CN101687253A - Spherical copper fine powder and process for production of the same - Google Patents
Spherical copper fine powder and process for production of the same Download PDFInfo
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- CN101687253A CN101687253A CN200880021894A CN200880021894A CN101687253A CN 101687253 A CN101687253 A CN 101687253A CN 200880021894 A CN200880021894 A CN 200880021894A CN 200880021894 A CN200880021894 A CN 200880021894A CN 101687253 A CN101687253 A CN 101687253A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
Abstract
A spherical copper fine powder characterized by having a mean particle diameter of 0.05 to 0.25[mu]m; and a process for the production of spherical copper fine powder through disproportionation, characterized by adding copper suboxide to an aqueous medium containing an additive consisting of a natural resin, a polysaccharide, or a derivative thereof to prepare a slurry, adding a 5 to 50% aqueous solution of an acid to the slurry at once within 15 minutes, and then subjecting the resulting slurry to disproportionation. The process enables speedy, efficient and stable production of metallic copper particles controlled in particle shape or particle size, particularly copper fine powder having smaller particle sizes.
Description
Technical field
The present invention relates to a kind of manufacture method of spherical copper fine powder and the spherical copper fine powder that obtains by this manufacture method, described manufacture method can be fast effectively and stably make the controlled spherical metal shot copper of particle shape or granularity, particularly finer spherical copper fine powder.
Background technology
The manufacture method of copper powder has electrolysis and atomization all the time.The copper powder of making by these methods is good in powder used in metallurgy purposes such as oiliness bearing, brush, and still conductive fillers such as the coating that increases in demand expection in recent years, paste, resin are expected copper powder finer and that the granularity particle shape is controlled with in the purposes.
Manufacture method as the finer metal shot copper that is suitable for these purposes, have: (1) copper salt solution pressurized hydrogen reducing process, (2) copper salt solution chemical reduction method, (3) organic copper salt thermal decomposition method etc., but the problem that all has installation cost and traffic expense costliness, and exist in order to be controlled to be predetermined particle shape granularity and cause finished product rate variance, surface that shortcomings such as oxidation or reagent costliness take place easily, not gratifying method.
According to this situation, the known method that makes cuprous oxide particle and acid reaction can suitably be controlled the particle shape and the granularity of the metal shot copper of generation, and by reaction conditions such as management pH, temperature, mean residence times, can regulate predetermined particle shape granularity, thereby make highly purified metallic copper particulate.
In addition, by the choice reaction condition, the cohesion that can also obtain chain etc. connects powder (for example, referring to Patent Document 1).
This patent documentation is disclosed in 1985 (clear and 60 years), is the technology of highest level as copper powder manufacturing technology at that time.
The content of this technology comprises: 1) a kind of manufacture method of metal shot copper, it is characterized in that, by making cuprous oxide particle and acid reaction generate copper salt solution and metal shot copper, and reclaim by Separation of Solid and Liquid in the method for metal shot copper, make on one side dilute acid soln continuously flow into reactive tank with the flow of the corresponding predetermined mean residence time of targeted particle size of the metal shot copper that can access and will produce, maintain the interpolation speed interpolation cuprous oxide particle of predetermined value on one side with pH with reactive tank, react below 50 ℃ in the liquid temperature, the metal shot copper slurry that makes generation is to discharge with the corresponding speed of described solution influx, from the metal shot copper slurry of discharge like this, reclaim the metal shot copper by solid-liquid separation means, make the controlled metal shot copper of granularity thus; 2) a kind of manufacture method of metal shot copper, it is characterized in that, by making cuprous oxide particle and acid reaction generate copper salt solution and metal shot copper and reclaiming by Separation of Solid and Liquid in the method for metal shot copper, keep the liquid temperature that can obtain predetermined shape of particle and granularity on one side, Yi Bian react.
