KR20060019907A - Preparation method of micro line of aqueous metal nano sol on surface-modified ito glass for inkjet method - Google Patents

Abstract

The present invention relates to a method for forming a fine line of a high concentration aqueous metal nano sol for inkjet by surface modification of a hydrophobic substrate, and more particularly, to a layer-by-layer using a cationic polymer electrolyte or a nonionic surfactant. Hydrophobic substrates were hydrophilized to form a polymer-metal salt complex by adding a polymer electrolyte to an aqueous metal salt solution, and then using a high concentration aqueous metal nano sol having a size of 100 nm or less, prepared by reducing agent treatment, on a substrate by direct inkjet technique. The present invention relates to a method for forming a fine line of a high concentration aqueous metal nano sol for an ink jet by modifying a surface of a hydrophobic substrate capable of forming a fine line in a.

Polymer electrolyte, metal nano sol, surface modifier, hydrophobic substrate

Description

Preparation method of micro line of aqueous metal nano sol on surface-modified ITO glass for inkjet method}             

1 is a transmission electron microscope (TEM) photograph of a silver (Ag) nanopowder (10 wt% concentration) prepared according to Example 7 of the present invention.

Figure 2 is a diagram showing the rheological behavior of the silver nano sol of the preparation example.

Figure 3 is a photograph showing the contact angle of distilled water and silver nano sol for a glass substrate, a pure ITO substrate and a hydrophilic ITO substrate.

4 is a graph showing the change of silver nano sol contact angle according to the concentration of polyethyleneimine treated on the ITO substrate.

FIG. 5 is an optical microscope image of fine lines formed by spraying silver nanosols by an inkjet method on a glass substrate (a), a pure ITO substrate (b), and a hydrophilic ITO substrate (c).

The present invention relates to a method for forming a fine line of a high concentration aqueous metal nano sol for inkjet by surface modification of a hydrophobic substrate, and more particularly, to a layer-by-layer using a cationic polymer electrolyte or a nonionic surfactant. Hydrophobic substrates were hydrophilized to form a polymer-metal salt complex by adding a polymer electrolyte to an aqueous metal salt solution, and then using a high concentration aqueous metal nano sol having a size of 100 nm or less, prepared by reducing agent treatment, on a substrate by direct inkjet technique. The present invention relates to a method for forming a fine line of a high concentration aqueous metal nano sol for an ink jet by modifying a surface of a hydrophobic substrate capable of forming a fine line in a.

In general, in order to effectively transmit visible light generated from a phosphor in a flat panel display plasma display panel (PDP), a transparent electrode and a low resistance bus electrode for transmitting a signal to the transparent electrode are required.

Representative methods that have been put to practical use as a method for forming bus electrodes among the electrodes include screen printing of Ag electrodes, photolithography patterning of Ag electrodes, or photoetching of Cr / Cu / Cr electrodes. Although the photosensitive electrode paste manufactured by the photolithography method which is currently used most among the above methods has an excellent resolution when forming a fine pattern, it still takes a long time in the manufacturing process due to printing, exposure, drying and developing processes. It has a disadvantage.

Accordingly, there is a need for a new pattern formation technology using a new technique, which is improved in terms of manufacturing process and cost, compared to the photolithography method.

Currently, as the fine pattern forming technology, a solution or a suspension is added to several tens of pL (pico) through screen printing, a photolithography method that enables the formation of a small line width, and a micronozzle. ink jet techniques such as spraying with droplets of liters to form fine lines or dots of several tens of micrometers in width.

Comparing the inkjet technique with the screen printing or photolithography method, the following advantages are specifically mentioned. First, no mask for forming fine lines is necessary. Second, it is not affected by the size of the substrate to be printed. Third, the printing time is short and the process is simple. Fourth, it is an eco-friendly process with little waste, and consumes less material.

In other words, the current position of the inkjet technique lies between screen printing and photolithography methods in terms of manufacturing cost and resolution, and is expected to serve as a bridge between nano and micro fields, and may partially replace these two technologies. It is expected.

