (DAA) was used instead of acetonitrile.

Example A-6 Preparation of a Composition for Forming a Conductive Film

A composition for forming a conductive film was prepared in the same manner as in Example A-1, except that tetrahydrofuran (THF) was used instead of acetonitrile.

<Example A-7> Preparation of the composition for conductive film formation

In Step 1 of Example A-1, the same procedure as in Example A-1 was conducted except that the crystal violet was added to 0.5 wt% to prepare a composition for forming a conductive film.

Example A-8 Preparation of a Conductive Film Formation Composition

In Step 1 of Example A-1, a conductive film-forming composition was prepared in the same manner as in Example A-1, except that crystal violet was added to 0.7 wt%.

Example A-9 Preparation of a Composition for Forming a Conductive Film

In Step 1 of Example A-1, the same procedure as in Example A-1 was performed except that the crystal violet was added to 1.2 wt% to prepare a composition for forming a conductive film.

Example A-9 Preparation of a Composition for Forming a Conductive Film

In Step 1 of Example A-1, the same procedure as in Example A-1 was performed except that the crystal violet was added to 1.2 wt% to prepare a composition for forming a conductive film.

Example A-10 Preparation of a Composition for Forming a Conductive Film

In Step 1 of Example A-1, the same procedure as in Example A-1 was conducted except that the crystal violet was added to 1.5 wt% to prepare a composition for forming a conductive film.

Example A-11 Preparation of Conductive Film Formation Composition

In Step 1 of Example A-1, a conductive film-forming composition was prepared in the same manner as in Example A-1, except that the crystal violet was added to be 2.0 wt%.

Example A-12 Preparation of a Composition for Forming a Conductive Film

Step 1: A crystal violet solution was prepared by adding the acetonitrile to 1.2 wt% of Crystal Violet and 0.5 wt% of KOH.

Step 2: The composition for forming a conductive film was prepared by adding a silver nanowire ink obtained in the preparation example in a weight fraction such that the crystal violet solution was 0.5 wt%.

Example A-13 Preparation of a Composition for Forming a Conductive Film

In Step 1 of Example A-12, the same method as in Example A-12 was performed except that KOH was added to be 0.7 wt%, to prepare a composition for forming a conductive film.

Example A-14 Preparation of a Conductive Film Formation Composition

In Step 1 of Example A-12, except that KOH was added to 1.0 wt% was used in the same manner as in Example A-12 to prepare a composition for forming a conductive film.

<Example A-15> Preparation of the composition for conductive film formation

In Step 1 of Example A-12, except that KOH was added to 1.2 wt%, the same method as in Example A-12 was carried out to prepare a composition for forming a conductive film.

<Example A-16> Preparation of the composition for conductive film formation

Step 1: A crystal violet solution was prepared by adding the acetonitrile to 1.2 wt% of Crystal Violet and 1.0 wt% of KOH in 1.0 wt%, respectively.

Step 2: The composition for forming a conductive film was prepared by adding a silver nanowire ink obtained in the preparation example in a weight fraction such that the crystal violet solution became 0.1 wt%.

<Example A-17> Preparation of the composition for conductive film formation

In Step 2 of Example A-16, a conductive film-forming composition was prepared in the same manner as in Example A-16, except that the crystal violet solution was added to 0.3 wt%.

Example A-18 Preparation of a Composition for Forming a Conductive Film

In Step 2 of Example A-16, a conductive film-forming composition was prepared in the same manner as in Example A-16, except that the crystal violet solution was added to 0.7 wt%.

<Example A-19> Preparation of the composition for conductive film formation

In Example 2-16, a composition for forming a conductive film was prepared in the same manner as in Example A-16, except that the crystal violet solution was added so as to be 1.0 wt%.

<Comparative Example A-1> Preparation of the composition for conductive film formation

The silver nanowire ink obtained in the preparation example in which nothing was added as a comparative example was used without additional additives.

<Comparative Example A-2> Preparation of the composition for conductive film formation

A conductive film-forming composition was prepared in the same manner as in Example A-1, except that Rhodamine B was used instead of crystal violet.

<Comparative Example A-3> Preparation of a composition for forming a conductive film

A composition for forming a conductive film was prepared in the same manner as in Example A-1, except that Rhodamine 6G was used instead of crystal violet.

<Comparative Example A-4> Preparation of the composition for conductive film formation

A composition for forming a conductive film was prepared in the same manner as in Example A-1, except that methylene blue was used instead of crystal violet.

<Production of Transparent Conductive Membrane>

<Example B-1> to <Example B-19> Preparation of a Transparent Conductive Film

Step 1: A PET substrate was prepared.