But, require this copper powder micronizing and homogenising more recently, and require manufacturing technology fast.According to this situation, the inventor has proposed a kind of manufacture method of copper fine powder, it is characterized in that, in the aqueous medium of the additive that comprises natural resin, polysaccharide or derivatives thereof, utilize acid that cuprous oxide is carried out disproportionated reaction when coming the manufactured copper micro mist, disproportionated reaction is begun temperature be set at below 10 ℃ and (refer to Patent Document 2).
This method is the method for fine copper fine powder of making fast, and is unusual effective method.But the level of the average grain diameter of the copper fine powder of this method manufacturing is 0.5 μ m～3.0 μ m, also in the method for exploring further miniaturization.
Patent documentation 1: Japanese kokai publication sho 60-33304 communique
Patent documentation 2: TOHKEMY 2005-256012 communique
Summary of the invention
The objective of the invention is to, a kind of manufacture method of spherical copper fine powder and the spherical copper fine powder that is obtained by this manufacture method are provided, described manufacture method can be fast effectively and stably make the controlled spherical metal shot copper of particle shape or granularity, particularly finer copper fine powder.
The invention provides:
1) a kind of spherical copper fine powder is characterized in that, the average grain diameter of copper fine powder is more than the 0.05 μ m, below the 0.25 μ m;
2) above-mentioned 1) described spherical copper fine powder is characterized in that, the specific area of copper fine powder (BET) is 2.5m
2/ g is above, 15.0m
2Below/the g.
The minor axis that is meant each shot copper in this said sphere is below 150%, particularly below 120% with the ratio of major diameter.Therefore, the ratio of minor axis and major diameter surpasses 150% shot copper and has flat shape, can not be called sphere.
The present invention is under the situation of sneaking into flat copper fine powder, and its amount is for whole 20% below, preferred below 10%, further preferred below 5%.Be not advisable not contain this flat copper fine powder in fact.
In addition, the invention provides:
3) a kind of manufacture method of utilizing the copper fine powder of disproportionated reaction, wherein, in the aqueous medium of the additive that comprises natural resin, polysaccharide or derivatives thereof, add cuprous oxide and make slurry, 15 minutes with interior in this slurry disposable interpolation 5～50% aqueous acids, carry out disproportionated reaction.
As additive, can use natural rubber class or gelatin class.As the concrete example of this additive, rosin, gelatin, animal glue, carboxymethyl cellulose (CMC), starch, dextrin, gum arabic, casein are effective.
The slurry concentration of described cuprous oxide is to be suitable below the 500g/L, usually with 300g/L with the enforcement of getting off.This slurry concentration can suitably be selected, and is not particularly limited.If the slurry concentration of cuprous oxide is very low, then reaction can't be carried out, thereby just causes cost to raise.
For mol ratio (molal quantity of the equivalents/slurry of acid), preferably implement with 1.00～2.00.Mol ratio is as long as be that it is just no problem to react more than the equivalent (1.0).Even excessive interpolation also can't improve effect like that significantly.On the contrary, during the acid concentration overrich, thermal discharge increases when adding acid in the cuprous oxide slurry, and the temperature of reaction system rises, and can reckon with to be unfavorable for micronizing, therefore may be unfavorable aspect cost.
On the other hand, when acid concentration was rare, the result can cause reaction speed to descend, and therefore was unfavorable for micronizing.In sum, we can say that mol ratio (molal quantity of the equivalents/slurry of acid) is preferably set to 1.00～2.00.
In aqueous medium, utilize acid to carry out disproportionated reaction when coming the manufactured copper micro mist, preferably disproportionated reaction is begun temperature and be set at below 10 ℃.This is effective for forming fine copper fine powder.
In addition, this aqueous acid of disposable interpolation is very important.That is, at 15 minutes with interior disposable interpolation.Thus, can access average grain diameter is the following spherical copper fine powder of 0.25 μ m.Add the disproportionated reaction of carrying out fast by this and can access fine spherical copper powder.Disposable interpolation is still indeterminate to the effective reason of manufactured copper micro mist in this short time.
