WO2022044676A1 - Silver-coated flake-form copper powder, and method for manufacturing same - Google Patents

Abstract

In the present invention, the value of a brightness L* with respect to a degree of dispersion defined by D₉₀/D₁₀ is 13 or higher, where D₉₀ is the volume-cumulative grain diameter at an accumulated volume of 90 vol% according to a laser-diffraction-scattering grain distribution measurement method, and D₁₀ is the volume-cumulative grain diameter at an accumulated volume of 10 vol%. A silver-coated flake-form copper powder is manufactured by a method in which: a dispersion liquid containing a copper parent powder and a first complexing agent is processed by a medium-stirring mill device, and copper parent particles constituting the copper parent powder are deformed into a flaky form; and the copper parent powder, which includes the copper parent particles that were deformed into a flaky form, is processed by an aqueous liquid containing silver ions and a second complexing agent, and the silver is deposited onto the surface of the copper parent particles.

Description

Silver-coated flake-shaped copper powder and its manufacturing method

The present invention relates to silver-coated flake-shaped copper powder and a method for producing the same.

Since the flake-shaped copper particles have a large specific surface area due to their shape and the particles easily come into contact with each other, it is easy to impart conductivity to the resin by adding the flake-shaped copper particles to the resin. .. However, copper is easily oxidized, and as a result, the electrical resistance of the copper particles is likely to increase. For the purpose of compensating for this shortcoming, various techniques have been proposed in which the surface of copper particles is coated with silver, which is a metal having a lower electric resistance than copper, to suppress an increase in the electric resistance of the particles.

For example, Patent Documents 1 to 3 propose silver-coated flake-shaped copper powder having silver on the surface and containing flattened silver-coated flake-shaped copper particles.

Japanese Unexamined Patent Publication No. 2010-275638 JP-A-2015-71818 Japanese Unexamined Patent Publication No. 2016-35098

According to the techniques described in Patent Documents 1 to 3, the electrolytic copper powder is flattened using a crushing device such as an attritor, and then the surface of the copper powder is coated with silver by substitution plating. However, the silver-coated flake-shaped copper powder obtained by this method has a problem that the silver coating is not uniform and the surface of the copper powder tends to be partially exposed. This problem is particularly remarkable when the thickness of the electrolytic copper powder after flattening is thin. When the silver-coated flake-shaped copper powder in such a coated state is mixed with the resin, copper is likely to elute into the resin, and as a result, the resin is likely to deteriorate over time.
Therefore, an object of the present invention is to provide a silver-coated flake-shaped copper powder and a method for producing the same, which can eliminate various drawbacks of the above-mentioned prior art.

The present invention is a silver-coated flake-shaped copper powder containing at least silver-coated flake-shaped copper particles having silver on the surface.
For the silver-coated flake-shaped copper powder, the volume cumulative particle size at a cumulative volume of 90% by volume measured by the laser diffraction / scattering type particle size distribution measurement method is D ₉₀ (μm), and the volume cumulative particle size at a cumulative volume of 10% by volume is D ₁₀ . When (μm) is set
The problem is solved by providing the silver-coated flake-shaped copper powder having a lightness L * of 13 or more with respect to the dispersity defined by D ₉₀ / D ₁₀ . Is.

Further, in the present invention, the dispersion liquid containing the copper mother powder and the first complexing agent is treated with a medium stirring mill device to deform the copper mother particles constituting the copper mother powder into flakes.
The copper mother powder containing the copper mother particles deformed into flakes is treated with an aqueous solution containing silver ions and a second complexing agent to precipitate silver on the surface of the copper mother particles, in the form of silver-coated flakes. It provides a method for producing copper powder.

Hereinafter, the present invention will be described based on the preferred embodiment thereof.
The present invention relates to silver-coated copper powder, which is an aggregate of silver-coated copper particles having silver on at least the surface of copper particles as a base material. Silver-coated copper particles have one of the characteristics in their outer shape. Specifically, the silver-coated copper particles have a flake-like shape. Therefore, in the following description, the silver-coated copper particles are referred to as "silver-coated flake-shaped copper particles", and the silver-coated copper powder is referred to as "silver-coated flake-shaped copper powder".

In the present specification, "flake-like" is synonymous with "flat-like" and "flaky-like", and means that the particles have a thin-plate-like shape. Flake-like particles are specified by their aspect ratio. The aspect ratio is a value of D / T, which is the ratio of the major axis D on the plate surface when the flake-shaped particles are viewed in a plan view to the thickness T of the flake-shaped particles. The major axis D on the plate surface is the length of the longest line segment among the line segments crossing the plate surface. In the present invention, the aspect ratio of the silver-coated flake-shaped copper particles is preferably 5 or more and 160 or less, preferably 10 or more, from the viewpoint of imparting high conductivity when the silver-coated flake-shaped copper powder is added to the resin. It is more preferably 160 or less, further preferably 10 or more and 140 or less, further preferably 15 or more and 140 or less, further preferably 20 or more and 140 or less, and 30 or more and 120 or less. Is particularly preferable, and 30 or more and 80 or less are particularly preferable.

