KR20090021004A - Preparation of silver powder by using the insoluble silver salts - Google Patents

Abstract

A manufacturing method of silver powder using insoluble silver compounds is provided to manufacture a silver compound with low reduction temperature and the cheap cost by performing an oxidation and reduction process. A manufacturing method of silver powder using insoluble silver compounds comprises the following steps of: manufacturing slurry solution by dispersing an insoluble silver compound into distilled water; manufacturing silver oxide by reacting NaOH 10~40weight% and silver slurry solution 1 by weight; and collecting the disposed silver power. The insoluble silver compound is AgCl or AgBr.

Description

Preparation method of silver powder using insoluble silver compound {Preparation of silver powder by using the insoluble silver salts}

The present invention relates to a method for preparing silver powder from silver chloride and silver bromide used as an insoluble silver compound, and more particularly, to prepare a distilled water solution in which silver chloride and silver bromide are suspended, and to obtain silver oxide ( Ag ₂ O) and reducing the silver oxide (Ag ₂ O) to aqueous hypophosphorous acid solution to a method for producing a silver powder in a very simple process.

Recently, with the development of advanced industrial technology, the demand for high-performance precision materials is rapidly increasing. Accordingly, fine metal raw materials that can provide highly controlled physical and chemical properties while improving strength, hardness, wear resistance, weight, etc. Powder is required.

Silver powder is mixed with conductive fillers such as thick film integrated circuits, printed wiring circuits, thermosetting conductive pastes, diamond ceramic powders, tungsten carbides, tungsten powders, nickel powders, germanium powders and the like in the electronics industry to produce sintered alloys. .

As a method of producing silver powder, it is distinguished as a chemical reduction method and a physical (mechanical) method. As physical methods, gas phase (flame) decomposition by aerosol injection and pulverization of mass silver are known, but due to many limitations due to yield and harsh manufacturing process, chemical reduction is widely used due to relatively high reduction rate and efficient recovery of silver particles. It is becoming.

Korean Patent No. 10-181572 discloses a method of forming a precipitate from an aqueous solution of silver nitrate with sodium hydroxide or potassium hydroxide, preparing silver powder by adding formaldehyde as a reducing agent, and then treating the product with formic acid for 24 hours.

Korean Patent Laid-Open Publication No. 10-2005-40226 dissolves a silver mass in an aqueous solution of nitric acid to prepare an aqueous solution of silver nitrate, and adds ammonium hydroxide to form a silver-ammonium complex ion, followed by addition of a surfactant and pH adjustment to reduce formaldehyde. Known methods for producing silver particles are known.

Republic of Korea Patent No. 10-368055 was prepared by adding ammonia water to the aqueous solution of silver nitrate adjusted to pH 11 and dissolved in the hydroquinone as a separate reducing agent solution. Spherical silver powders were prepared by mixing the two solutions at room temperature.

Korean Patent Laid-Open Publication No. 10-2005-116544 discloses a method of preparing silver plate-shaped particles by reacting a solution of silver nitrate with a solution of hydroquinone and potassium sulfite (or ammonium sulfite) dissolved in distilled water and adding ammonia water.

Republic of Korea Patent No. 10-449369 step 1 of adding ammonium hydroxide to ethylene glycol; Dissolving silver nitrate and PVP in a solution in which ethylene glycol and ammonium hydroxide are mixed; It is known to prepare a plate-like silver powder through step 3 of adding hydrogen peroxide and chloroplatinic acid (H ₂ PtCl ₆ ) to ethylene glycol.

Korean Patent Laid-Open Publication No. 10-12141 is immersed in a concentrated nitric acid and maintained at a temperature of 70 ℃ to 80 ℃ dissolved to prepare a silver chloride aqueous solution of sodium chloride and adjusted to pH 4 by adding an aqueous hydrochloric acid solution. Silver powder was recovered when the stirrer with the iron pieces attached to the solution was rotated.

Most domestic patents for preparing silver powder are composed of a silver powder aqueous solution and a method for preparing silver powder by a reducing agent. However, the disadvantage of the prior art for the production of silver powder is that silver nitrate is more than four times more expensive than silver ingots, and it has a long and complicated operation such as separate reducing agent and surfactant, long reduction time, pH control, organic solvent, and temperature rise. It was a fair. Therefore, there is a need for a relatively short reduction time, inexpensive silver compound, and silver powder production technology that does not require excessive temperature rise.