Therefore, the recent movement of the inkjet technique in the production of electrodes in all flat panel display fields, such as liquid crystal displays (LCDs), organic light emitting diodes (OLEDs), field emission displays (FEDs), etc. It is actively underway.

In order to apply the inkjet technique to the display manufacturing process, it is very important to diversify inkjet ink materials and control the wettability of the substrate to be printed. In view of the diversification of the inkjet ink material, not only a metal nanosol having dispersion stability and uniformly sized particles is required for stable inkjet injection, but also the connection and high conductivity of the electrode after formation and sintering of fine lines High concentrations of metal nano sol are required.

At present, the method for producing the metal nanoparticles is known as a physical method such as a gas phase method and a chemical synthesis method using a liquid phase reaction. There is a prior art.

However, it would be more useful to employ a method of improving the production efficiency of high concentration of metal nanosol by using a relatively simple synthesis device as an environmentally friendly aqueous solution chemical method, rather than using an expensive device such as using a laser. It is feed.

When preparing metal nanoparticles by chemical method, control of particle size and particle size distribution is an important requirement, and most suitable surfactants (anti-agglomerating agent or Dispersing agent).

Many researches have been conducted in relation to the preparation method of the metal powder using such a surfactant, and Korea Patent Publication No. 2002-0022168, 2001-0070070, 2000-0012423, 2000-0011546, etc. Several inventions have been filed and published.

However, when the metal nanoparticles are prepared using the surfactant as described above, the smaller the size of the metal nanoparticles to be prepared, the exponentially increasing the amount of the surfactant to be used to prevent the growth and aggregation of the particles. . Therefore, there is a disadvantage that simply by using a surfactant can not control the concentration of the metal nanoparticles above a certain concentration.

In order to overcome the above-mentioned drawbacks, the chemical manufacturing method of the metal nanoparticles was improved to reduce the metal ions in the metal salt solution with a suitable reducing agent, and then a surfactant was added to the surface of the metal particles to be reduced to adsorb the surface. By allowing the growth of particles to be suppressed, it is possible to produce fine metal particles without using an excessive amount of surfactant.

MEANS TO SOLVE THE PROBLEM The present inventor adds a polymer electrolyte to a metal salt aqueous solution, forms a polymer-metal ion complex, and then processes it with a reducing agent to produce high concentration metal particles of fine and uniform size without aggregation or sedimentation of the metal particles. Application No. 2003-0015923 has been proposed.

The metal nano sol prepared by the above method has a contact angle characteristic similar to that of distilled water. In this case, the contact angle is generally a measure of the wettability of the solid surface, and is measured by mostly fixed water droplets, and a low contact angle indicates high wettability and a high contact angle indicates low wettability. Therefore, the wettability of the water-based metal nano sol to the glass substrate has almost the same characteristics as distilled water.

However, the wettability of distilled water and metal nano sol on hydrophobic substrates such as pure ITO substrates is very different from the wettability on glass substrates. For example, the contact angles measured for glass of distilled water and silver nano sol are as low as 27.1 ㅀ and 21.6 반면, while the contact angles are very large at 82.7 ㅀ and 66.1 에서는 on pure ITO substrates.

That is, the aqueous metal nano sol prepared by the proposed method up to now has a high hydrophilicity and is difficult to print directly due to the low wettability of the hydrophobic ITO substrate, and the formation of fine lines used for electrodes such as flat panel displays This is absolutely impossible.

Therefore, the present inventors studied the inkjet patterning technology of the electrode for the synthesis of the inkjet metal nanosol and the formation of the fine line as the electrode material that can be used for PDP, etc. As a result, the lamination method using a cationic polymer electrolyte or a nonionic surfactant -by-layer) by modifying the surface of the hydrophobic substrate and hydrophilized, it is possible to form uniform fine lines directly on the substrate by inkjet technique using a high concentration aqueous metal nano sol manufactured to a fine size of 100 nm or less. Knowing to complete the present invention.