For the aspect ratio, the operation of measuring the major axis D and the thickness T for one particle and calculating the D / T value is performed for 50 or more particles, and the D / T value obtained by the operation is performed. The arithmetic mean value of.
The method for measuring the major axis D and the thickness T is as follows.
Major axis D: After taking a sample at an arbitrary magnification with an electron microscope, the major axis is measured using image analysis particle size distribution measurement software (Mac-View manufactured by Mountech Co., Ltd.).
Thickness T: The sample is filled with resin, and the cross section is processed with a cross section polisher. Then, after taking an image at an arbitrary magnification using an electron microscope, the measurement is performed in the same manner as in the major axis D.

The silver-coated flake-shaped copper particles have no particular limitation on the shape in a plan view, that is, the shape of the plate surface, and may have a shape such as a substantially circular shape, a substantially oval shape, a substantially elliptical shape, or an amorphous shape. Of these shapes, a substantially circular shape is preferable from the viewpoint of imparting high conductivity when the silver-coated flake-shaped copper powder is added to the resin.

When the shape of the plate surface of the silver-coated flake-shaped copper particles is substantially circular, the circularity of the plate surface is preferably 0.60 or more and 0.95 or less, and 0.65 or more and 0.90 or less. Is more preferable, and more preferably 0.65 or more and 0.85 or less. The circularity is defined as 4πS / L ² when the area of the plate surface is S and the peripheral length of the plate surface is L. The circularity is an arithmetic mean value of the values measured for 50 or more particles.

The specific method for measuring the circularity is as follows.
Image analysis Measurement is performed using particle size distribution measurement software (Mac-View manufactured by Mountech Co., Ltd.). Using this software, trace the contours of 50 or more samples to determine the area within the contours. Calculate the equivalent circle diameter from the area and average it.

In the silver-coated flake-shaped copper particles, if a part of the surface of the flake-shaped copper particles as the base material is exposed, that is, if the silver coating is non-uniform, the silver-coated flake-shaped copper powder When mixed with the resin, the resin may be denatured due to the contact of copper with the resin. Therefore, in the silver-coated flake-shaped copper particles, it is preferable that the surface of the flake-shaped copper particles as a base material is coated with silver as uniformly as possible. In particular, it is preferable from the viewpoint of economy that the surface of the flake-shaped copper particles is uniformly covered with as little silver as possible.

The state of silver coating on the silver-coated flake-shaped copper particles can be evaluated by the value of the brightness L * of the silver-coated flake-shaped copper powder. The reason for this is that the brightness of silver itself is higher than the brightness of copper itself. However, even if the surface of the flake-shaped copper particles is coated with silver with a large thickness to increase the brightness, not only is it economically disadvantageous, but also the dispersibility of the silver-coated flake-shaped copper powder in the resin is lowered. It became clear as a result of the examination of the present inventor. Therefore, it cannot be said that the silver-coated flake-shaped copper powder is preferable only because the value of the lightness L * of the silver-coated flake-shaped copper powder is high.

As a result of diligent studies by the present inventor from the viewpoint of preventing denaturation of the resin when mixed with the resin and enhancing the dispersibility in the resin, the value of D ₉₀ / D ₁₀ and the brightness of the silver-coated flake-shaped copper powder are obtained. It turned out to be advantageous to adopt the ratio with the value of L * as a measure. D ₉₀ is the volume cumulative particle size (μm) at the cumulative volume of 90% by volume by the laser diffraction scattering type particle size distribution measurement method, and D ₁₀ is the volume cumulative grain at the cumulative volume of 10% by volume by the same measurement method. It is the diameter (μm). Further, the value of D ₉₀ / D ₁₀ is a value that serves as a measure of the particle size distribution of the powder, and is generally called the degree of dispersion. The smaller the dispersity value, the lower the degree of particle agglomeration and the sharper the particle size distribution of the powder. Therefore, the value of L * / dispersity means that the larger the value, the more uniform the coating with silver and the lower the degree of aggregation of the silver-coated flake-shaped copper powder.

In the silver-coated flake-shaped copper powder of the present invention, the value of L * / dispersity is preferably 13 or more, more preferably 14 or more, and even more preferably 15 or more. The larger the value of L * / dispersion is, the more preferable it is, but if the value is as large as about 25, the desired effect of the present invention is sufficiently exhibited.

The value of L * / dispersion is preferably as described above, whereas the value of L * itself is preferably 70 or more, more preferably 73 or more, from the viewpoint of uniform coating with silver. It is more preferably 76 or more. The silver-coated flake-shaped copper powder having such an L * value can be produced by a method described later. The upper limit of L * is not particularly limited, and the closer it is to 100, the more preferable, but if the value of L * is as large as about 86, the desired effect of the present invention can be sufficiently achieved. The value of L * is measured using a diffused illumination vertical light receiving method described in JIS Z 8722 (conforming to geometric condition c / including specular reflected light), for example, a color difference meter (CR-400) manufactured by Konica Minolta Co., Ltd. To.