But, consider that the disproportionated reaction of this short time has the effect that shot copper is grown up that suppresses.Therefore, in order to realize miniaturization, the disposable interpolation in the short time is effective.The interpolation time of aqueous acid is preferably 3 minutes with the interior short time, is preferably especially in 1 minute.
In addition, the invention provides:
4) the above-mentioned 3) manufacture method of described copper fine powder, wherein, the copper fine powder slurry that obtains after the disproportionated reaction is carried out Separation of Solid and Liquid and water clean, and utilize aqueous slkali that it is reduced processing, and then the micro mist slurry that obtains is repeated Separation of Solid and Liquid and water clean, obtain copper powder; This utilizes reduction that aqueous slkali carries out to handle, by oxide residual on the copper fine powder that will obtain and the reduction of unreacted cuprous oxide and effective to the homogenising of the chemical composition of shot copper.
5) above-mentioned 3) or 4) manufacture method of described copper fine powder, wherein, in the process that the Separation of Solid and Liquid that repeats described micro mist slurry and water clean, utilize acid to carry out acidification and handle;
This sour acidification is handled can further improve rust-proof effect when carrying out antirust processing.
6) manufacture method of each described copper fine powder above-mentioned 3)～5), wherein, carry out the water cleaning treatment at last after, filter copper powder, and then, obtain copper powder its vacuum drying;
7) manufacture method of each described copper fine powder above-mentioned 3)～6), wherein, the average grain diameter of copper fine powder is more than the 0.05 μ m, below the 0.25 μ m;
8) manufacture method of each described copper fine powder above-mentioned 3)～7), wherein, the specific area of copper fine powder (BET) is 2.5m
2/ g is above, 15m
2Below/the g.
The manufacture method of copper fine powder of the present invention has following excellent results: can be fast effectively and stably make particle shape for spherical and can control the finer copper fine powder of granularity arbitrarily.
Description of drawings
Fig. 1 is the figure of the manufacturing process summary of expression spherical copper fine powder.
Fig. 2 is the FE-SEM photo of spherical copper fine powder.
The specific embodiment
Cuprous oxide particle can be by being made via the known method of stannous chloride etc. by copper salt solution.That is, therefore the granularity of the cuprous oxide particle of use and utilize between the granularity of the metal shot copper that method of the present invention obtains and do not have direct relation also can use the cuprous oxide particle of coarse grain.
Sulfuric acid is used in acid usually, but also can use nitric acid, phosphoric acid, acetic acid.The kind that does not need special provision acid.When using sulfuric acid, disproportionated reaction generates copper sulfate solution and metal shot copper according to following reaction equation.
Cu
2O+H
2SO
4＝Cu↓+CuSO
4+H
2O
If acid is increased with respect to the interpolation ratio of cuprous oxide, then the pH of reaction system descends, and the next pH of opposite situation raises, and therefore, by the interpolation ratio of acid or cuprous oxide, can control pH.
In reaction, generate contamination precipitation and under the situation of cuprous oxide noresidue, react fast, pH is maintained below 2.5, preferably maintain near 1.0.
As mentioned above, when utilizing the disproportionated reaction manufactured copper micro mist of cuprous oxide, in the aqueous medium of the additive (protecting colloid) that comprises natural resin, polysaccharide or derivatives thereof, utilize acid to carry out disproportionated reaction.This is of the present invention one big feature.
This additive (protecting colloid) has the effect that suppresses the particle growth, also has the effect that reduces the contact frequency between the particle.Thereby, effective to making minuteness particle.
As described additive, natural rubber class or gelatin class are effective especially.More specifically, can use rosin, gelatin, animal glue, carboxymethyl cellulose (CMC), starch, dextrin, gum arabic, casein as additive.Particularly when using animal glue, can be micronized to average grain diameter is below the 0.25 μ m, has the effect that suppresses cohesion.