The present invention relates to a process for the production of silver powders using insoluble silver salts which are inexpensive and require no special heating operation at room temperature.

The present invention is a step of preparing a slurry solution by dispersing silver bromide or silver chloride used as an insoluble silver compound in distilled water; 2 steps of preparing silver oxide (Ag ₂ O) by reacting 10 to 40% by weight of sodium hydroxide with 1 part of the silver slurry solution; And a three step of recovering the precipitated silver powder by performing a reduction reaction on the silver oxide (Ag ₂ O) and an aqueous hypophosphorous acid solution as a reducing agent in a weight ratio of 1: 1 to 1:10. There is a characteristic.

The present invention utilizes oxidation and reduction processes of insoluble silver compounds so that silver powders can be produced without the need to use conventional high reduction temperatures and expensive silver salts. The silver powder obtained by this invention is used for the manufacture of the film which has antibacterial, bactericidal, antistatic, electromagnetic wave shielding, insect repellency, photosensitivity, and deodorizing property disperse | distributed to water-soluble polymer substrates, such as water-dispersed polyurethane and water-dispersed acryl.

The insoluble silver compound used in the present invention is silver chloride, silver bromide, and has a solubility product (K _sp , solubility product) of 10 ^-10 or less, and can be used as a raw material for preparing silver powder according to the prior art because it has substantially no solubility in water. There was no. Thus, the present invention was to produce the silver oxide as an intermediate in order to improve the above problems and to enable the production of silver powder using the same.

Hereinafter, the production method of the silver powder according to the present invention will be described in more detail.

The reactions of the present invention are all performed at room temperature, i.e., about 25 ° C., which does not require the high temperature conditions (80 ° C. to 120 ° C.) required for silver powder production in the prior art.

First, silver chloride or silver bromide is dispersed in distilled water to prepare a slurry solution. The concentration of silver chloride or silver bromide in the distilled water is in the range of 1 to 50% by weight, preferably in the range of 15 to 30% by weight, and if it is out of the range, the amount of silver powder to be recovered is small and the filtration time is long. It is good to keep it.

Next, sodium hydroxide is reacted with the slurry solution to produce silver oxide (Ag ₂ O). At this time, when sodium hydroxide is added at about 10% by weight to 40% by weight with respect to the slurry, the oxidation reaction of the silver compound proceeds rapidly. If the amount of sodium hydroxide is less than 10% by weight, the pH of the solution is not reached to recover enough silver oxide, and if it exceeds 40% by weight, the silver oxide is contaminated during recovery because the sodium hydroxide content is high in the recovered silver oxide. It is preferable to maintain the above range because there is a problem of deterioration.

The silver oxide (Ag ₂ O) powder obtained in the above step was filtered, washed with water and dried at 80 ° C to 100 ° C. The drying temperature does not significantly affect the deterioration and purity of silver oxide (Ag ₂ O) in this range, but in order to proceed with the reduction reaction smoothly in consideration of sodium hydroxide which may remain, it is dried for 1 hour as close as possible to 100 ° C. It is desirable to be.

Next, the silver oxide (I) is mixed with a reducing agent to prepare silver powder precipitated by a reduction reaction. The reducing agent uses hypophosphorous acid (phosphinic acid) in the aqueous phase, the reducing agent may be used an extra-pure grade generally used in the art.

This reaction of silver oxide with a reducing agent is shown in the following scheme 1.

At this time, the reduction potential and equilibrium constant of Scheme 1 is 0.841 V, 10 ²⁸ , the reduction reaction proceeds spontaneously. From the scheme 1, silver oxide (Ag ₂ O) and hypophosphorous acid solution (phosphinic acid) used in the direct silver reduction reaction is very suitable for the reduction reaction.