Step 2: The conductive film forming compositions of Examples A-1 to A-19 were applied to the PET substrate prepared in Step 1, respectively, and dried in a 50 ° C. oven for 3 minutes and dried in a 120 ° C. oven for 2 minutes. Transparent conductive films B-1 to B-19 were prepared.

Comparative Example B-1 to Comparative Example B-4 Preparation of Transparent Conductive Film

Step 1: A PET substrate was prepared.

Step 2: Applying the conductive film-forming compositions of Comparative Examples A-1 to A-4 on each of the PET substrate prepared in Step 1, dried for 3 minutes in a 50 ℃ oven, dried for 2 minutes in a 120 ℃ oven Comparative Example Transparent conductive films B-1 to B-4 were prepared.

Table 1 summarizes the manufacturing conditions of the prepared composition for forming a conductive film, and also shows the Example number of the conductive film prepared using each composition for forming a conductive film.

Conductive film Composition Step 1 Step 1 Step 1 Step 1 Step 1 Step 2 Example Example dyes
Kinds dyes
Amount menstruum
Kinds KOH
Addition KOH
Amount Dye solution
usage B-1 A-1 crystal
Violet 1.0 wt% Aceto
Nitrile X - 0.5 wt% B-2 A-2 “ “ Deionized water X - “ B-3 A-3 “ “ ethanol X - “ B-4 A-4 “ “ DMSO X - “ B-5 A-5 “ “ DAA X - “ B-6 A-6 “ “ THF X - “ B-7 A-7 “ 0.5 wt% Aceto
Nitrile X - “ B-8 A-8 “ 0.7 wt% “ X - “ B-9 A-9 “ 1.2 wt% “ X - “ B-10 A-10 “ 1.5 wt% “ X - “ B-11 A-11 “ 2.0 wt% “ X - “ B-12 A-12 “ 1.2 wt% “ O 0.5 wt% “ B-13 A-13 “ “ “ O 0.7 wt% “ B-14 A-14 “ “ “ O 1.0 wt% “ B-15 A-15 “ “ “ O 1.2 wt% “ B-16 A-16 “ “ “ O 1.0 wt% 0.1 wt% B-17 A-17 “ 0.3 wt% B-18 A-18 “ 0.7 wt% B-19 A-19 “ 1.0 wt% Comparative example
B-2 Comparative example
A-2 Rhodamine B 1.0 wt% Aceto
Nitrile X - 0.5 wt% Comparative example
B-3 Comparative example
A-3 Rhodamine 6G 1.0 wt% Aceto
Nitrile X - 0.5 wt% Comparative example
B-4 Comparative example
A-4 Methylene
blue 1.0 wt% Aceto
Nitrile X - 0.5 wt%

Experimental Example 1 Analysis of Optical Properties and Sheet Resistance According to Dye Types

Optical Properties of Conductive Membranes According to Dye Type (Permeability, Haze, b * and a *) And the surface resistance is analyzed and the results are shown in Table 2 below. Permeability and haze were measured using CM-5 (Konica minolta).

Dye Type T.T (%) Haze b * a * Sheet resistance Bare PET - 92.17 0.12 0.48 -0.01 N / A Comparative Example B-1 dyes
No use 90.06 0.92 1.61 -0.21 40 Comparative Example B-2 Rhodamine B 89.10 0.95 0.05 1.11 40 Comparative Example B-3 Rhodamine 6G 88.85 1.05 0.01 0.91 41 Comparative Example B-4 Methylene blue 89.50 0.89 0.78 -1.21 40 Example B-1 crystal
Violet 89.81 0.71 0.18 -0.21 35

In Table 2 above,

T.T (%) is the transmittance,

b * is yellowness,

a * is the redness.

As shown in Table 2 above, when using the silver nanowire ink without the dye solution (Comparative Example 1), when the dye solution is added, the b * reduction effect is shown, and the transmittance shows that the similar value as a whole Able to know.

However, the conductive film of Example B-1 prepared using the composition for forming a conductive film according to the present invention using crystal violet as a dye has the best optical properties when considering haze, b * and a * values. It can be seen that the crystal violet is the most suitable dye.

Experimental Example 2 Analysis of Optical Properties, Sheet Resistance, Solubility and UV Light Resistance According to the Types of Solvents

The optical properties (transmittance, Haze (turbidity) and b *), sheet resistance, solubility, and UV light resistance of the conductive film according to the solvent type were analyzed, and the results are shown in Table 3 below. Permeability and haze were measured using CM-5 (Konica minolta).

Solvent Type T.T (%) Haze b * Sheet resistance Solubility Light resistance Comparative Example B-1 - 90.06 0.92 1.61 40 - - Example B-2 Deionized water 89.43 0.78 0.89 36 O X Example B-3 ethanol 89.33 0.76 0.78 38 O X Example B-4 DMSO 89.32 0.74 0.68 37 O X Example B-1 Aceto
Nitrile 89.81 0.71 0.18 35 O Δ Example B-5 DAA 89.46 0.73 0.59 38 O X Example B-6 THF X X X X X X

In Table 3 above,

T.T (%) is the transmittance,

b * is yellowness.