On the other hand, the value of the degree of dispersion is preferably 5.3 or less, particularly 5.0 or less, particularly 4.5 or less, from the viewpoint of enhancing the dispersibility of the silver-coated flake-shaped copper powder in the resin. The silver-coated flake-shaped copper powder having such a degree of dispersion can be produced by a method described later. The lower limit of the dispersity is not particularly limited, and the closer it is to 1, the more preferable it is, but if the value of the dispersity is as small as about 3.0, the desired effect of the present invention is sufficiently exhibited.
The value of the degree of dispersion can be calculated by, for example, the following method. Take a small amount of silver-coated flake-shaped copper powder in a beaker, add a few drops of 3% by mass Triton X solution (manufactured by Kanto Chemical Co., Inc.), and let it blend into the powder, then 0.1% by mass SN Dispersant 41 solution. (Manufactured by Sannopco Co., Ltd.) Add 50 mL. Then, a sample for measurement is prepared by dispersion treatment for 2 minutes using an ultrasonic disperser TIPφ20 (manufactured by Nissei Tokyo Office, OUTPUT: 8, TUNING: 5). The particle size distribution of this measurement sample is measured using a laser diffraction / scattering type particle size distribution measuring device MT3300 (manufactured by Microtrac Bell Co., Ltd.) to obtain values of D ₉₀ and D ₁₀ . The degree of dispersion is calculated from these values.

From the viewpoint of preventing denaturation of the resin when mixed with the resin and enhancing the dispersibility in the resin, the ratio of the thickness T (μm) of the silver-coated flake-shaped copper particles to D ₅₀ (μm) is adopted as a scale. As a result of the study of the present inventor, it was found that it is also advantageous to do so. D ₅₀ is a volume cumulative particle size (μm) at a cumulative volume of 50% by volume by a laser diffraction / scattering type particle size distribution measurement method. In the present invention, the value of T / D ₅₀ is preferably 0.04 or less, and more preferably 0.03 or less. On the other hand, the value of T / D ₅₀ is preferably 0.005 or more, more preferably 0.01 or more, and even more preferably 0.01 or more and 0.02 or less. The value of T / D ₅₀ means that the thickness T of the silver-coated flake-shaped copper particles is smaller than the particle size D ₅₀ when the particle size D ₅₀ is fixed. If the thickness is too small, the surface area of the particles becomes too large, and the reactivity with the resin becomes strong. The silver-coated flake-shaped copper powder is effective in preventing denaturation with the resin when it is mixed with the resin, and is effective in improving the dispersibility in the resin. Generally, in order to reduce the thickness T, it is sufficient to apply an external force to the copper mother powder as a raw material for a long time to deform it sufficiently flat, but the copper mother powder aggregates when the external force is applied for a long time. D ₅₀ tends to be large. That is, there is an antinomy between reducing the thickness T and reducing the D ₅₀ . However, in the present invention, it is possible to reduce the thickness T while suppressing the increase in D ₅₀ by flake the copper mother powder by the method described later.

The thinner the thickness T, the more preferable it is, specifically, it is preferably 0.5 μm or less, particularly 0.3 μm or less, particularly 0.25 μm or less, and particularly preferably 0.20 μm or less. The lower limit of the thickness T is not particularly limited, but if the thickness T is as small as about 0.10 μm, the desired effect of the present invention can be sufficiently achieved.

On the other hand, the value of D ₅₀ is preferably 7 μm or more and 17 μm or less, more preferably 8 μm or more and 16 μm or less, and 9 μm or more and 15 μm or less, from the viewpoint of enhancing the dispersibility of the silver-coated flake-shaped copper powder in the resin. Is more preferable. The value of D ₅₀ can be measured by the same method as the above-mentioned measurement of the degree of dispersion.

As described above, the silver-coated flake-shaped copper powder of the present invention has a low degree of aggregation, that is, the above-mentioned dispersity (D ₉₀ / D ₁₀ ) is small. Therefore, in the silver-coated flake-shaped copper powder of the present invention, it is preferable that the values of D ₉₀ and D ₁₀ are not significantly different from the values of D ₅₀ . From this viewpoint, the value of D ₉₀ is preferably 15 μm or more and 35 μm or less, more preferably 16 μm or more and 31 μm or less, and further preferably 17 μm or more and 30.5 μm or less. On the other hand, the value of D ₁₀ is preferably 3.0 μm or more and 8.0 μm or less, more preferably 3.9 μm or more and 7.0 μm or less, and further preferably 5.0 μm or more and 6.2 μm or less. preferable.

As described above, in the silver-coated flake-shaped copper powder of the present invention, the thickness of the silver-coated flake-shaped copper particles constituting the copper powder is thin, and the degree of aggregation of the particles is low. Due to this, the silver-coated flake-shaped copper powder of the present invention has a low tap density. Specifically, the tap density of the silver-coated flake-shaped copper powder of the present invention is preferably 0.5 g / cm ³ or more and 2.5 g / cm ³ or less, and more preferably 0.5 g / cm ³ or more 2. It is 0 g / cm ³ or less, more preferably 0.7 g / cm ³ or more and 2.0 g / cm ³ or less, still more preferably 0.7 g / cm ³ or more and 1.8 g / cm ³ or less, and further more. It is preferably 0.7 g / cm ³ or more and 1.5 g / cm ³ or less, and particularly preferably 0.8 g / cm ³ or more and 1.3 g / cm ³ or less. Tap density is measured according to JIS Z 2512.