Therefore, the present invention forms a polymer-metal salt complex by adding a polymer electrolyte to an aqueous metal salt solution, and then forms a micro-line by inkjet technique using a high concentration aqueous metal nano sol prepared in a fine and uniform size by treating it with a reducing agent. SUMMARY OF THE INVENTION An object of the present invention is to provide a method for forming a fine line of a high concentration aqueous metal nano sol for inkjet by surface modification of a hydrophobic substrate.

The present invention forms a polymer-metal salt complex by adding a polymer electrolyte to an aqueous metal salt solution, and then processes it with a reducing agent to prepare a small and uniform high-concentration metal nano sol. The hydrophobic substrate is washed with acetone and dried at room temperature to 60 ° C. After immersing in a 10 to 10,000 ppm aqueous solution of the surface modifier, and then dried at 80 ~ 120 ℃ hydrophilic treatment, and a metal nano sol comprising the step of spraying the metal nano sol to the hydrophilized substrate by an inkjet technique It characterized by the method of forming a fine line.

The present invention is to form a polymer-metal salt complex by adding a polymer electrolyte to the aqueous metal salt solution by modifying and hydrophilizing the hydrophobic substrate by a layer-by-layer using a cationic polymer electrolyte or a nonionic surfactant. Fine line of high density water based metal nano sol for inkjet by surface modification of hydrophobic substrate which enables formation of fine lines on substrate by direct inkjet method using high concentration water based metal nano sol of 100 nm or less prepared by reducing agent treatment It relates to a formation method.

Referring to the present invention in more detail as follows.

The present invention is characterized in that it is intended to improve the physical properties of the substrate in order to form fine lines used for electrodes such as flat panel displays. As described above, the water-based metal nano sol manufactured by the method proposed so far is hydrophilic. This strong and hydrophobic ITO substrate has a low wettability is difficult to print directly, and therefore it is proposed to improve the problem that it was impossible to form a fine line used for electrodes such as flat panel display at all.

First, in order to form fine lines used for electrodes such as flat panel displays, metal nano sol prepared by various conventional methods may be used. Among them, the metal nano sol prepared by the method proposed by the present inventors has a fine and uniform size, and thus, when applied to the method for forming a fine line of the present invention, a more preferable effect may be obtained.

The present inventors prepared an aqueous high concentration metal nano sol using the polymer electrolyte represented by the following Chemical Formula 1. That is, as shown in Chemical Formula 1, since the metal ions to be reduced in each structural unit are substituted, particle growth is suppressed from the reduction process of ions, and thus, smaller particles may be prepared as compared to using a general surfactant. Furthermore, since the polymer electrolyte has a large number of functional groups capable of substituting metal ions in one electrolyte, it is possible to effectively control the aggregation and growth of particles even when using a very small amount compared to the general surfactant.

The process of synthesizing a metal nano sol using the polymer electrolyte proposed by the inventor is as follows.

First, a soluble metal salt is added to distilled water to prepare an aqueous metal salt solution. The polymer-metal salt complex is then formed by adding and stirring the polymer electrolyte to the aqueous metal salt solution. Then, a reducing agent is added to the polymer-metal salt complex-containing solution to reduce metal ions to obtain a metal particle solution.

Looking at each component of the metal nano sol used to form the fine line of the present invention described above are as follows.

As an aqueous metal salt solution, soluble metal salts such as nitrates, sulfates, carbonates or chlorides of metal ions selected from silver (Ag), copper (Cu), gold (Au) and palladium (Pd) are dissolved in water and used. Specifically, silver nitrate (AgNO ₃ ), copper nitrate (Cu (NO ₃ ) ₂ ), or the like can be used.

As the reducing agent, NaBH ₄ , LiAlBH ₄ , hydrazine, hydrazine hydrate, formaldehyde and the like can be used. The reducing agent uses 1 to 1.2 equivalents based on 1 equivalent of the metal salt to be reduced. If the amount of the reducing agent is less than 1 equivalent, there may be a problem that the metal salt cannot be reduced by 100%. It is undesirable because it is wasted.

