KR100844861B1 - A composition for preparing electronic ink and a preparation method thereof - Google Patents

Abstract

The present invention relates to a composition for preparing an electronic ink and a method for preparing the same, and specifically, (i) a composition for preparing an electronic ink including (i) a silver ionic solution, (ii) a conductive polymer, (iii) a reducing agent, and (iv) a super solid acid and The present invention relates to a manufacturing method, and in particular, exhibits a resistivity value low enough to be used as an electronic ink for wiring, electronic and electrode printing in electronic device fabrication without performing a separate high temperature sintering process. It relates to a water dispersion or a solvent dispersion electron ink which does not affect phosphorus.

Conductive Polymer, Super Solid Acid, High Temperature Sintering, Water Disperse Electronic Ink

Description

A composition for preparing an electronic ink and a method for manufacturing the same

The present invention relates to a composition for preparing an electronic ink and a method for preparing the same, and specifically, (i) a composition for preparing an electronic ink including (i) a silver ionic solution, (ii) a conductive polymer, (iii) a reducing agent, and (iv) a super solid acid and The present invention relates to a manufacturing method, and in particular, exhibits a resistivity value low enough to be used as an electronic ink for wiring, electronic and electrode printing in electronic device fabrication without performing a separate high temperature sintering process. It relates to a water dispersion or a solvent dispersion electron ink which does not affect phosphorus.

Conventionally, electron inks using metal nanoparticles of 60 nm or less include metal oxides (AgNO ₃ , AuCl ₄ , PdCl ₂ , Cu ₂ O, etc.), polyvinylpyrrolidone ('PVP'), polyethylene glycol ('PEG'), After dissolving a polymer dispersant such as polyethyleneimine ('PEI'), polyesteramide ('PEA') and polyester in a solvent, the metal oxides are nano-sized metal particles by adding a reducing agent such as NaBH ₄ , formaldehyde or amine. Techniques to grow to become stabilized colloidal dispersions have been common.

However, the nanoparticles prepared as described above have a technical and cost problem because they have to be subjected to a high temperature sintering process in order to connect the nanoparticles in order to realize sufficient conductivity by using the electronic ink as a size of 50 to 100 nm. . In addition, despite the high temperature sintering process, if the used polymer dispersant is not sufficiently removed, the specific resistance value is more than 10 ^-2 Ωcm, so that its electrical characteristics are not sufficient. There was a serious inconvenience in the process of difficult to remove the polymer dispersant, and there was a problem that the price of the electronic ink can be expensive.

The present invention is an invention that can exhibit excellent conductivity without removing the polymer dispersant added to prepare the silver nanoparticles by using a conductive polymer in place of the polymer dispersant used in the manufacture of silver nanoparticles.

In addition, the present invention is a conductive polymer used in the process of reducing the silver oxide to convert the silver oxide dedopping (dedopping) to lose the electrical conductivity, the super solid acid prevents the dedoping of the conductive polymer By discovering a special action effect and adding super solid acid, it has low resistivity enough to be used as electronic ink for wiring, electronic and electrode printing in electronic device fabrication without the need for separate high temperature sintering process. In addition, it was confirmed by the fact that it is possible to produce an aqueous dispersion or solvent-dispersed electronic ink that does not have a chemical effect on the substrate.

Accordingly, an object of the present invention is to provide a composition for preparing an electronic ink including a silver ion solution, a conductive polymer, a reducing agent, and a super solid acid.

Still another object of the present invention is to provide a method for preparing the composition for preparing an electronic ink.

Another object of the present invention to provide an electronic ink prepared by using the composition for preparing an electronic ink.

Other objects, specific embodiments, and the like of the present invention will be presented below.

In one aspect, the present invention relates to a composition for preparing an electronic ink comprising a silver ion solution, a conductive polymer, a reducing agent and a super solid acid.

In the present invention, the silver ion solution includes all kinds of silver ion solutions that can be obtained by a conventional method. As a solvent of the solution, water, an organic solvent or a mixed solvent of water and an organic solvent may be used, and it is preferable to use a polar organic solvent as the organic solvent. Different silver ion solutions, for example, are silver ion solutions prepared by dissolving silver in a nitric acid solution, or include all silver ion solutions obtained by dissolving silver salts such as AgNO ₃ or AgCH ₃ CO ₂ in water or a polar organic solvent. It should be understood as Examples of the polar organic solvent include alcohols such as ethanol, methanol, and isopropyl alcohol, dimethyl acetamide (DMAC), dimethyl sulfoxide (DMSO), ethyl carbitol, and ethyl cellosolve. (Ethyl cellosolve), dimethylformamide (DMF), N-methyl formaide (NMF) or methylpyrrolidone (1-Methyl-2-pyrrolidone; NMP). .