In the silver-coated flake-shaped copper powder of the present invention, it is desirable that the surface of the flake-shaped copper particles as the base material is coated with silver as thinly and uniformly as possible. Therefore, it is not desirable to increase the proportion of silver in the silver-coated flake-shaped copper powder of the present invention. Specifically, the proportion of silver in the silver-coated flake-shaped copper powder of the present invention is 5% by mass or more and 20% by mass or less, more preferably 7% by mass or more and 16% by mass or less, and further preferably 9% by mass. It is 14% by mass or less. The proportion of silver in the silver-coated flaky copper powder can be measured by ICP emission spectroscopy.

Next, a suitable method for producing the silver-coated flake-shaped copper powder of the present invention will be described. The production method of the present invention is roughly classified into a flake-forming step of copper particles as a base material and a silver coating step of flake-shaped copper particles.
In the flake formation step, the dispersion liquid containing the copper mother powder and the first complexing agent is treated with a medium stirring mill device to deform the copper mother particles constituting the copper mother powder into flakes.
In the silver coating step, the copper mother powder containing the copper mother particles deformed into flakes is treated with an aqueous solution containing silver ions and a second complexing agent to precipitate silver on the surface of the copper mother particles. ..
Hereinafter, each step will be described.

In the process of flake-forming the copper mother powder, an external force is applied to the copper mother powder having a shape other than the flake shape to deform the copper mother powder into a flat shape. The copper mother powder includes, for example, a spherical copper mother powder produced by a wet reduction method, an electrolytic copper mother powder obtained by electrolyzing an electrolytic solution containing copper ions, and a spherical copper mother powder produced by an atomizing method. And so on. Of these copper mother powders, it is preferable to flake the dendrite-like copper mother powder produced by the electrolytic method because the flake-like copper powder having a small thickness can be successfully produced.

When the dendrite-like copper particles produced by the electrolytic method are used as the mother powder, crushing the dendrite-like copper particles prior to flake formation makes it possible to more successfully produce the flake-like copper powder having a small thickness. Is preferable. The crushing means is not particularly limited, and examples thereof include a disk type, a roller type, a cylinder type, an impact type, a jet type, and a high-speed rotary type crushing method. Further, either dry pulverization or wet pulverization may be used. Dry pulverization is preferable from the viewpoint of surely separating the branch portion and the trunk portion of the dendrite-like copper particles. For dry pulverization, for example, it is preferable to use a jet mill of a collision plate type or a jet mill of a type in which particles collide with each other.

The particle size _D50 of the pulverized copper particles is preferably 2 μm or more and 8 μm or less, and more preferably 3 μm or more and 7 μm or less, from the viewpoint of obtaining flake-shaped copper particles having a desired particle size and thickness. It is more preferably 4 μm or more and 6 μm or less.

Next, flakes of copper particles, which are the base material, are performed. A medium stirring mill such as a bead mill, a ball mill, or an attritor can be used for flake formation.
Prior to flake formation using a medium stirring mill, copper particles are dispersed in a liquid medium to prepare a dispersion liquid. Examples of the liquid medium used for preparing the dispersion liquid include water and an organic solvent. A mixed solvent of water and an organic solvent can also be used. Examples of the organic solvent include lower monoalcohols having 1 to 4 carbon atoms such as methanol and ethanol; lower polyhydric alcohols having 1 to 4 carbon atoms such as ethylene glycol; lower carboxylic acids having 1 to 4 carbon atoms; and 1 to 4 carbon atoms. The lower amines and the like can be used alone or in combination of two or more. Of these liquid media, it is preferable to use an organic solvent because the dispersibility of the copper particles in the dispersion liquid is improved and the quality stability when treated with the medium stirring mill is improved. In particular, it is preferable to use lower alcohols such as methanol because the medium can be easily volatilized and the medium does not easily remain in the target flake-shaped copper particles.

The concentration of copper particles in the dispersion is preferably 10% by mass or more and 60% by mass or less, preferably 20% by mass or more and 50% by mass or less, from the viewpoint of productivity and prevention of generation of coarse particles. Is preferable.

To prepare a dispersion, simply mix the copper particles and the liquid medium. In some cases, a dispersion may be prepared using a stirring and dispersing device. Examples of such a device include a fluid mill and T.I. K. Examples include Philmix (registered trademark).

In this production method, it is preferable to contain the first complexing agent in the dispersion liquid. The action of the first complexing agent effectively suppresses the aggregation of copper particles during flake formation. Further, the oxide present on the surface of the copper particles is removed by the first complexing agent, and the surface of the flake-shaped copper particles can be coated with silver thinly and uniformly. From this viewpoint, the concentration of the first complexing agent contained in the dispersion liquid is 0.1% by mass or more and 40% by mass or less, provided that the concentration of the copper particles in the dispersion liquid is within the above range. It is more preferable, and it is more preferably 0.5% by mass or more and 20% by mass or less, and further preferably 1% by mass or more and 10% by mass or less.

