CN101394961A - Process for production of copper powder and copper powder obtained by the process - Google Patents

Process for production of copper powder and copper powder obtained by the process Download PDF

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Publication number
CN101394961A
CN101394961A CNA2007800073532A CN200780007353A CN101394961A CN 101394961 A CN101394961 A CN 101394961A CN A2007800073532 A CNA2007800073532 A CN A2007800073532A CN 200780007353 A CN200780007353 A CN 200780007353A CN 101394961 A CN101394961 A CN 101394961A
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slurry
copper powder
value
copper
cuprous oxide
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坂上贵彦
吉丸克彦
中村芳信
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Mitsui Mining and Smelting Co Ltd
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Mitsui Mining and Smelting Co Ltd
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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
    • 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
    • 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
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/052—Metallic powder characterised by the size or surface area of the particles characterised by a mixture of particles of different sizes or by the particle size distribution
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/52—Electrically conductive inks

Abstract

The invention aims at providing a process for producing copper powder composed of uniform fine particles by a wet reduction method efficiently and high-quality copper powder excellent in particle size distribution. In order to attain the aim, a process for the production of copper powder is employed, which comprises reacting an aqueous solution of copper ions with an alkali solution to form a copper hydroxide slurry, adding a reducing agent to the slurry to conduct the first reduction treatment of the slurry and thereby form a copper suboxide slurry, allowing the copper suboxide slurry to stand to precipitate copper suboxide particles, removing the formed supernatant, washing the copper suboxide particles by the addition of water to form a washed copper suboxide slurry, and adding a reducing agent to the suboxide slurry to conduct the second reduction treatment of the slurry and thereby form copper powder, characterized in that in the first reduction treatment, both a hydrazine as a reducing agent and aqueous ammonia as a pH regulator are added to the copper hydroxide slurry.