In the present invention, as the conductive polymer, all kinds of conductive polymers known as conductive polymers may be used, and a polythiophene substituted with an alkyl chain is more preferable, more preferably, a conductive polymer soluble in water or an organic solvent. polythiophene), undoped polyaniline and polypyrrole are suitable for organic solvents and are suitable conductive polymers for preparing gravure inks.

It is particularly preferable to use a water dispersible or solvent dispersible conductive polymer such as poly (3,4-ethylenedioxythiophene), polypyrrole, polyaniline or a mixture thereof to prepare an electronic ink for water dispersion or solvent dispersion inkjet. It is more preferable to use poly (3,4-ethylenedioxythiophene; PEDOT) or polyaniline in view of the improvement of other physical properties such as conductivity. When PEDOT or polyaniline is used as the preferred conductive polymer in the present invention, its molecular weight can be adjusted to obtain the desired final conductivity, which is possible by conventional methods known to those skilled in the art.

Reducing agents in the present invention may also be used regardless of the type of reducing agents conventionally used, for example sodium borohydride (NaBH ₄ ), formaldehyde, amine, hydrazine, ethylene glycol, diethylene glycol, triethylene glycol And the like can be used. However, when hydrazine is used, the reaction solution turns acidic and the conductivity contribution by the conductive polymer is increased, so it is preferable to use hydrazine to increase the final conductivity.

In the present invention, the super solid acid refers to a material that is capable of reducing the material itself and at the same time doping the conductive polymer. Examples of super solid acids include silver alkylacetate, silver alkylsulfonate, and silver p substituted with acid groups such as carboxylic acid groups, sulfonic acid groups, and phosphoric acid groups on the surface of metals or inorganic oxides. Toluenesulfonate (Ag p-toluene sulfonate), silver camphorsulfonate, silver 2-acrylamido-1-propane sulfonate (Ag 2-acrylamido-1-propane sulfonate, silver polystyrene sulfonate ( Ag polystyrene sulfonate), Au alkylacetate, Au alkylsulfonate, S ₂ O ₈ ^2- / TiO ₂ -SiO ₂ , SO ₄ ^2- / Ti-La-O (Sulfonated La Ti- oxide), ZrO ₂ -SO ₄ ^2- , CsHSO ₄ , CsHSeO ₄ , CsH ₂ PO ₄ , a-Cs ₃ (HSO ₄ ) ₂ (H ₂ PO ₄ ), b-Cs ₃ (HSO ₄ ) ₂ [H _{2 -x} (P _1-x , S _x ) O ₄ ] (0 <x <1), Cs ₂ (HSO ₄ ) (H ₂ PO ₄ ) and Cs ₅ (HSO ₄ ) ₃ (H ₂ PO ₄ ) _2, etc. a can be exemplified, in addition includes the _{SiO 2 -Al 2 O 3, ZSM} -5, MgO-Y. the solid super acid in alkyl acetate Te Ag alkylacetate, silver alkylsulfonate, silver p-toluene sulfonate, silver camphorsulfonate, silver 2-acrylamido-1-propane sulfo Nate (Ag 2-acrylamido-1-propane sulfonate, Ag polystyrene sulfonate), gold alkyl acetate (Au alkylacetate), gold alkylsulfonate (Au alkylsulfonate0) It is more preferable to use any one or more selected from the above, the alkyl acetate Or the alkyl group of the alkylsulfonate is selected from C1 to C30 straight or branched chain alkyl groups. It is not necessary to limit the particle size of the super solid acid, but having a size of 100 nm or less and 1 to 100 nm may be advantageous in terms of stability after ink production.