The silver oxide (Ag ₂ O) and the reducing agent is used in a mixture of 1: 1 to 10: 10 by weight ratio, if the amount is out of the range used in the reduction reaction is rapidly progressed excess water vapor or the reduction reaction occurs slowly It is advisable to keep this range because it appears. At this time, the hypophosphorous acid is used as an aqueous solution, the concentration of commercially available industrial hypophosphorous acid is 37% by weight or 50% by weight, both types can be used in the present invention.

After the reduction reaction was completed, the silver precipitate was filtered, washed with water and dried at 80 ° C to 100 ° C.

Silver (Ag) powder prepared by the above method is polyethylene, polypropylene, polyvinyl chloride, polystyrene, acrylonitrile-butadiene-styrene (ABS), polymethyl methacrylate (PMMA), polycarbonate, polyester, etc. It has excellent compatibility and is used in the production of plastic molded articles, fibers, paints and inks having antibacterial and bactericidal properties, abrasive properties, UV protection properties, photosensitivity, antistatic properties, electromagnetic shielding and deodorization properties.

Hereinafter, the present invention will be described in more detail based on the following examples, but the present invention is not limited to the examples.

Preparation Example 1 Oxidation (I) from Silver Bromide

3.91 g of silver bromide was dispersed in 12.78 g of distilled water at 20 ° C. Thereafter 4.654 g of sodium hydroxide was added to the solution and a precipitate formed at the bottom of the solution when the sodium hydroxide was dissolved. The precipitate was recovered from the reaction mother liquor as GF / C filter paper with a pore size of about 1.3 μm and washed three times with distilled water. After washing, the silver oxide powder was dried at 100 ° C. for 1 hour.

Preparation Example 2 (I) Oxidation from Silver Chloride

1.4 g of silver chloride was dispersed in 4 g of distilled water at 20 ° C. Thereafter, 2.56 g of sodium hydroxide was added to the solution, and a precipitate formed at the bottom of the solution when the sodium hydroxide was dissolved. The precipitate was recovered from the reaction mother liquor as GF / C filter paper with a pore size of about 1.3 μm and washed three times with distilled water. After washing, the silver oxide powder was dried at 100 ° C. for 1 hour.

Example 1

1 g of silver oxide (I) prepared in Preparation Example 1 and 3.78 g of an aqueous hypophosphorous acid solution (37 wt% concentration) were mixed at 20 ° C. Silver oxide and aqueous hypophosphite solution caused a violent reduction reaction. The white silver particles were recovered from the reaction mother liquor as GF / C filter paper having a pore size of about 1.3 μm and washed three times with distilled water. The washed silver powder was dried at 100 ° C.

In order to confirm the structure of the silver powder prepared above, XRD diffractograms were measured and the results are shown in FIG. 4.

Example 2

1 g of silver oxide (I) prepared in Preparation Example 2 and 4.17 g of an aqueous hypophosphite solution (37 wt% concentration) were mixed at 20 ° C. The silver oxide and hypophosphite aqueous solution caused a vigorous reduction reaction. The white silver particles were recovered from the reaction mother liquor as GF / C filter paper having a pore size of about 1.3 μm and washed three times with distilled water. The washed silver powder was dried at 100 ° C.

XRD diffractograms were measured to confirm the structure of the silver powder prepared above, and the results are shown in FIG. 4.

Figure 1 shows a manufacturing process of the silver powder according to the present invention.

Figure 2 shows the XRD diffractogram of the silver oxide (Ag ₂ O) prepared in Preparation Example 2 of the present invention.

Figure 3 shows the XRD diffractogram of the silver bromide and silver chloride powder used in the present invention.

Figure 4 shows the XRD diffractogram of silver (Ag) powder obtained from silver bromide and silver chloride in accordance with the present invention.

Claims (2)

Dispersing an insoluble silver compound in distilled water to prepare a slurry solution; 2 steps of preparing silver oxide (Ag ₂ O) by reacting 10 to 40% by weight of sodium hydroxide with 1 part of the silver slurry solution; And Preparation of silver powder comprising the three steps of recovering the silver powder precipitated by performing a reduction reaction in the silver oxide (Ag ₂ O) and an aqueous hypophosphorous acid solution as a reducing agent in the range of 1: 1 to 1:10. Way. The method of claim 1, wherein the insoluble silver compound is AgCl or AgBr.

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