When making the metallic copper particulate, the liquid temperature in the reaction is set at below 30 ℃, preferred below 10 ℃.This is when surpassing 30 ℃ because of the liquid temperature, the tendency that has cohesion to connect between the metallic copper particulate.In order to realize miniaturization, especially preferably disproportionated reaction is begun temperature and be set at below 10 ℃.By reducing this reaction temperature, can effectively suppress particle and grow up, thereby further make its micronizing.
If make this temperature below 10 ℃ last till that reaction finishes under the possible situation, then can be more effective.Reaction temperature also can be set at and surpass 30 ℃ temperature.Be to be conceived to the situation that cohesion connects between the metal shot copper at this moment, to obtain the shot copper of special particle shape.Thus, can control the particle shape and the granularity of the metal shot copper of generation by reaction temperature.The present invention comprises all such temperature controls.
In addition, among the present invention, when the disproportionated reaction of utilizing acid to carry out cuprous oxide was come the manufactured copper micro mist, this aqueous acid of disposable interpolation was very important.That is, 15 minutes with interior, preferred 3 minutes with interior, further preferred 1 minute with interior disposable interpolation.Thus, can access average grain diameter is the following spherical copper fine powder of 0.25 μ m.
Add the disproportionated reaction of carrying out fast by this and can access fine spherical copper powder.That is,, nucleation is grown up than particle more preponderate, thereby make copper powder miniaturization more by accelerating the interpolation speed of acid.
Think that the disproportionated reaction of this short time plays the effect that shot copper is grown up that suppresses.In order to realize miniaturization, the disposable interpolation of short time is absolutely necessary.
Average grain diameter of the present invention is preferably got littler value, than average grain diameter (D
50) little value D
10Actual value be 0.06 μ m, the minimum of a value D of size distribution
MinThen littler.But because the lower limit that can make as the discrimination method of wet type reaction is 0.05 μ m, so average grain diameter is set at 0.05 μ m.
Because the minimum of a value D of size distribution
MinLittler, therefore comprise finer copper fine powder.Infer thus as what the discrimination method of wet type reaction can be made to be limited to about 0.05 μ m down, so the lower limit set of average grain diameter is 0.05 μ m.
On the other hand, average grain diameter is thin more, and then specific area is tended to big more, but not necessarily proportional.In addition, the measured value of specific area is different with theoretical value.
If the supposition copper fine powder is positive spherical, the real density of copper is 8.93g/cm
3, with average grain diameter (D
50) be diameter, by volume, surface area, Mass Calculation specific area, then D
50=0.05 μ m, theoretical specific area are 13.44m
2/ g.
But, with regard to average grain diameter (D
50) with the relation of specific area, average grain diameter is more little, then the difference of theoretical value and measured value is tended to disappearance more.This is because when average grain diameter was big, surface state (the most surperficial concavo-convex etc.) contrast table area had considerable influence; When average grain diameter diminishes, compare with surface state, it is big that the influence of size itself becomes, and the difference of theoretical value and measured value disappears.
In sum, if with D
50Lower limit be set at 0.05 μ m, then can predict specific area on be limited to about 15.0m
2/ g.Thereby, be limited to 15.0m on the BET specific area
2/ g.
The ultra tiny spherical copper powder that so obtains may condense in air or in the liquid.But, utilize in the aqueous solution means such as this agglomerate being applied ultrasonic wave that it is disperseed once more.Should understand this is to be that spherical copper fine powder below the average grain diameter 0.25 μ m is a prerequisite with the initial stage particle.This is because can not obtain spherical fine copper powder by carry out miniaturization with the pulverizing means.
When carrying out intermittent reaction, can in the cuprous oxide particle slurry, add acid, otherwise also can in acid solution, add cuprous oxide particle or cuprous oxide particle slurry.
No matter be which kind of situation, the metal shot copper that obtains is high-purity, and is rich in surface-active.Therefore, the metal shot copper that obtains by Separation of Solid and Liquid is carried out being dried after the suitable antirust processing.Fig. 1 represents the summary of the manufacturing process of spherical copper fine powder.