As shown in Table 3, the conductive film of the embodiment according to the present invention has a b when a crystal violet solution dispersed in various solvents is added, than when using a silver nanowire ink (Comparative Example 1) without adding a dye solution. * It can be seen that the reduction effect.

However, when acetonitrile is used as the solvent, it can be seen that the highest permeability, the lowest haze value, and the lowest b * value. In addition, the other solvents do not exhibit UV light resistance, and using acetonitrile as a solvent can be seen that the most suitable when considering the transmittance, Haze, b *, sheet resistance and UV light resistance values.

Experimental Example 3 Analysis of Optical Properties, Sheet Resistance and Solubility According to Dye Usage

Composition for Forming a Conductive Film In Step 1 of Example A, the optical properties (transmittance, Haze, and b *), sheet resistance, and solubility of the conductive film according to the amount of crystal violet used in the preparation of the crystal violet solution were analyzed. It is shown in Table 4 below. Permeability and haze were measured using CM-5 (Konica minolta).

dyes
Amount T.T (%) Haze b * Sheet resistance Solubility Comparative Example B-1 - 90.06 0.92 1.61 40 - Example B-7 0.5 wt% 89.73 0.77 1.19 35 O Example B-8 0.7 wt% 89.56 0.73 0.74 35 O Example B-1 1.0 wt% 89.81 0.71 0.18 35 O Example B-9 1.2 wt% 89.28 0.72 0.11 34 O Example B-10 1.5 wt% 89.15 0.71 0.01 34 O Example B-11 2.0 wt% 88.80 0.69 -0.31 51 X

In Table 4 above,

T.T (%) is the transmittance,

b * is yellowness.

As shown in Table 4, the conductive film of the embodiment according to the present invention exhibits a b * reduction effect when the crystal violet is added, than when using the silver nanowire ink without the dye solution (Comparative Example 1). .

In addition, the permeability, haze and b * value tended to decrease as the amount of crystal violet added, but when added more than 2.0 wt%, it did not dissolve in acetonitrile and b * value decreased excessively and the sheet resistance It can be seen that this rises sharply.

In addition, when added at 0.5 wt% or less, despite the decrease in the b * value, it is still difficult to prevent yellowing by maintaining a high value.

Therefore, in consideration of optical properties, sheet resistance, and solubility, it is suitable to use crystal violet at 0.5 to 2.0 wt%, and most preferably at 1.2 to 1.5 wt%.

<Experiment 4> Analysis of optical properties, sheet resistance, solubility, light resistance and heat resistance according to the amount of KOH used

Composition for Forming Conductive Film In step 1 of Example A, the optical properties of the conductive film (permeability, Haze (turbidity) and b *), sheet resistance, solubility, light resistance and heat resistance were analyzed according to the amount of KOH used in preparing the crystal violet solution. The results are shown in Table 5 below. Permeability and haze were measured using CM-5 (Konica minolta).

KOH addition amount T.T (%) Haze b * Sheet resistance Solubility Light resistance Heat resistance Comparative Example B-1 - 90.06 0.91 1.61 40 Example B-9 - 89.28 0.72 0.11 34 O Δ X Example B-12 0.5 wt% 89.36 0.73 0.74 38 O Δ Δ Example B-13 0.7 wt% 89.53 0.73 0.65 37 O Δ O Example B-14 1.0 wt% 89.53 0.73 0.18 35 O O O Example B-15 1.2 wt% 89.53 2.19 0.34 62 X O O

In Table 5, T.T (%) is the transmittance,

b * is yellowness.

As shown in Table 5, the conductive film of the embodiment according to the present invention, when using the composition for forming a conductive film according to the present invention, than when using a silver nanowire ink (Comparative Example 1) without the dye solution, All examples show an effect of reducing b *.

It was found that when KOH was added at 0.5 wt% (Example B-12), the b * value was higher than that without addition (Example B-9), but the heat resistance was significantly increased. Can be. It can be seen that KOH can bring about an effect of improving heat resistance and light resistance, but the effect of dye is reduced.

On the other hand, when KOH is added at 0.7 wt% (Example B-13), the b * value is reduced than when KOH is added at 0.5 wt% (Example B-12), and the heat resistance is 0.5 wt% added. It turns out that it rises more remarkably.

In addition, when KOH was added at 1.0 wt% (Example B-14), the b * value was significantly reduced than when KOH was added at 0.5 wt% (Example B-12), and the heat resistance. In addition, the UV light resistance also showed a significant increase.