The conductive polymer is dedoped as silver ions are reduced to silver nanoparticles, thereby losing electrical conductivity. The super solid acid according to the present invention prevents the reduction of the conductive polymer and at the same time, a doping action, that is, a role of dopant, By providing a function of increasing the conductivity by the conductive polymer plays a role as a conductive binder between the dispersing agent and the silver particles, it has a function that can exhibit excellent conductivity without removing the dispersant (or stabilizer) separately. Therefore, in the present invention, the super solid acid is a material capable of preventing the reduction of the conductive polymer and at the same time doping action.

According to a specific embodiment according to this, the present invention is (i) silver ionic solution, (ii) conductive polymer, (iii) reducing agent and (iv) silver alkylacetate (Ag alkylacetate), silver alkylsulfonate (Ag alkylsulfonate), Silver p-toluene sulfonate, silver camphorsulfonate, silver 2-acrylamido-1-propane sulfonate, silver polystyrene Ag polystyrene sulfonate, Au alkylacetate, Au alkylsulfonate, S ₂ O ₈ ^2- / TiO ₂ -SiO ₂ , SO ₄ ^2- / Ti-La-O ( Sulfonated La Ti-oxide), ZrO ₂ -SO ₄ ^2- , CsHSO ₄ , CsHSeO ₄ , CsH ₂ PO ₄ , a-Cs ₃ (HSO ₄ ) ₂ (H ₂ PO ₄ ), b-Cs ₃ (HSO ₄ ) ₂ [H _2-x (P _1-x , S _x ) O ₄ ] (0 <x <1), Cs ₂ (HSO ₄ ) (H ₂ PO ₄ ), Cs ₅ (HSO ₄ ) ₃ (H ₂ PO ₄ ) ₂ , It provides a composition for preparing an electronic ink comprising at least one super solid acid selected from SiO ₂ -Al ₂ O ₃ , ZSM-5 or MgO-Y.

In addition, the present invention relates to (i) 0.00001 to 0.5 g / mL, preferably 0.004 to 0.2 g / mL, of the conductive polymer (iii) 0.00001 with respect to the volume (mL) of the silver ion solution and the solvent of the silver ion solution. ˜0.05 g / mL, preferably 0.003-0.05 g / mL reducing agent and (iv) 0.0004 g / mL or more of a super solid acid. The content of the conductive polymer, the reducing agent, and the super solid acid means the content of the solvent in the silver ion solution, and the content of silver ions in the silver ion solution can be variously adjusted according to the desired physical properties, so the present invention is not particularly limited. On the basis of the silver nitrate, it is advantageous in terms of performance and working to adjust to have a solid content of 0.5 to 50% by weight.

Here, if the content of the conductive polymer is out of the above range, the dispersion of the silver particles is not sufficient, so that the nozzle clogging phenomenon may occur due to the condensation of the silver particles and the electrical conductivity of the conductive polymer is not shown. Since the conductivity is mainly appeared, there may be a problem of lowering the conductivity of the conductive polymer level. In addition, when the content of the reducing agent is out of the above range, the phenomenon of falling in conductivity may occur. In addition, in the case of a super solid acid, it is advantageous to include 0.0004 g / mL to 0.5 g / mL in terms of conductivity and viscosity improvement.

In addition, as can be seen in the following examples, the conductivity and viscosity of the final composition can be controlled by changing the content of the conductive polymer, the content of silver ions, and the content of the super solid acid. Through such conductivity control, the present invention can be applied not only to the field of electronic circuits requiring high conductivity, but also to an antistatic agent and a semiconductor requiring low conductivity. In addition, by controlling the viscosity at the same time, it is possible to easily manufacture from low viscosity inkjet to medium viscosity gravure and high viscosity screen ink.

According to another aspect of the invention, the present invention relates to a method for producing the composition for preparing an electronic ink.

According to a specific embodiment according to this, the present invention (1) preparing a silver ion solution, (2) in the silver ion aqueous solution, with respect to the volume (mL) of the solvent of the silver ion solution 0.00001 ~ 0.5 g / adding mL, preferably 0.004-0.2 g / mL of conductive polymer and 0.00001-0.05 g / mL, preferably 0.003-0.05 g / mL reducing agent, and (3) at least 0.0004 g / mL to the solution It relates to a method for producing an electronic ink, characterized in that the addition of a super solid acid.

More preferably, the step of adjusting the pH of the solution may be further performed after the step (2), and more preferably, adjusting the pH to 2 to 5 is advantageous for conductivity and other physical properties of the final ink. . The pH can be adjusted by using an inorganic acid or an organic acid such as sulfuric acid, and when preparing a neutral and basic ink, amines or salts thereof, or ammonium hydroxide can be used.