As shown in Figure 1, make via the operation of additive dissolving → slurryization (in comprising the aqueous medium of additive, adding the operation that cuprous oxide is made slurry) → disproportionated reaction (interpolation aqueous acid) → cleaning → antirust → filtration → drying → pulverizing → screening.
Embodiment
Below, embodiments of the invention are described.Need to prove that present embodiment is an example, the present invention is not subjected to the restriction of this example.That is, in the scope of technological thought of the present invention, comprise embodiment all modes or change in addition.
(embodiment 1)
8g animal glue is dissolved in 7 liters of pure water, adds cuprous oxide 1000g, make suspension, the cuprous oxide slurry is cooled to 7 ℃ while stir.Cuprous oxide amount in the slurry is about 143g/L.
Then, be cooled to 7 ℃ dilute sulfuric acid (concentration 24%:9N, mol ratio (aqueous acid/slurry): 1.5) 2000cc with interpolation in 1 minute.The copper fine powder that generates is carried out being dried after cleaning rust-proof is handled, obtain the 420g copper fine powder.
Adding back reaction in about 1 minute finishes.The FE-SEM photo of the spherical copper fine powder that so obtains is shown in Fig. 2.As shown in Figure 2, the average grain diameter of copper fine powder is 0.09 μ m.Hence one can see that, and the dilute sulfuric acid that added cooling with 1 minute is very effective to copper fine powderization.Specific area BET is 6.66m
2/ g.This embodiment 1 also is more preferred example in the condition of other embodiment.
(embodiment 2～8)
Embodiment when rosin, gelatin, carboxymethyl cellulose (CMC), starch, dextrin, gum arabic, casein are used in expression as additive.At this moment, except the conversion additive, with all identical conditions of embodiment 1 under generate copper powder.As a result, above-mentioned additive is all effective, and the result of the interpolation of embodiment 1 " animal glue " is best.
(comparative example 1～2)
Select polyethylene glycol (PEG) as the situation of additive under and do not have and investigate copper fine powderization under the situation of adding.It the results are shown in comparative example 1～2.At this moment, under all identical conditions of other condition and embodiment 1, generate copper powder.As a result, the additive of comparative example 1 is invalid, in addition, does not have under the situation of adding, and the particle diameter that obtains copper powder becomes big and the also low copper powder of BET specific area, and the result is relatively poor.
For the spherical copper fine powder of the foregoing description and comparative example, measure its average grain diameter and specific area.Average grain diameter utilizes laser diffraction and scattering formula particle size distribution method to measure, and adopts weight build-up particle diameter D
50Value.Specific area utilizes the BET method to measure.
Above embodiment 1～8 and comparative example 1～2 the results are shown in table 1.
Table 1
| Additive | The acid interpolation time | Reaction beginning temperature ℃ | Average grain diameter μ m | BET specific area m 2/g | |
| Embodiment 1 | Animal glue | 1 minute | ??7 | ??0.09 | ??6.66 |
| Embodiment 2 | Rosin | 1 minute | ??7 | ??0.21 | ??4.67 |
| Embodiment 3 | Gelatin | 1 minute | ??7 | ??0.20 | ??4.56 |
| Embodiment 4 | ??CMC | 1 minute | ??7 | ??0.18 | ??5.05 |
| Embodiment 5 | Starch | 1 minute | ??7 | ??0.19 | ??4.95 |
| Embodiment 6 | Dextrin | 1 minute | ??7 | ??0.20 | ??4.66 |
| Embodiment 7 | Gum arabic | 1 minute | ??7 | ??0.25 | ??4.00 |
| Embodiment 8 | Casein | 1 minute | ??7 | ??0.19 | ??4.85 |
| Comparative example 1 | ??PEG | 1 minute | ??7 | ??7.32 | ??6.46 |
| Comparative example 2 | Do not have and add | 1 minute | ??7 | ??4.90 | ??4.50 |
CMC: carboxymethyl cellulose; PEG: polyethylene glycol
(embodiment 9～12,16)
Below, will be that benchmark changes sour interpolation and the results are shown in embodiment 9～12 during the time with representational embodiment 1.At this moment, make the sour interpolation time be changed to 15 minutes by 5 seconds.At this moment, except the conversion acid interpolation time, with all identical conditions of embodiment 1 under generate copper powder.As a result, the example of shortening of sour interpolation time obtains the copper powder that copper powder size is littler, the BET specific area is also low.Because the sour interpolation time also can influence the size and the BET specific area of particle diameter, so the preferred acid interpolation time is short as far as possible.Be not that spended time adds, but preferably at about 15 minutes with interior interpolation.This result also is same when using rosin, gelatin, carboxymethyl cellulose (CMC), starch, dextrin, gum arabic, casein as additive.