The polymer electrolyte is a conventional polymer electrolyte having the properties that are dissociated soluble in water by the presence dissociation group in the polymer chain, dissociation groups present in the polymer chain, for example, carboxyl carbonate group (-COO ^-), sulfonate group ( -SO ₃ ^- can be included, and so on) ^-), sulfate group (-OSO ₃ ^-), phosphate groups (-OPO ₃ ^-) and a phosphonate group (-PO _3. Specific examples of the polymer electrolyte that can be applied to the present invention may be polyacrylic acid, polymethacrylic acid, polystyrene sulfonic acid, lignin sulfonic acid or salts thereof. In addition, as the polymer electrolyte, a copolymer copolymerized with the above dissociated group and a water-soluble polymer having no dissociation group, such as polyethylene, polyacrylamide, polyethylene glycol, or the like may be used. And the counter ion to combine with the dissociation of the electrolyte to form a salt may include a metal cation such as sodium, ammonium cation, amine cation and the like.

Although the amount of the polymer electrolyte may vary depending on the degree of polymerization of the polymer, it is generally preferred to add 10 to 150 parts by weight based on 1 part by weight of the metal salt. If the amount of the polymer electrolyte is less than 10 parts by weight, the fixing effect of the metal ions is remarkably decreased, so that the metal ions are freely present in the solution, and the agglomeration occurs in the reduction process. If the portion is exceeded, there is a problem that the solution gels due to a decrease in solubility.

According to the production method of the present invention as described above, it is possible to prepare a high concentration metal nano sol of 100 nm or less, and also in the concentration of the metal particle solution, as well as a high concentration solution of 10% by weight or more can be prepared. In addition, it was confirmed that the metal particles solution of high concentration prepared by the method of the present invention did not easily aggregate or settle even after being left for a long time.

In the present invention, to form a fine line on the substrate by the inkjet method using the metal nano-sol synthesized as described above.

The metal nano sol prepared by using the polymer electrolyte as described above is very hydrophilic, and is very suitable for coating and micropatterns on hydrophilic surfaces such as glass substrates. However, when the water-based metal nano sol prepared as described above is intended to form a fine line on a hydrophobic substrate such as an ITO substrate or a polymer resin flexible substrate by an inkjet technique, the wettability of the water-based metal nano sol is not as good as that of the hydrophobic substrate. It is not possible (see Fig. 5 (b)).

In the method for forming a fine line of the present invention, by hydrophilizing the hydrophobic substrate as described above, it is possible to print directly using a hydrophilic metal nano sol.

First, as the hydrophobic substrate, any hydrophobic substrate that can be used for flat panel display electrodes can be used. Specifically, examples thereof include a pure ITO substrate, a flexible substrate made of a polymer resin, and the like.

The hydrophobic substrate is washed with acetone and then dried at room temperature to 60 ° C., which is immersed in an aqueous solution in which the surface modifier is dissolved. As described above, the surface of the hydrophobic substrate is hydrophilic by a lamination technique which is washed with acetone and immersed in an aqueous solution of the surface modifier.

The surface modifiers used in the present invention include ionic polymer surfactants or nonionic surfactants, and specific examples thereof include polyethyleneimine, poly (sodium styrenesulfonate), poly (acrylic acid), and poly (N-vinyl-2). Ionicity such as -pyrrolidone), polyallylamine hydrochloride), poly (diallyldimethylammonium chloride), diazoresin, a polymer containing bipyridinium units, poly (4-vinylpyridine) Polymeric surfactants and the like, polyethylene glycol type nonionic surfactants, polyethylene glycol type nonionic surfactants, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbbi SPAN series, polyoxyethelene (20) selected from tan sesquioleates and sorbitan trioleates TWEEN series selected from tan monolaurate, polyoxyethylene (20) sorbitan monopalmitate, polyoxyethylene (20) sorbitan monostearate and polyoxyethylene (20) sorbitan monooleate , Polyoxy ethylene (10) isooctyl cyclohexyl ether, polyoxy ethylene (40) isooctyl cyclohexyl ether, polyoxy ethylene (10) isooctyl phenyl ether, polyoxy ethylene (8) isooctyl phenyl ether And polyhydric alcohol-type nonionic surfactants such as a surface modifier selected from polyhydric-alcohol-type nonionic surfactants selected from one or a mixture of two or more selected from the selected NP series. Can be used.