Description

The manufacture method of copper powder and the copper powder that obtains with this manufacture method
Technical field
The present invention relates to a kind of manufacture method of the copper powder that is undertaken by the wet type reducing process, particularly, relate to and a kind ofly make particulate effectively evenly and the method for the high copper powder of electric conductivity and with the copper powder of this manufacture method manufacturing.
Background technology
All the time, copper powder is widely used as the raw material of copper slurry or copper printing ink.Copper slurry is because its processing ease, therefore, can be applicable to adopt the circuit of the printed wiring board of screen printing method to form, various electric electric shock portion etc., and is used for guaranteeing the method that conducts.In order to control the copper slurry viscosity, also must consider the various characteristics of copper powder according to its application.
For example, copper slurry is that an amount of resinous principle that cooperates forms in the copper powder that the fine particle that is several microns constitutes by particle diameter, and it is used for the formation of circuitry shapes etc., and it is burnt till or solidifies and as conducting film performance electric conductivity.Owing to be subjected to the influence of the miniaturization of printed wiring board etc., be used for the copper powder of copper slurry and have higher characteristic in aspect requirements such as the electric conductivity of the circuit that forms by this slurry, reliabilities.
And, wish that the copper powder that is used for the copper slurry can reduce slurry viscosity, can make the operability of slurry easy, and can improve the landfill of the via of printed wiring board.In order to satisfy this market demand, adopt suitableization of the granularity that makes copper powder or specific area and with organic substance the powder surface is carried out various solutions such as surface treatment, with the reduction of seeking the copper slurry viscosity etc.
As the manufacture method of this copper powder, adopt the wet type reducing process usually.The manufacture method that adopts the manufacturing of wet type reducing process to be controlled as the copper fine-particle powder of excellent particle size is disclosed in the patent documentation 1.The manufacture method of the copper powder that adopts spray-on process to make effectively to have the fine particle size that can tackle fine wiring and surface smoothing is disclosed in patent documentation 2 on the other hand.
Special fair 5-No. 57324 communiques of patent documentation 1:JP
Patent documentation 2:JP spy opens communique 2002-No. 343135
Summary of the invention
The problem that invention will solve
In recent years, along with the development of application technology, the further improvement of the powder characteristics of market demand copper powder.That is, wish to have a kind of method that can make surface smoothing, the fine and copper powder that the particle diameter uniform conductive is high with low cost.At this, under the situation that is the fine-particle copper powders made by spray-on process, though it is low to produce the carbon amount, size distribution, dispersed aspect also excellent copper powder, but it contains seedy, is not suitable for fine wiring etc., meanwhile, have impure and the low tendency of yield.And, if removal coarse grain and strengthen classification, then exist the problem that manufacturing cost improves.On the other hand, the copper powder that adopts the wet type reducing process that obtains evenly fine particle easily in the past to obtain, though its primary particle itself is uniform particulate, but because most organic reducing agents that adopt, be contained in the organic substance adsorbance that the dispersant etc. of reduction system causes and improve, therefore, the volatilization that is accompanied by adsorb organic compound matter when burning till produces gas, thereby cause burning till the film rough surface, and be easy to generate internal flaw, aspect electric conductivity, problem is arranged.
In addition, as described in patent documentation 1, under for the situation of wet type reducing process that has adopted inorganic reducing agent, can address the above problem, but exist the problem that on the granularity of gained copper powder or yield, is easy to generate deviation.
At this, the result who adopts the manufacture method shown in the above-mentioned patent documentation 1 to make copper powder is shown.That is, 80kg (320mol) copper sulphate is dissolved in the water, in the temperature of 40 ℃ of maintenances, adds ammoniacal liquor, pH value of aqueous solution is adjusted to 4.0, behind the formation copper hydroxide slurry, add water, the solution total amount is adjusted into 160 liters.Add 6.01kg (120.1mol) hydrazine hydrate when this solution is kept 50 ℃ temperature, make it to react 60 minutes, thereby generate the cupric oxide slurry.After reaction finishes, left standstill 60 minutes, add water after removing supernatant, make the solution total amount be adjusted into 160 liters.
Then, add the hydrazine hydrate of 8.01kg (160.0mol) when this solution is kept 50 ℃ temperature, make it to react 60 minutes.Thus, cuprous oxide is reduced, and becomes copper powder.
Then; with the natural gravity filter it is filtered; after washing with water; 40 liters of gum concentrations sol solution that is 0.5g/l is led to liquid filter that (water leads to the liquid washing and filtering; leading to liquid with 9 liters of oleic acid concentrations methanol solution that is 0.2 volume % filters) each handle after; under 80 ℃ common environment, carry out drying, thereby obtain 20kg copper fine-particle powder.
About 10 groups of copper powders that obtain as mentioned above, adopt existing analytical equipment to carry out D to every group 10, D 50, D 90, standard deviation (SD), D 90/ D 10, specific area, jolt ramming packed density evaluation, in the lump each powder characteristics is calculated mean value, each data of standard deviation of 10 groups.
10 cell means of the copper powder powder characteristics that the above-mentioned operation of process obtains are D 10=1.03 μ m, D 50=3.42 μ m, D 90=7.46 μ m, standard deviation (SD)=2.58 μ m, D 90/ D 10=7.29, specific area (SSA) is 0.89m 2/ g, jolt ramming packed density (TD) are that 3.4g/cc, average yield are 85.8%.It is the results are shown in the table 1.In addition, yield calculates the theoretic copper powder amount of calculating from used mantoquita amount with the actual copper powder amount that obtains.
The result of implementation of table 1 patent documentation 1
Figure A200780007353D00051
As known from Table 1, by patent documentation 1 disclosed copper powder, its average yield is 85.8%, and the deviations of yield is 8.5, and the fluctuation between visible every group is big.In addition, and the characteristic of granular relevant also between every group, have sizable deviation.That is,, aspect steady production, remain further to be improved though we can say according to patent documentation 1 invention disclosed and show good powder characteristics sometimes.
So the inventor has verified above-mentioned patent documentation 1.Its result, in patent documentation 1, attempt in keeping the copper hydroxide slurry, to have added interpolation hydrazine hydrate in the pH value of solution of water, and make it reaction and generation cuprous oxide slurry, though but can keep its pH value within the specific limits, the pH value that the constant maintenance of reaction paste in the reduction reaction is certain is difficult.Therefore, the change of pH value must be arranged when reducing, think that the upset condition of this pH value hinders stable yield or powder characteristics is brought bad influence.