Conventionally, when copper mother powder is made into flakes by a medium stirring mill, fatty acids are often contained in a dispersion liquid containing the copper mother powder to suppress aggregation of copper particles constituting the copper mother powder. However, when fatty acids are used, the fatty acids adhere to and remain on the surface of the flaked copper particles. Therefore, in order to coat the surface of the flaked copper particles with silver, it is necessary to remove the fatty acids prior to that. there were. In order to remove the fatty acid, a degreasing step is required and the number of steps is increased, and there is a disadvantage that the surface of the copper particles is oxidized by the degreasing step. On the other hand, according to the present production method in which the dispersion liquid does not contain fatty acids and instead contains the first complexing agent, such inconvenience does not occur.

The first complexing agent may be a single-seat one, or may be a multi-seat one such as two-seat, three-seat and four-seat. From the viewpoint of high coordination with copper, examples of the first complexing agent include citric acid, ascorbic acid, ethylenediaminetetraacetic acid and the like. One of these complexing agents may be used alone, or two or more thereof may be used in combination. Among these complexing agents, it is preferable to use ethylenediaminetetraacetate from the viewpoint of effectively suppressing the aggregation of copper particles in the flake formation step.

In the flake formation step, the dispersion liquid and the pulverized medium are placed in a medium stirring mill device and mixed and stirred.
The diameter of the pulverized media is preferably 0.1 mm or more and 1 mm or less. The material of the pulverized media is generally zirconia or alumina.
The operation time, rotation speed, number of passes, etc. of the medium stirring mill device may be appropriately adjusted so that the desired flake-shaped copper powder can be obtained.

After the copper mother particles constituting the copper mother powder are deformed into flakes in this way, the silver coating step is performed next. In the silver coating step, as described above, the copper mother powder containing the copper mother particles deformed into flakes is treated with an aqueous liquid containing silver ions and a second complexing agent. This process preferably includes the following process 1 and process 2.
[Process 1]
The silver ions and the flake-shaped copper particles are brought into contact with each other in water to perform replacement plating, and silver is deposited on the surface of the flake-shaped copper particles. Precursor particles are obtained by this precipitation.
[Process 2]
The precursor particles obtained in Treatment 1, silver ions, and a reducing agent for silver ions are brought into contact with each other in water to further precipitate silver on the surface of the precursor particles.

The silver ions used in treatment 1 and treatment 2 are generated from a silver compound that is a silver source. As the silver compound, for example, a water-soluble silver compound such as silver nitrate can be used. The concentration of silver ions in water is preferably set to 0.01 to 10 mol / L, particularly 0.04 to 2.0 mol / L, from the viewpoint that a desirable amount of silver can be deposited on the surface of the flake-shaped copper particles. ..

In the treatment 1, the amount of the flake-shaped copper particles in water is preferably 1 to 1000 g / L, particularly preferably 50 to 500 g / L from the viewpoint that a desirable amount of silver can be deposited on the surface of the flake-shaped copper particles. ..

In process 1, there is no particular limitation on the order of addition of flake-shaped copper particles and silver ions. For example, flake-shaped copper particles and silver ions can be added to water at the same time. From the viewpoint of ease of controlling the precipitation of silver by substitution plating, it is preferable to prepare a dispersion liquid by pre-dispersing flake-shaped copper particles in water and add a silver compound as a silver source to the dispersion liquid. .. In this case, the dispersion liquid may be at room temperature or may be in the temperature range of 0 to 80 ° C.

Prior to the addition of the silver compound, it is preferable to add a second complexing agent to the dispersion liquid to control the reduction of silver. Examples of the second complexing agent include ethylenediaminetetraacetic acid salt, triethylenediamine, iminodiacetic acid and its salts, citric acid and its salts, and tartaric acid and its salts.

The first complexing agent described above and the second complexing agent described above may be of the same type or different types, but from the viewpoint of matching the stability constants of the complex. Therefore, it is preferable that the first complexing agent and the second complexing agent are of the same type. In particular, from the viewpoint of effectively suppressing the aggregation of copper particles in the flake formation step and from the viewpoint of coating silver thinly and uniformly in the silver coating step, the first complexing agent and the second complexing agent are Both are preferably ethylenediaminetetraacetic acid salts.

It is preferable to add the silver compound in the treatment 1 in the state of an aqueous solution. This aqueous solution can be added all at once to the dispersion, or can be added continuously or discontinuously over a predetermined time. From the viewpoint of easy control of the reaction of the replacement plating, it is preferable to add the aqueous solution of the silver compound to the dispersion liquid over a predetermined time.

For the treatment 1, it is preferable to irradiate the dispersion liquid with ultrasonic waves before or at the same time as adding the silver compound to the dispersion liquid. The irradiation of ultrasonic waves promotes the dispersion of the flake-shaped copper particles in the dispersion liquid, and the uniform coating of the flake-shaped copper particles with silver is likely to occur. Ultrasound has a certain effect when irradiated with it, but the frequency is particularly preferably 200 kHz or less, and more preferably 45 kHz or less. A lower limit of 10 kHz is sufficient.

In process 1, silver is deposited on the surface of the flake-shaped copper particles by the above-mentioned substitution plating, and precursor particles are obtained. The amount of silver deposited in the precursor particles is 0.1 to 50% by mass, particularly 1 to 10% by mass, of the amount of silver in the finally obtained silver-coated flake-shaped copper powder, which is thin and uniform silver. It is preferable because it can form a coating of.