Another aspect of the present invention is an electronic ink composition comprising the composition for preparing an electronic ink for ink jet according to the present invention, in particular, the viscosity of 1.0 to 10000.0 cp, 10 to 60 mN / m, preferably 40 to 60 mN / m It is preferable to adjust the surface tension to have a silver content of 2.5 to 10% by weight in view of high resolution.

In order to further improve the resolution, especially when using an inkjet printer, a printing speed of 150 to 250 Hz, a temperature of 40 to 50 ° C., a printing voltage of 35 to 55 V, and a printing speed of 0.05 to 0.1 m / s It is desirable to operate the printer.

In addition, as a composition material for manufacturing gravure and electronic ink for screen printing, it is suitable to adjust and use the composition to have a viscosity of 100 to 10000cp, a surface tension of 10 to 60 mN / m, and a silver content of 10 to 70% by weight. Electronic ink is more suitable to adjust the viscosity to 100 ~ 200 cp, surface tension of 20 ~ 60 mN / m, silver content of 20 ~ 60% by weight.

As described above, the composition for preparing an electronic ink of the present invention can obtain a specific resistance range of less than 10 ⁻⁵ μm cm, which is essentially required to be used exclusively for ink jet as a water dispersion or a solution dispersion ink that does not chemically affect a substrate. In addition, the physical properties of the present invention can be obtained by controlling the addition amount of the super solid acid as well as controlling the conductivity and viscosity without additional physical properties.

The following examples and the like are intended to describe the present invention in more detail, and the present invention is not limited thereto.

Example 1

An aqueous silver ion solution was prepared by dissolving 0.3 g of AgNO _{3 in} 10 mL of distilled water. To this aqueous solution was added 2 g of 10% by weight PEDOT (dispersed to an average size of 60 nm particle size) aqueous dispersion and stirred with a homogenizer to uniformly disperse. 0.5 g of a 10 wt% aqueous solution of hydrazine was slowly added thereto, followed by stirring for an additional 6 hours to prepare a dark gray solution. The dark gray solution was adjusted to pH 2 with sulfuric acid (H ₂ SO ₄ ). 8 mg of super solid acid Au (CH ₂ ) ₃ SO ₃ H was added to the reaction solution, followed by stirring for 3 hours. The conductivity obtained after printing the silver colloidal solution obtained by printing on a film was 4.56 × 10 ⁵ S / cm.

Example 2

Except for using Ag (CH ₂ ) ₃ SO ₃ H as a super solid acid in Example 1 and was carried out in the same manner as in Example 1. The resulting silver colloidal solution was printed on a film and the conductivity obtained after drying was 4.71 × 10 ⁵ S / cm.

Example 3

Example 1 was carried out in the same manner as in Example 1 except that Cs ₅ (HSO ₄ ) ₃ (H ₂ PO ₄ ) ₂ was used as the super solid acid. The resulting silver colloidal solution was printed on a film and the conductivity obtained after drying was 4.54 × 10 ⁵ S / cm.

Examples 4-9: Changes in Conductivity with pH of Black Gray Solution

Under the same conditions as in Example 1, the pH of the preparation solution was 4 (Example 4), 6 (Example 5), 7 (Example 6), 8 (Example 7), 10 (Example 8), The experiment was carried out by adjusting to 12 (Example 9). At this time, the pH was adjusted by adding acetic acid and ammonium hydroxide. The conductivity of the obtained silver colloidal solution was 4.08 × 10 ⁵ , 4.34 × 10 ⁵ , 3.67 × 10 ⁵ , 5.01 × 10 ⁴ , 3.56 × 10 ⁴ S / cm, respectively.

Examples 10 to 16: change in conductivity according to the content of super solid acid

Under the same conditions as in Example 1, the pH of the black gray solution was adjusted to 4, and the amount of nano super solid acid was 0.1 mg (Example 10), 0.4 mg (Example 11), and 0.8 mg (Example), respectively. 12), 1.2 mg (Example 13), 1.6 mg (Example 14), 2.0 mg (Example 15), 2.4 mg (Example 16) were added to the experiment. The conductivity of the obtained silver colloidal solution was 3.34 × 10 ⁴ , 3.11 × 10 ⁵ , 3.56 × 10 ⁵ , 3.32 × 10 ⁵ , 3.31 × 10 ⁵ , 3.54 × 10 ⁵ , 3.98 × 10 ⁵ S / cm, respectively.