(comparative example 3～4)
Below, the example when 16 minutes, 80 minutes of exceeding condition of the present invention with the acid interpolation time are carried out is shown in comparative example 3, comparative example 4.At this moment, except the conversion acid interpolation time, with all identical conditions of embodiment 1 under generate copper powder.All obtain copper powder size under two kinds of situations and become big and the also low copper powder of BET specific area, the result is relatively poor.
Embodiment 9～12 and comparative example 3～4 the results are shown in table 2.
Table 2
Additive: animal glue, reaction beginning temperature: 7 ℃
| The acid interpolation time | Average grain diameter μ m | BET specific area m 2/g | |
| Embodiment 1 | 1 minute | ??0.09 | ??6.66 |
| Embodiment 9 | 3 minutes | ??0.18 | ??4.39 |
| Embodiment 10 | 2 minutes | ??0.15 | ??4.94 |
| Embodiment 11 | 30 seconds | ??0.09 | ??6.70 |
| Embodiment 12 | 5 seconds | ??0.08 | ??6.75 |
| Embodiment 16 | 15 minutes | ??0.20 | ??6.15 |
| Comparative example 3 | 16 minutes | ??0.40 | ??3.80 |
| Comparative example 4 | 80 minutes | ??0.80 | ??3.50 |
(embodiment 13～17)
Below, will be that benchmark the results are shown in embodiment 13～17 when changing reaction beginning temperature with representational embodiment 1.At this moment, make reaction beginning temperature 0～30 ℃ of variation.At this moment, except transformationreation begins temperature, with all identical conditions of embodiment 1 under generate copper powder.
As a result, the example of reaction beginning temperature reduction obtains the copper powder that copper powder size is littler, the BET specific area is bigger.This result also is same when using rosin, gelatin, carboxymethyl cellulose (CMC), starch, dextrin, gum arabic, casein as additive.
(comparative example 5)
Below, the example in the time of will exceeding 50 ℃ of condition of the present invention and carry out with reaction beginning temperature is shown in comparative example 5.At this moment, except transformationreation begins temperature, with all identical conditions of embodiment 1 under generate copper powder.As a result, obtain copper powder size and become big and the also low copper powder of BET specific area, the result is relatively poor.
Embodiment 13～17 and comparative example 5 the results are shown in table 3.
Table 3
Additive: animal glue, sour interpolation time: 1 minute
| Reaction beginning temperature ℃ | Average grain diameter μ m | BET specific area m 2/g | |
| Embodiment 1 | ??7 | ??0.09 | ??6.66 |
| Embodiment 13 | ??30 | ??0.25 | ??6.10 |
| Embodiment 14 | ??20 | ??0.18 | ??6.00 |
| Embodiment 15 | ??10 | ??0.12 | ??6.10 |
| Comparative example 5 | ??50 | ??1.20 | ??5.76 |
As mentioned above, by condition of the present invention, promptly, in the aqueous medium of the additive that comprises natural resin, polysaccharide or derivatives thereof, add cuprous oxide and make the slurry that contains 10～300g/L cuprous oxide, 3 minutes with interior in this slurry the disposable interpolation mol ratio molal quantity of equivalents/slurry (acid) be that 1.00～2.00 5～50% aqueous acids carry out disproportionated reaction, can access suitable spherical copper fine powder.