Next, process 2 will be described. In the treatment 2, a silver ion and a silver ion reducing agent are added to the dispersion liquid containing the precursor particles obtained in the treatment 1. In this case, the precursor particles obtained in the treatment 1 may be once solid-liquid separated and then dispersed in water to form a dispersion liquid, or the dispersion liquid of the precursor particles obtained in the treatment 1 may be directly used in the treatment 2. May be served. In the latter case, the silver ion added in the treatment 1 may or may not remain in the dispersion liquid.

The silver ion added in the treatment 2 is generated from the water-soluble silver compound as in the treatment 1. The silver compound is preferably added to the dispersion in the form of an aqueous solution. The concentration of silver ions in the aqueous solution is preferably 0.01 to 10 mol / L, more preferably 0.1 to 2.0 mol / L. An aqueous solution having silver ions having a concentration in this range is 0.1 to 55 mass by mass with respect to 100 parts by mass of the precursor particles in the dispersion liquid containing 1 to 1000 g / L, particularly 50 to 500 g / L of precursor particles. It is preferable to add parts, particularly 1 to 25 parts by mass, from the viewpoint that a thin and uniform silver coating can be formed.

As the reducing agent added in the treatment 2, a reducing agent having a reducing power enough to allow silver substitution plating and reduction plating to proceed at the same time is used. By using such a reducing agent, a thin and uniform silver coating can be successfully formed. If a reducing agent having a strong reducing property is used, the reducing plating proceeds unilaterally, and it is not easy to form a silver coating having a desired structure. On the other hand, when a reducing agent having a weak reducing property is used, the reduction plating of silver ions is difficult to proceed, and due to this, it is not easy to form a silver coating having a desired structure. From the above viewpoint, as the reducing agent, it is preferable to use an organic reducing agent that shows acidity when it is dissolved in water. Specifically, there are formic acid, oxalic acid, L-ascorbic acid, erythorbic acid, formaldehyde and the like. These organic reducing agents may be used alone or in combination of two or more. Among them, it is preferable to use L-ascorbic acid. The term "acidic" as used herein means that an aqueous solution prepared by dissolving 0.1 mol of an organic reducing agent in 1000 g of water exhibits a pH of 1 to 6 at 25 ° C.

The amount of the reducing agent added is 0.5 to 5.0 equivalents, particularly 1.0 to 2.0 equivalents with respect to the silver ions in the aqueous solution to be added, so that the silver substitution plating and the reducing plating proceed simultaneously. It is preferable because it is easy to make it.

There is no particular limitation on the order in which the reducing agent and silver ions are added to the dispersion liquid containing the precursor particles. From the viewpoint of controlling the reduction of silver ions to form a thin and uniform silver coating, it is preferable to add silver ions after adding the reducing agent to the dispersion. The silver compound serving as a silver source can be added all at once to the dispersion liquid, or can be added continuously or discontinuously over a predetermined time. From the viewpoint that the reduction of silver ions can be easily controlled, it is preferable to add the silver compound to the dispersion liquid in the state of the aqueous solution for a predetermined time.

In the process 2, when the silver substitution plating and the reduction plating are carried out at the same time, the dispersion may be kept at room temperature or heated in a temperature range of 0 to 80 ° C.

Similar to the case of the treatment 1, in the treatment 2, it is preferable to irradiate the dispersion liquid with ultrasonic waves before or at the same time as adding the reducing agent to the dispersion liquid. The irradiation of ultrasonic waves promotes the dispersion of the precursor particles in the dispersion liquid, and the uniform coating of the precursor particles with silver is likely to occur. Ultrasound has a certain effect when irradiated with it, but the frequency is particularly preferably 200 kHz or less, and more preferably 45 kHz or less. A lower limit of 10 kHz is sufficient.

The silver-coated flake-shaped copper powder thus obtained is suitably used in the state of a conductive composition containing the copper powder and the resin. For example, silver-coated flake-shaped copper powder can be mixed with a resin, an organic solvent, glass frit, or the like to form a conductive paste. Alternatively, the silver-coated flake-shaped copper powder can be mixed with an organic solvent or the like to form a conductive ink. By applying the conductive paste or conductive ink thus obtained to the surface of the object to be applied, a conductive film having a desired pattern can be obtained.
In the silver-coated flake-shaped copper powder of the present invention, the silver coating is thin and uniform, so that the silver-coated flake-shaped copper powder effectively suppresses the elution of copper in the conductive composition. As a result, the modification of the resin contained in the conductive composition is suppressed.
Further, since the silver-coated flake-shaped copper powder of the present invention has a low degree of aggregation, it has good dispersibility in the conductive composition. Therefore, the conductive film obtained from the conductive composition has high conductivity.

Hereinafter, the present invention will be described in more detail by way of examples. However, the scope of the invention is not limited to such examples. Unless otherwise specified, "%" and "parts" mean "% by mass" and "parts by mass", respectively.