Changes in Conductivity According to Kinds of Conductive Polymers

Under the same conditions as in Example 1, instead of PEDOT, experiments were performed using polypyrrole and polyaniline, respectively.

Example 17

The same experiment as in Example 1, except that 2 g of polypyrrole (dispersed to an average size of 50 nm particle size) aqueous dispersion (3 wt%) was added instead of PEDOT and stirred with a homogenizer to uniformly disperse the same. Was carried out. The conductivity after printing was 3.34 × 10 ³ S / cm.

Example 18

The same experiment was carried out in Example 1 except that 2 g of polyaniline (number average molecular weight 50000) aqueous dispersion 3 wt%) was added instead of PEDOT and stirred with a homogenizer to disperse uniformly. The conductivity after printing was 2.64 × 10 ⁴ S / cm.

Example 19-24: Control of Conductivity According to Content of Conductive Polymer

The amount of PEDOT in Example 1 was 0.004 g / mL (Example 19), 0.005 g / mL (Example 20), 0.01 g / mL (Example 21), 0.015 g / mL (Example 22), 0.25 g Except for changing to / mL (Example 23), 0.3g / mL (Example 24), the same experiment as in Example 1 was observed to change the conductivity. As a result, as the amount of the conductive polymer increases, the conductivity of the ink is expressed only as much as the conductivity of the polymer, because it does not have a sufficient bridging effect when the amount of the polymer is larger than that of the silver nanoparticles. Table 1 shows the results obtained when the conductive high molecular weight is controlled. When the conductive polymer uses 0.25 g / mL or more, silver particle condensation occurs.

TABLE 1

Example 25

A silver ion solution was prepared by dissolving 0.3 g of AgNO _{3 in} 10 mL of N-methyl pyrrolidone, a polar organic solvent. 0.02 g of polymer aniline (number average molecular weight 50000) was added to the solution and stirred with a homogenizer to disperse uniformly. To the dispersed solution, 0.2 g of Ag (CH ₂ ) ₃ COOH was added as a super solid acid, followed by further stirring for 3 hours. 0.5 g of a 10% aqueous hydrazine solution was slowly added to the mixed solution, followed by stirring for an additional 6 hours to prepare a dark gray solution. The conductivity obtained after printing the obtained solution onto a film and drying was 5.1 × 10 ⁵ S / cm.

Example 26

The same procedure as in Example 25 was carried out except that silver camphorsulfonate was used as the super solid acid in Example 25. The resulting silver colloidal solution was printed on a film and the conductivity obtained after drying was 4.7 × 10 ⁵ S / cm.

Example 27

The same procedure as in Example 25 was carried out except that silver 2-acrylamido-1-propane sulfonate was used as the super solid acid in Example 25. The resulting silver colloidal solution was printed on a film and the conductivity obtained after drying was 4.5 × 10 ⁵ S / cm.

Comparative Examples 1 to 7: When Super Solid Acid is Not Used

An aqueous silver ion solution was prepared by dissolving 0.3 g of AgNO _{3 in} 10 mL of distilled water. 0.02 g of the polymer aniline (number average molecular weight 50,000) was added to the aqueous solution, followed by stirring with a homogenizer so as to be uniformly dispersed. 0.5 g of 10% hydrazine was slowly added thereto and stirred for an additional 6 hours to prepare a dark gray solution. Acetate and ammonium hydroxide were added to the dark gray solution, and the pH was 4 (Comparative Example 1), 6 (Comparative Example 2), 7 (Comparative Example 3), 8 (Comparative Example 4), 10 (Comparative Example 5). ), 12 (Comparative Example 6), and 14 (Comparative Example 7). When pH = 6 or more, it was possible to obtain low conductivity of 2.46 × 10 ² S / cm or less, and it was also confirmed that it was impossible to use it as an electronic ink because precipitation occurred severely.