Such surface modifiers are prepared and used in an aqueous solution containing 10 to 10,000 ppm concentration, preferably 100 to 1000 ppm concentration. If the concentration of the surface modifier is less than 10 ppm, the contact angle between the metal nano sol and the substrate is high, and thus fine lines are not formed. If the concentration of the surface modifier exceeds 10,000 ppm, there is a problem such as unevenness of the surface treated surface.

The hydrophobic substrate to be hydrophilized in the aqueous surface modifier solution prepared as described above is immersed for 30 minutes to 3 hours, taken out, and dried at 80 to 120 ° C.

The hydrophilized substrate thus exhibits hydrophilic property of the hydrophobic surface, lowers the contact angle with the hydrophilic metal nano sol, and improves wettability. When the metal nano-sol is sprayed on the surface of the substrate hydrophilized by the above method by the inkjet method, fine lines of 10 to 100 μm are uniformly formed and applied to the microelectrodes.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited by the following Examples.

Preparation Example: Preparation of Silver Nano Sol

First, 6.5 g of silver nitrate was dissolved in 40 g of distilled water as a soluble metal salt. Then, 8 g of a polymer electrolyte (polyelectrolyte of sodium polyacrylate, 44S) was dispersed and stirred for 1 hour to replace the silver ions in the polymer electrolyte functional group. Nitric acid formed a complex. Separately, 0.1 g of NaBH ₄ , the equivalent of which is required to reduce the silver nitrate, was dissolved in 5 g of distilled water to prepare a reducing agent solution. The silver-Ag ions were reduced by slowly dropwise adding the reducing agent solution prepared above while strongly stirring the solution containing the polymer-silver nitrate. After the reduction reaction, the solution appeared dark black, and when diluted, the solution appeared light yellow. The metal particle solution containing the silver particles prepared as described above was analyzed by particle size analyzer and transmission electron microscope (TEM), and the particle shape and particle size distribution are shown in FIG. 1. The particle size of the prepared silver nano sol is 10 nm or less. It can be seen that the concentration is 10% by weight.

The silver nano sol contained 1 equivalent of polyacrylic ammonium salt with respect to the silver ion concentration, and the surface charge of the silver nano particles was determined to be a high concentration sol having excellent dispersibility of about -45 mV.

The high concentration of the silver nano sol rheological behavior is shown in Figure 2, which shows a so-called "thixotropic behavior" showing a slightly high viscosity at a low shear rate but a low viscosity at a high shear rate. Therefore, the silver nano sol of the present invention prepared as described above is expected to have a characteristic that it is easy to spray at low viscosity when sprayed through the micropores of the inkjet head, and that the viscosity is restored after spraying, so that the formation of fine lines is easy. do.

Examples 1 to 13: Hydrophilicity Treatment of Hydrophobic Substrates Using Cationic Polymer Surfactants

The pure ITO substrate was prepared by washing with acetone and drying at room temperature. Cationic surfactant polyethyleneimine (PEI; H (-NHCH ₂ CH _2- ) _n NH ₂ , Aldrich) as a surface modifier was dissolved in tertiary distilled water, prepared at the concentration shown in Table 1 below, and then washed After dipping for 2 hours and drying for 12 hours at 80 ℃ air atmosphere to prepare a hydrophilized ITO substrate.

Type and concentration of the surface modifier The ITO substrate was hydrophilized while changing as shown in Table 1 below.