[Example 1]
(1) Production of electrolytic copper powder Nine cathode plates each of size (1.0 m x 1.0 m) are placed in an electrolytic cell having a size of 2.5 m x 1.1 m x 1.5 m (about 4 m ³ ). And an insoluble anode plate (DSE (manufactured by Permerek Electrode Co., Ltd.)) were suspended so that the distance between the electrodes was 5 cm. A copper sulfate solution as an electrolytic solution was circulated in the electrolytic cell at 20 L / min. An anode and a cathode were immersed in this electrolytic solution, and a direct current was passed through the anode to perform electrolysis, and powdered copper was deposited on the surface of the cathode.
Electrolysis was carried out for 40 minutes by adjusting the concentration of copper ions in the circulating electrolytic solution to 5 g / L, the concentration of sulfuric acid (H ₂ SO ₄ ) to 100 g / L, and the current density to 100 A / m ² .
The copper deposited on the surface of the cathode was mechanically scraped off and recovered, and then washed to obtain a hydrous copper powder cake. This cake was dispersed in 3 L of water, stirred for 10 minutes, filtered through a Büchner funnel, washed, and dried at 80 ° C. for 6 hours under reduced pressure (1 × 10 ^-3 Pa) to obtain electrolytic copper powder.

(2) Crushing of electrolytic copper powder Using a collision plate type jet mill (IDS type jet mill manufactured by Nippon Pneumatic Industries Co., Ltd., IDS-5), a crushing pressure of 6 kgf / cm ² and a supply speed of 6.7 kg / hr. Electrolyzed copper powder was crushed under the conditions. The particle size D ₅₀ of the copper powder after pulverization was 4.5 μm.

(3) Flake formation A methanol dispersion of copper powder was prepared by mixing 3 kg of pulverized electrolytic copper powder, 9 kg of methanol, and 1 kg of disodium ethylenediaminetetraacetate (hereinafter, also referred to as “EDTA2Na”). 12 kg of this dispersion was placed in Star Mill (registered trademark) LMZ, which is a bead mill manufactured by Ashizawa Finetech Co., Ltd., and 4.85 kg of zirconia beads having a diameter of 0.2 mm was further placed. The bead mill was operated for 180 minutes to flake the copper powder. Then, after separating the dispersion liquid and the beads by filtration, the dispersion liquid was allowed to stand to settle the flake-shaped copper particles. The supernatant was removed and filtered to collect flaky copper particles. The flake-shaped copper particles were then washed with water, followed by washing with methanol twice.

(4) Silver coating 100 g of flake-shaped copper particles were put into 500 mL of pure water heated to 40 ° C. to prepare a dispersion liquid. While stirring this dispersion, 4.3 g of EDTA2Na was added and dissolved. Further, 48 mL of a 0.44 mol / L silver nitrate aqueous solution was continuously added to this dispersion for 6 minutes for substitution plating, and silver was precipitated on the surface of the flake-shaped copper particles to obtain precursor particles. At this time, the dispersion liquid was irradiated with ultrasonic waves (100 W, 28 kHz).
Next, L-ascorbic acid as a reducing agent was added to the dispersion and dissolved. Further, 192 mL of a 0.44 mol / L silver nitrate aqueous solution was continuously added to the dispersion for 24 minutes. As a result, reduction plating and substitution plating were simultaneously carried out to further precipitate silver on the surface of the precursor particles, and the desired silver-coated flake-shaped copper powder was obtained. During this time, ultrasonic irradiation was continued.

[Examples 2 to 8]
A silver-coated flake-shaped copper powder was produced in the same manner as in Example 1 except that the conditions shown in Table 1 below were adopted.

[Comparative Example 1]
In the flake formation step of Example 1, EDTA2Na was not used, and the flake formation time was set to 20 minutes. In addition, ultrasonic irradiation was not performed in the silver coating process. Except for these, silver-coated flake-shaped copper powder was produced in the same manner as in Example 1.

[Evaluation 1]
For the silver-coated flake-shaped copper powders obtained in Examples and Comparative Examples, the particle size distribution, lightness, circularity of the plate surface of the particles, particle thickness, tap density, and silver content ratio were measured by the above-mentioned methods. The results are shown in Table 2 below.

[Evaluation 2]
A conductive composition was prepared using the silver-coated flake-shaped copper powder obtained in Examples and Comparative Examples.
Epoxy resin (EPICLON 850 manufactured by DIC) and butyl carbitol were mixed at a mass ratio of 35:65, and silver-coated flake-shaped copper powder was added to the mixture so as to have a concentration of 70% to prepare a paste-like conductive composition. ..
A conductive composition was applied to one surface of a polyethylene terephthalate (PET) film using a bar coater. The coating width was 200 mm. The gap of the bar coater was set to 30 μm.
The formed coating film was dried in a vacuum dryer at 90 ° C. for 60 minutes. Then, the PET film on which the coating film was formed was sandwiched between sheets and vacuum pressed at 160 ° C. and 20 kN. With respect to the sample thus obtained, the thickness of the conductive film was measured using a micrometer (Nikon Digimicro MF-501). Moreover, the resistance value of the conductive film was measured. The resistance value was measured by a four-probe method using a resistivity measuring device (Mitsubishi Chemical MCP-T600). The results are shown in Table 2.