Comparative Examples 8-14: When Super Solid Acid is Not Used

As in Comparative Examples 1 to 7, but instead of the polymer aniline, the experiment was performed using PVP (polyvinylpyrrolidone) (number average molecular weight: 40000). The pH of the solution was 4 (Comparative Example 8), 6 (Comparative Example 9), 7 (Comparative Example 10), 8 (Comparative Example 11), 10 (Comparative Example 12), 12 (Comparative Example 13), 14 (Comparative). Example 14) was adjusted. When pH = 7 or more, it was possible to obtain a low conductivity of 2.74 × 10 ² S / cm or less, and it was also confirmed that it was impossible to use the electronic ink because precipitation occurred severely.

Comparative Examples 15 to 16: When sintering at high temperature was performed without using a super solid acid.

The silver colloidal solution, which did not generate the precipitates obtained in Comparative Examples 10 to 11, was further heat-treated at 200 ° C. for 5 minutes after printing. Nevertheless, the electrical conductivity was 2.74 × 10 ² and 4.52, which are the conductivity of Comparative Examples 10-11. It was confirmed that there was no substantial increase at x10 ² S / cm.

Experimental Example 1

The viscosity and surface tension of the solution prepared in Example 1 were adjusted to the required viscosity and surface tension using water and surfactant polyethylene oxide-b-polypropylene oxide, respectively, and the filter of 5 μm pore without additional formula. Passed through to prepare a ready-to-use inkjet ink. The characteristics of the prepared ink are shown in Table 2. By using the inkjet printer to adjust the width and length of the line to print under the conditions of Table 2 to obtain a variety of printing patterns, as shown in Figure 1 was able to obtain a very clear and high resolution printing pattern.

TABLE 2

Experimental Example 2

The results of measuring the contact resistances at the beginning and the end of the printed pattern obtained in Experimental Example 1 are shown in Table 3, before and after the 80 ° C heat treatment, and the surface morphology before and after the 80 ° C heat treatment was analyzed using AFM. And FIG. 3. Comparing FIG. 2 and FIG. 3, it can be seen that the contact between the particles is improved despite the heat treatment at low temperature. After drying at room temperature after printing, the resistivity of the printed pattern before and after the heat treatment at 80 ° C. was about 10 ⁻⁵ Ω · cm, indicating no significant change, and the sheet resistance was about 2 times higher than the heat treatment transition.

TABLE 3

Experimental Example 3

Viscosity and surface tension of the silver colloidal solution of Example 27 using superacrylic acid as 2-acrylamido-1-propane sulfonate were measured using N-methylpyrrolidone and surfactant. Polyethylene oxide-b-polypropylene oxide was used to adjust the amount of addition to the required viscosity and surface tension, respectively, and prepared ready-to-use gravure ink. Table 4 shows the characteristics of the prepared ink. By using the gravure printer to adjust the width and length of the line to print under the conditions of Table 3 to obtain a variety of printing patterns, as shown in Figure 4 was able to obtain a very clear and high resolution printing pattern.

TABLE 4

1 is an antenna-shaped printing pattern printed by an inkjet printer using an electronic ink according to the present invention.

Figure 2 is a form observing the surface of the printed electronic ink at room temperature by AFM.

Figure 3 shows the surface of the printed electronic ink after 80 ℃ heat treatment.

4 is an antenna-shaped printing pattern printed by a gravure printer using an electronic ink according to the present invention.

Claims (13)