Experimental Example 1: Measurement of Contact Angle

Contact angle is generally a measure of the wettability of a solid surface, mostly measured by sessile drop, with low contact angles showing high wettability and high contact angles showing low wettability. In order to observe the wettability, a contact angle measuring device (Phoenix-300, SEO, Korea) was used, and the contact angle of distilled water and silver nano sol was measured for each substrate.

1) Contact angle of distilled water and silver nano sol according to substrate type

Substrates were (a) glass substrates, (b) pure ITO substrates, and (c) ITO substrates (Example 2) coated with 100 ppm PEI. The results are shown in FIG. 3. According to FIG. 3, the contact angles measured for distilled water and silver nano-sols are low at 27.1 ㅀ and 21.6 ㅀ in glass substrates ((a), (d)], while the contact angles are 82.7 ㅀ and 66.1 ㅀ in pure ITO substrates. It was large [(b), (e)]. Distilled water and silver nano sol showed similar contact sensation characteristics, so that the wettability of the aqueous silver nano sol to the substrate was almost the same as that of distilled water.

On the other hand, the wettability in a pure ITO substrate suggests that it is very different from the wettability in a glass substrate.

2) Measurement of contact angle according to surfactant concentration

On the other hand, in order to find the proper concentration range of the PEI to be coated for the purpose of improving the printability of the ITO substrate, the contact angle was measured by coating a PEI having a different concentration on the ITO substrate and the results are shown in the accompanying drawings. The contact angle of the silver nano sol decreased rapidly until the amount of the polymer electrolyte was 10 ppm, but gradually decreased thereafter. Therefore, it was judged that about 100 ppm of PEI was sufficient to improve the printability of the silver nano sol on the ITO substrate. [Attachments (c) and (f) of FIG. The contact angles with respect to distilled water and silver nanosol of an ITO substrate are shown, respectively.

Experimental Example 2: Formation of Fine Lines

The silver nano sol of the preparation example was printed with an ITO substrate (Example 2) coated with PEI, and the silver nano sol was printed by an inkjet technique using a glass substrate.

Fine lines were formed with an inkjet printer, and the printed fine lines were observed at 300 times using an optical microscope (ICS-305A, Sometech, Korea), and the results are shown in the accompanying drawings of FIG. 5.

According to the accompanying drawings, when the fine lines were printed on the glass substrate, the line formation was possible, and the line width of about 40 μm was shown (FIG. 5 (a)). This is thought to be due to the large spreading of the lines due to the good wettability of the substrate and the silver nano sol. In the case of printing fine lines on a pure ITO substrate, no lines were formed, but only dots having a size of about 50 μm were formed (FIG. 5B). As shown in (b) and (e) of FIG. 3, respectively, the contact angles of distilled water and silver nanosol were observed to be high at 82.7 kPa and 66.1 kPa on pure ITO substrates, which do not form fine lines because of their low wettability. I don't think so.

Therefore, in this study, the contact angle between distilled water and silver nanosol was measured on an ITO substrate (Example 2) surface-treated with 100 ppm of cationic polyelectrolyte (PEI) to improve the wettability of the metal nanosol on the ITO substrate. As shown in (c) and (f) of FIG. 3, the contact angle of distilled water was 53.4 kPa and the contact angle of silver nano sol was significantly lowered to about 40.3 kPa. In this case, as shown in (c) of FIG. 5, the fine line was formed with a line having a uniform line width of about 30 μm. It is thought that the wettability of the silver nano sol is increased as the ITO substrate is coated with a surface modifier, that is, cationic polymer surfactant (PEI), thereby improving the printability of the line.

division Surface modifier Concentration (ppm) Print width (㎛) Whether fine lines are formed Comparative example - - Impossible (dot formation) Example 1 PEI 100 50-100 possible Example 2 PEI 1,000 50-100 possible Example 3 PEI 10,000 30-100 possible Example 4 SPAN 80 100 50-100 possible Example 5 SPAN 80 1,000 50-100 possible Example 6 SPAN 80 10,000 30-100 possible Example 7 PSS 100 50-100 possible Example 8 PSS 1,000 50-100 possible Example 9 PSS 10,000 30-100 possible Example 10 PDDA 100 50-100 possible Example 11 PDDA 1,000 50-100 possible Example 12 PDDA 10,000 30-100 possible PEI; Polyethyleneimine SPAN 80; sorbitan monooleate PSS; poly (sodium styrenesulfonate) PDDA; poly (diallyldimethylammonium chloride)