[Evaluation 3]
The elution amount of copper ions was measured for the silver-coated flake-shaped copper powders obtained in Examples and Comparative Examples.
A dispersion was prepared by mixing 0.2 g of silver-coated flake-shaped copper powder, 10 mL of hydrochloric acid having a concentration of 15%, and 2 mL of methanol. This dispersion was allowed to stand in an environment of 25 ° C. for 10 minutes. Then, the dispersion was filtered, and the concentration of copper ions contained in the filtrate was measured by ICP emission spectroscopy. The results are shown in Table 2.

As is clear from the results shown in Table 2, the conductive film formed by using the silver-coated flake-shaped copper powder obtained in each example was formed by using the silver-coated flake-shaped copper powder obtained in the comparative example. It can be seen that the conductivity is higher than that of the conductive film.
Further, it can be seen that the silver-coated flake-shaped copper powder obtained in each example has more suppressed elution of copper ions than the silver-coated flake-shaped copper powder obtained in the comparative example.

According to the present invention, when mixed with a resin, the dispersibility in the resin is good, the deterioration of the resin is suppressed, and the electrical resistance of the film formed from the resin can be reduced. Flake-shaped copper powder and a method for producing the same are provided.

Claims (16)

1. A silver-coated flake-shaped copper powder containing silver-coated flake-shaped copper particles having silver on the surface at least.
   For the silver-coated flake-shaped copper powder, the volume cumulative particle size at a cumulative volume of 90% by volume measured by the laser diffraction / scattering type particle size distribution measurement method is D ₉₀ (μm), and the volume cumulative particle size at a cumulative volume of 10% by volume is D ₁₀ . When (μm) is set
   A silver-coated flake-shaped copper powder having a lightness L * value of 13 or more with respect to the dispersity defined by D ₉₀ / D ₁₀ .
2. A silver-coated flake-shaped copper powder containing silver-coated flake-shaped copper particles having silver on the surface at least.
   The cumulative volume of the silver-coated flake-shaped copper powder at a cumulative volume of 50% by volume measured by the laser diffraction / scattering particle size distribution measurement method is D ₅₀ (μm), and the thickness of the silver-coated flake-shaped copper particles is T (μm). )
   A silver-coated flake-shaped copper powder having a thickness T of 0.04 or less with respect to a particle size D ₅₀ .
3. The silver-coated flake-shaped copper powder according to claim 1 or 2, wherein the thickness T of the silver-coated flake-shaped copper particles is 0.1 μm or more and 0.5 μm or less.
4. The silver-coated flake-shaped copper powder according to claim 3, wherein the thickness T of the silver-coated flake-shaped copper particles is 0.1 μm or more and 0.3 μm or less.
5. The silver-coated flake-shaped copper powder according to any one of claims 1 to 4, wherein the tap density is 0.5 g / cm ³ or more and 2.5 g / cm ³ or less.
6. The silver-coated flake-shaped copper powder according to any one of claims 1 to 5, wherein the proportion of silver is 5% by mass or more and 20% by mass or less.
7. The silver-coated flake-shaped copper powder according to any one of claims 1 to 6, wherein the silver-coated flake-shaped copper particles have a circularity of 0.60 or more and 0.95 or less.
8. The silver-coated flake-shaped copper powder according to any one of claims 1 to 7, wherein the brightness L * is 70 or more and 86 or less.
9. According to any one of claims 1 to 8, the cumulative volume particle size D ₉₀ of the silver-coated flake-shaped copper powder at a cumulative volume of 90% by volume measured by a laser diffraction / scattering particle size distribution measurement method is 15 μm or more and 35 μm or less. The silver-coated flaky copper powder described.
10. According to any one of claims 1 to 9, the cumulative volume particle size D ₁₀ of the silver-coated flake-shaped copper powder at a cumulative volume of 10% by volume measured by a laser diffraction / scattering particle size distribution measurement method is 3 μm or more and 8 μm or less. The silver-coated flaky copper powder described.
11. The silver-coated flaky copper powder according to claim 10, wherein the dispersity defined by D ₉₀ / D ₁₀ is 3.0 or more and 5.3 or less.
12. According to any one of claims 1 to 11, the cumulative volume particle size D ₅₀ of the silver-coated flake-shaped copper powder at a cumulative volume of 50% by volume measured by a laser diffraction / scattering particle size distribution measurement method is 7 μm or more and 17 μm or less. The silver-coated flaky copper powder described.
13. The dispersion liquid containing the copper mother powder and the first complexing agent is treated with a medium stirring mill device to deform the copper mother particles constituting the copper mother powder into flakes.
    The copper mother powder containing the copper mother particles deformed into flakes is treated with an aqueous solution containing silver ions and a second complexing agent to precipitate silver on the surface of the copper mother particles, in the form of silver-coated flakes. How to make copper powder.
14. The production method according to claim 13, wherein the first complexing agent and the second complexing agent are of the same type or different types.
15. The production method according to claim 14, wherein both the first complexing agent and the second complexing agent are ethylenediaminetetraacetic acid salts.
16. The production method according to any one of claims 13 to 15, wherein the copper mother powder is an electrolytic copper powder obtained by electrolyzing an electrolytic solution containing copper ions.