And the average grain diameter that can access micro mist is the following spherical copper fine powder of 0.25 μ m.And the specific area of these spherical copper fine powders (BET) can reach 4.0m
2More than/the g.
Utilize possibility on the industry
Spherical copper fine powder constructed in accordance, the particle diameter of powder is little and even, and the powder of not only using as oiliness bearing or brush is useful, and useful as electroconductive stuffings such as coating, paste, resins.
Claims (8)
1. a spherical copper fine powder is characterized in that, the average grain diameter of copper fine powder is more than the 0.05 μ m, below the 0.25 μ m.
2. spherical copper fine powder as claimed in claim 1 is characterized in that, the specific area of copper fine powder is that BET is 2.5m
2/ g is above, 15.0m
2Below/the g.
3. manufacture method of utilizing the spherical copper fine powder of disproportionated reaction, it is characterized in that, in the aqueous medium of the additive that comprises natural resin, polysaccharide or derivatives thereof, add cuprous oxide and make slurry, 15 minutes with interior in this slurry disposable interpolation 5～50% aqueous acids, carry out disproportionated reaction.
4. the manufacture method of spherical copper fine powder as claimed in claim 3, it is characterized in that, the copper fine powder slurry that obtains after the disproportionated reaction is carried out Separation of Solid and Liquid and water cleaning, and utilize aqueous slkali that it is reduced processing, and then the micro mist slurry that obtains is repeated Separation of Solid and Liquid and water clean, obtain copper powder.
5. as the manufacture method of claim 3 or 4 described spherical copper fine powders, it is characterized in that, in the process of Separation of Solid and Liquid that repeats described micro mist slurry and water cleaning, utilize acid to carry out acidification and handle.
6. as the manufacture method of each described spherical copper fine powder in the claim 3～5, it is characterized in that, carry out the water cleaning treatment at last after, filter copper powder, and then, obtain copper powder its vacuum drying.
7. as the manufacture method of each described spherical copper fine powder in the claim 3～6, it is characterized in that the average grain diameter of copper fine powder is more than the 0.05 μ m, below the 0.25 μ m.
8. as the manufacture method of each described spherical copper fine powder in the claim 3～7, it is characterized in that the specific area of copper fine powder is that BET is 2.5m
2/ g is above, 15.0m
2Below/the g.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007169869 | 2007-06-28 | ||
| JP169869/2007 | 2007-06-28 | ||
| PCT/JP2008/061033 WO2009001710A1 (en) | 2007-06-28 | 2008-06-17 | Spherical copper fine powder and process for production of the same |
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| Publication Number | Publication Date |
|---|---|
| CN101687253A true CN101687253A (en) | 2010-03-31 |
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|---|---|
| US (1) | US20100192728A1 (en) |
| JP (2) | JP5235193B2 (en) |
| KR (2) | KR20120116013A (en) |
| CN (1) | CN101687253A (en) |
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| JP2012126942A (en) * | 2010-12-14 | 2012-07-05 | Jx Nippon Mining & Metals Corp | Fine spherical copper powder and method for producing the same |
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| JP2014034697A (en) * | 2012-08-08 | 2014-02-24 | Furukawa Co Ltd | Method for producing copper fine particle, conductive paste and method for producing conductive paste |