On the other hand, when KOH was added at 1.2 wt% (Example B-15), not only did b * values increase rather than when 1.0 wt% was added, but also the haze value increased rapidly and the sheet resistance was remarkably increased. High value was shown and the solubility was drastically lowered.

Therefore, optical properties, sheet resistance, solubility. In consideration of both light resistance and heat resistance, it is suitable to use KOH at 0.5 to 1.0 wt%, and most suitable to use KOH at 1.0 wt%.

Experimental Example 5 Analysis of Optical Properties, Sheet Resistance, Solubility, Light Resistance and Heat Resistance According to Addition of Crystal Violet Solution to Silver Nanowire Ink

Composition for Forming Conductive Film In step 2 of Example A, the optical properties (permeability, Haze (turbidity) and b *), sheet resistance, solubility, and light resistance according to the addition amount of the crystal violet solution prepared in step 1 to the silver nanowire ink And the heat resistance was analyzed and the results are shown in Table 6 below. Permeability and haze were measured using CM-5 (Konica minolta).

crystal
Violet solution
Amount T.T (%) Haze b * Sheet resistance Solubility Light resistance Heat resistance Comparative Example B-1 - 90.06 0.91 1.61 40 Example B-16 0.1 wt% 89.90 0.77 1.43 36 O O O Example B-17 0.3 wt% 89.57 0.73 0.71 38 O O O Example B-14 0.5 wt% 89.53 0.73 0.18 35 O O O Example B-18 0.7 wt% 89.39 0.71 0.08 35 O O O Example B-19 1.0 wt% 89.19 0.69 -0.01 60 O O O

In Table 6 above,

T.T (%) is the transmittance,

b * is yellowness.

As shown in Table 6, the conductive film of the embodiment according to the present invention, when using the composition for forming a conductive film according to the present invention, than when using a silver nanowire ink (Comparative Example 1) without the dye solution, All examples show an effect of reducing b *.

Specifically,

Composition for Forming Conductive Film In step 2 of Example A, when the crystal violet solution was added to the silver nanowire ink at 0.1 wt% (Example B-16), the degree of reduction of b * value was not added (compared to the comparison). Although it did not show a significant improvement over Example B-1), it can be seen that the haze value is reduced.

In addition, in the step 2 of the composition A for forming a conductive film, in the case of adding 0.3 wt% of the crystal violet solution to the silver nanowire ink (Example B-17), when the b * value was not added (Comparative Example) It can be seen that it is significantly reduced by more than 55% than B-1).

In addition, in the step 2 of the composition A for forming a conductive film, when the crystal violet solution was added to the silver nanowire ink at 0.5 wt% (Example B-14), when the b * value was not added (Comparative Example) It can be seen that it is significantly reduced by more than 80% than B-1).

In addition, in the case of adding a crystal violet solution in 0.7 wt% to the silver nanowire ink in Example 2 of the conductive film forming composition example A (Example B-18), when the b * value was not added (Comparative Example) It can be seen that it is significantly reduced by more than 90% than B-1).

On the other hand, in the case of adding a crystal violet solution in 1.0 wt% to the silver nanowire ink in Example 2 of the conductive film-forming composition Example A (Example B-19), when the b * value is not added (Comparative Example) Although it is significantly reduced by more than 95% than B-1), the effect of the rapid increase in sheet resistance is also shown.

Therefore, in consideration of both optical properties and sheet resistance, in step 2 of composition A for forming a conductive film, it is suitable to make the crystal violet solution 0.3 to 0.7 wt% in silver nanowire ink.

Claims (12)

A conductive film containing silver nanowires,
And the conductive film comprises crystal violet.
The method of claim 1,
And the crystal violet is dispersed in the conductive film.
The method of claim 1,
The conductive film further comprises a KOH.
A composition for forming a conductive film containing silver nanowire ink,
A composition for forming a conductive film, wherein the composition comprises crystal violet dispersed in a solvent.
The method of claim 4, wherein
The crystal violet is dispersed in the composition, the composition for forming a conductive film.
The method of claim 4, wherein
The solvent is any one selected from the group consisting of water, ethanol, DMSO (dimethylsulfoxide), acetonitrile, diacetone alcohol (dicetone alcohol) and tetrahydrofuran.
The method of claim 4, wherein
The solvent is acetonitrile composition for forming a conductive film, characterized in that.
The method of claim 4, wherein
The composition may further comprise KOH, composition for forming a conductive film.
Transparent substrates; And
Transparent conductive film comprising silver nanowires and crystal violet on one surface of the transparent substrate.
The method of claim 9,
And the crystal violet is dispersed in the conductive film.
The method of claim 9,
The conductive membrane may further comprise KOH.
Preparing a transparent substrate (step 1);
And depositing a conductive film comprising silver nanowires and crystal violet on one surface of the transparent substrate (step 2).