As described above, in the present invention, the polymer electrolyte is added to the aqueous solution in which the metal salt is dissolved to form a polymer-metal salt complex, which is reduced to control the growth and agglomeration of the particles to control ultra-sized uniform metal particles of 100 nm or less. And hydrophilic treatment of the hydrophobic substrate by layer-by-layer using acetone cleaning and a surface modifier, the hydrophilic metal nano sol can be sprayed by inkjet technique to form uniform narrow narrow lines. .

According to the present invention, since the microline can be formed by a simple method of hydrophilic treatment of the hydrophobic substrate, it is expected to be very useful as an electrode material for a flat panel display panel. do.

Claims (8)

Adding a polymer electrolyte to an aqueous metal salt solution to form a polymer-metal salt complex, and then treating it with a reducing agent to produce a small and uniform high concentration metal nano sol, Washing the hydrophobic substrate with acetone, drying at room temperature to 60 ° C., immersing in a 10 to 10,000 ppm aqueous surface modifier, and drying at 80 to 120 ° C. for hydrophilic treatment, and The method of forming a fine line of a metal nano-sol, characterized in that comprising the step of spraying the metal nano-sol on the hydrophilized substrate by an inkjet technique. The method of claim 1, wherein the aqueous metal salt solution is nitrate, sulfate, carbonate or salt of a metal ion selected from silver (Ag), nickel (Ni), copper (Cu), gold (Au), cobalt (Co) and palladium (Pd). Method for forming a fine line of metal nano sol, characterized in that the chloride solution is dissolved. The method of claim 1, wherein the polymer electrolyte has a dissociation group in the polymer chain and is dissolved in water to dissociate. The polymer electrolyte of claim 1, wherein the polymer electrolyte is a polymer material having a dissociation group selected from polyacrylic acid, polymethacrylic acid polystyrenesulfonic acid, lignin sulfonic acid, and salts thereof, or a polymer material having no dissociation group bonded thereto. Method for forming a fine line of a metal nano-sol, characterized in that selected from copolymers of other water-soluble polymers. The method of claim 1, wherein the polymer electrolyte is used in an amount of 0.1 to 30 parts by weight based on 1 part by weight of the metal salt. The method of claim 1, wherein the metal nanoparticles produced are ultrafine powders of 100 nm or less. The method of claim 1, wherein the surface modifier is a cationic polymer electrolyte or a nonionic surfactant. 8. The surface modifier of claim 1 or 7, wherein the surface modifier is polyethyleneimine, poly (sodium styrenesulfonate), poly (acrylic acid), poly (N-vinyl-2-pyrrolidone), polyallylamine hydrochloride), Cationic polymeric surfactants or polyethylene glycol type nonionic surfactants, selected from poly (diallyldimethylammonium chloride), diazoresins, a polymer containing bipyridinium units and poly (4-vinylpyridine) SPAN series selected from tan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate and sorbitan trioleate, polyoxyethelene ( 20) sorbitan monolaurate, polyoxyethylene (20) sorbitan monopalmitate, polyoxyethylene (20) sorbitan monostearate and polyoxyether (20) TWEEN series selected from sorbitan monooleate, polyoxyethylene (10) isooctylcyclohexyl ether, polyoxyethylene (40) isooctylcyclohexyl ether, polyoxyethylene (10) iso Among polyhydric alcohol type nonionic surfactants selected from one or a mixture of two or more selected from octylphenyl ether, polyoxyethylene (8) isooctylphenyl ether, and polyoxyethylene (40) isooctylphenyl ether selected NP series Method for forming a fine line of metal nano sol, characterized in that the selected surface modifier is used.

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