| KR102118308B1 (en) * | 2012-11-26 | 2020-06-03 | 미쓰이금속광업주식회사 | Copper powder and method for producing same |
| JP2014129609A (en) * | 2014-03-07 | 2014-07-10 | Hokkaido Univ | Method for producing copper fine particle |
| JP6549298B1 (en) | 2018-09-21 | 2019-07-24 | Ｊｘ金属株式会社 | Pulverizable copper powder and method for producing the same |
| WO2023126830A1 (en) | 2021-12-27 | 2023-07-06 | Tata Steel Limited | A method of producing spherical copper powder and a product thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP4701426B2 (en) * | 1999-12-01 | 2011-06-15 | Ｄｏｗａエレクトロニクス株式会社 | Copper powder and copper powder manufacturing method |
| KR100743844B1 (en) * | 1999-12-01 | 2007-08-02 | 도와 마이닝 가부시끼가이샤 | Copper powder and process for producing copper powder |
| JP4185267B2 (en) * | 2001-07-25 | 2008-11-26 | 三井金属鉱業株式会社 | Copper powder, method for producing the copper powder, copper paste using the copper powder, and printed wiring board using the copper paste |
| JP4204849B2 (en) * | 2002-11-12 | 2009-01-07 | Ｄｏｗａエレクトロニクス株式会社 | Production method of fine copper powder |
| JP4242176B2 (en) * | 2003-02-25 | 2009-03-18 | 石原産業株式会社 | Copper fine particles and method for producing the same |
| JP2005023417A (en) * | 2003-07-04 | 2005-01-27 | Fukuda Metal Foil & Powder Co Ltd | Production method of ultra-fine copper powder |
| JP4085049B2 (en) * | 2003-08-21 | 2008-04-30 | Ｊｆｅミネラル株式会社 | Copper alloy powder for conductive paste, method for producing copper alloy powder for conductive paste excellent in oxidation resistance, copper alloy powder for inkjet, and method for producing the same |
| JP4868329B2 (en) * | 2004-03-09 | 2012-02-01 | Ｊｘ日鉱日石金属株式会社 | Method for producing copper fine powder |
| JP4662760B2 (en) * | 2004-12-22 | 2011-03-30 | 三井金属鉱業株式会社 | Ultrafine copper powder, ultrafine copper powder slurry, and method for producing ultrafine copper powder slurry |
| JP4687599B2 (en) * | 2006-07-26 | 2011-05-25 | 住友金属鉱山株式会社 | Copper fine powder, method for producing the same, and conductive paste |
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2008
- 2008-06-17 KR KR1020127022980A patent/KR20120116013A/en active Search and Examination
- 2008-06-17 US US12/666,864 patent/US20100192728A1/en not_active Abandoned
- 2008-06-17 KR KR1020097026905A patent/KR20100024431A/en active Search and Examination
- 2008-06-17 WO PCT/JP2008/061033 patent/WO2009001710A1/en active Application Filing
- 2008-06-17 CN CN200880021894A patent/CN101687253A/en active Pending
- 2008-06-17 JP JP2009520481A patent/JP5235193B2/en active Active
- 2008-06-20 TW TW097123005A patent/TW200914166A/en unknown
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103079732A (en) * | 2010-09-30 | 2013-05-01 | 同和电子科技有限公司 | Copper powder for conductive paste and method for manufacturing same |
| CN103079732B (en) * | 2010-09-30 | 2015-09-02 | 同和电子科技有限公司 | Copper powder for conductive paste and manufacture method thereof |
| CN107921532A (en) * | 2015-09-03 | 2018-04-17 | 同和电子科技有限公司 | Phosphorous copper powder and its manufacture method |
| CN114178523A (en) * | 2017-10-04 | 2022-03-15 | Ｊｘ金属株式会社 | Method for producing surface-treated copper fine particles |
| CN114178523B (en) * | 2017-10-04 | 2024-03-01 | Ｊｘ金属株式会社 | Method for producing surface-treated copper microparticles |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI370033B (en) | 2012-08-11 |
| JP5235193B2 (en) | 2013-07-10 |
| JPWO2009001710A1 (en) | 2010-08-26 |
| KR20100024431A (en) | 2010-03-05 |
| WO2009001710A1 (en) | 2008-12-31 |
| TW200914166A (en) | 2009-04-01 |
| JP2013057128A (en) | 2013-03-28 |
| US20100192728A1 (en) | 2010-08-05 |
| KR20120116013A (en) | 2012-10-19 |
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