(i) silver ionic solution, (ii) conductive polymer, (iii) reducing agent and (iv) silver alkylacetate, silver alkylsulfonate, silver p-toluene sulfonate ), Silver camphorsulfonate, silver 2-acrylamido-1-propane sulfonate, silver polystyrene sulfonate, gold alkyl acetate Au alkylacetate), Au alkylsulfonate, S ₂ O ₈ ^2- / TiO ₂ -SiO ₂ , SO ₄ ^2- / Ti-La-O (Sulfonated La Ti-oxide), ZrO ₂ -SO ₄ ^{2 -} , CsHSO ₄ , CsHSeO ₄ , CsH ₂ PO ₄ , a-Cs ₃ (HSO ₄ ) ₂ (H ₂ PO ₄ ), b-Cs ₃ (HSO ₄ ) ₂ [H _2-x (P _1-x , S _x ) O ₄ ] (0 <x <1), Cs ₂ (HSO ₄ ) (H ₂ PO ₄ ), Cs ₅ (HSO ₄ ) ₃ (H ₂ PO ₄ ) ₂ , At least one solid acid selected from SiO ₂ -Al ₂ O ₃ , ZSM-5, and MgO-Y, wherein the conductive polymer is 0.00001-0.5 g / mL based on the solvent volume (mL) of the silver ion solution. , The reducing agent is 0.00001 ~ 0.05 g / mL, the solid acid is a composition for producing an electronic ink, characterized in that it is contained in an amount of 0.0004 ~ 0.5 g / mL. delete The method of claim 1, The solid acid silver alkyl acetate (Ag alkylacetate), silver alkylsulfonate (Ag alkylsulfonate), silver p-toluene sulfonate (Ag p-toluene sulfonate), silver camphorsulfonate (Ag camphorsulfonate), silver 2-acrylamido 1-propane sulfonate (Ag 2-acrylamido-1-propane sulfonate), silver polystyrene sulfonate (Ag polystyrene sulfonate), gold alkyl acetate (Au alkylacetate) or gold alkyl sulfonate (Au alkylsulfonate) Composition for producing an electronic ink, characterized in that. The method of claim 1, The conductive polymer is a composition for producing an electronic ink, characterized in that selected from poly (3,4-ethylenedioxythiophene), polyaniline, polypyrrole and mixtures thereof. The method of claim 1, The reducing agent is a composition for producing an electronic ink, characterized in that hydrazine. (1) preparing a silver ionic solution, (2) adding 0.00001 to 0.5 g / mL of a conductive polymer and 0.00001 to 0.05 g / mL of reducing agent to the silver ion solution with respect to the solvent volume (mL) of the silver ion solution, and (3) In the solution, silver alkylacetate, silver alkylsulfonate, silver p-toluene sulfonate, silver camphorsulfonate, silver 2- Ag 2-acrylamido-1-propane sulfonate, Silver polystyrene sulfonate, Au alkylacetate, Au alkylsulfonate, S ₂ O ₈ ^2- / TiO ₂ -SiO ₂ , SO ₄ ^2- / Ti-La-O (Sulfonated La Ti-oxide), ZrO ₂ -SO ₄ ^2- , CsHSO ₄ , CsHSeO ₄ , CsH ₂ PO ₄ , a- Cs ₃ (HSO ₄ ) ₂ (H ₂ PO ₄ ), b-Cs ₃ (HSO ₄ ) ₂ [H _2-x (P _1-x , S _x ) O ₄ ] (0 <x <1), Cs ₂ (HSO ₄ ) (H ₂ PO ₄ ), Cs ₅ (HSO ₄ ) ₃ (H ₂ PO ₄ ) ₂ , Adding at least one solid acid selected from SiO ₂ -Al ₂ O ₃ , ZSM-5 and MgO-Y at 0.0004-0.5 g / mL relative to the solvent volume (mL) of the silver ion solution, Electronic ink manufacturing method comprising a. The method of claim 6, After adding the conductive polymer and the reducing agent, the electronic ink manufacturing method, characterized in that it further comprises the step of adjusting the pH. delete The method of claim 6, The solid acid silver alkyl acetate (Ag alkylacetate), silver alkylsulfonate (Ag alkylsulfonate), silver p-toluene sulfonate (Ag p-toluene sulfonate), silver camphorsulfonate (Ag camphorsulfonate), silver 2-acrylamido 1-propane sulfonate (Ag 2-acrylamido-1-propane sulfonate), silver polystyrene sulfonate (Ag polystyrene sulfonate), gold alkyl acetate (Au alkylacetate) or gold alkyl sulfonate (Au alkylsulfonate) Electronic ink manufacturing method, characterized in that. The method according to claim 6 or 7, Wherein said conductive polymer is selected from poly (3,4-ethylenedioxythiophene), polyaniline, polypyrrole, and mixtures thereof. The method according to claim 6 or 7, The reducing agent is an electronic ink manufacturing method, characterized in that hydrazine. Claim 1, comprising the composition for preparing an electronic ink of any one of claims 3 to 5, the viscosity is 1.0 to 10000.0 cp, the surface tension is 40 to 60 mN / m, the silver content is 2.5 to 10% by weight Electronic ink for inkjet printers. Claim 1, comprising the composition for producing an electronic ink of any one of claims 3 to 5, the viscosity is 100 ~ 200 cp, the surface tension is 20 ~ 60 mN / m, silver content 20 ~ 60 wt% Electronic ink for gravure printers.

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