In view of above-mentioned problem, the object of the present invention is to provide a kind of manufacture method of copper powder and the copper powder that obtains with this manufacture method, the manufacture method of described copper powder is to make the method for microgranular and the uniform copper powder of particle with the wet type reducing process, can be stably and obtain conductance height, even and high-quality copper powder efficiently according to this method.
Solve the method for problem
So the inventor in order to solve above-mentioned problem, has adopted following method through concentrated research.
The manufacture method of copper powder of the present invention: it is the copper powder manufacture method of being undertaken by wet type reduction, comprising: the copper ions aqueous solution and alkaline solution are reacted and obtain Kocide SD slurry (operation 1); Add reducing agent and carry out the first reduction processing to this Kocide SD slurry, obtain cuprous oxide slurry (operation 2); Leave standstill this cuprous oxide slurry, thereby make the cuprous oxide particle precipitation, wash the cuprous oxide slurry that obtains cleaning by adding water after removing supernatant, in this cuprous oxide slurry of cleaning, add reducing agent and carry out the second reduction processing, thereby obtain copper powder (operation 3), it is characterized in that, during first reduction is handled, add as the hydrazine class of reducing agent in the lump and adjust the ammonia spirit of agent as pH to the Kocide SD slurry.
At this, the manufacture method of above-mentioned copper powder is characterised in that, adds as the hydrazine class of reducing agent in the lump and adjusts the ammonia spirit of agent as pH to the Kocide SD slurry in operation 2.In above-mentioned manufacture method,, think to be divided into operation 1～operation 3 if with the operation rough classification.Detailed content then is illustrated in embodiment described later.
In addition, in above-mentioned operation 2 (first reduction handle), preferably adjust the ammonia spirit of agent, thereby make the variation of pH value be controlled at the scope of pH3.0～pH7.0 by adding in the lump to the Kocide SD slurry as the hydrazine class of reducing agent with as pH.
In addition, the variation of above-mentioned pH value control, the difference of the endpoint pH of the initial pH value the when interpolation of preferably reducing agent and pH value being adjusted agent begins during with the interpolation end is controlled at below 3.0.
At this, " initial pH value " be meant add in the lump begin as the hydrazine class of reducing agent with as the ammonia spirit that pH adjusts agent before the pH value of solution.On the other hand, " endpoint pH " is meant the pH value of the solution the when interpolation of reducing agent and pH adjustment agent finishes.
In addition, in above-mentioned operation 2 (first reduction is handled), preferably, the minimum pH value of the pH value that changes is controlled at more than 2.8 by adding in the lump to the Kocide SD slurry as the hydrazine class of reducing agent and the ammonia spirit of adjusting agent as pH.
And in the manufacture method of copper powder of the present invention, during preparation Kocide SD slurry, the alkaline solution that reacts with the copper ions aqueous solution is preferably ammonia spirit.
In addition, in the manufacture method of copper powder of the present invention, preferred above-mentioned clean cuprous oxide pH value of slurry is pH4.1～pH6.0.
The copper powder that obtains by manufacture method of the present invention: it is characterized in that the manufacture method manufacturing of the copper powder by the invention described above.
The invention effect
The manufacture method of copper powder of the present invention, adopt the 2 step reducing process that copper particle is separated out in reduction through cuprous oxide, particularly, by the process that is reduced to cuprous oxide from copper ion and be used as the hydrazine class of reducing agent and adjust the ammonia spirit of agent as pH, the variation of the pH value of control reaction solution is as far as possible little, thereby can make reaction paste be in good reducing condition.Thus, can improve the process stability of copper powder manufacturing process, suppress the generation of cohesion, reduce the deviation of particle, can access the copper powder of narrow particle size distribution, and can make the powder characteristics of copper powder more even, thereby also improve yield.
And, by adopting the manufacture method of above-mentioned copper powder, can stably make copper powder, not only can suppress manufacturing cost, can also provide the deviation of particle little, narrow particle size distribution and high-quality copper powder.
Description of drawings
Fig. 1 is the figure that is illustrated in the pH value of solution value variable condition of beginning when the Kocide SD slurry adds the hydrazine class to operation 2 end in the operation 2.
The specific embodiment
Below, the specific embodiment of copper powder manufacture method of the present invention is illustrated.
Copper powder manufacture method of the present invention: copper powder manufacture method of the present invention can be divided into following operation 1～operation 3.Below, describe at each operation.
Operation 1: in operation 1, the copper ions aqueous solution and alkaline solution are reacted and obtain the Kocide SD slurry.This Kocide SD slurry is meant the slurry that contains Kocide SD, also comprises other the constituent beyond the Kocide SD sometimes.At this, " the copper ions aqueous solution " and " alkaline solution " are described.
At this said copper ions aqueous solution, be meant the solution that in water, adds water-soluble mantoquita and dissolved, be the solution that contains bivalent cupric ion.At this said mantoquita, be meant copper sulphate, copper nitrate, Schweinfurt green, copper chloride etc., be preferably copper sulphate, copper nitrate especially.In addition, the content of this mantoquita is calculated as 2.2mol/l～3.0mol/l with the copper concentration in the copper ions aqueous solution, more preferably the concentration of 2.5mol/l～3.0mol/l.When the copper concentration in the copper ions aqueous solution was lower than 2.2mol/l, the copper concentration in the solution was too low, and it is even that the particle diameter of copper powder particle is difficult to reach.On the other hand, when the copper concentration in the copper ions aqueous solution surpasses 3.0mol/l, the copper excessive concentration, the cohesion of the copper powder particle that reduction is separated out is obvious, thereby not preferred.
In addition, at this said alkaline solution, can use potassium hydroxide, NaOH, ammonia spirit etc.But, most preferably be ammonia spirit.This is because the variation of the pH value can easily control reduction reaction in the operation 2 described later the time, and the few cause of the residual component on the particle surface of resultant copper powder.With respect to 1mol copper, the addition of this alkaline solution is 1.4mol～1.8mol.When the addition with respect to the alkali of 1mol copper is lower than 1.4mol, can't obtain being suitable for the Kocide SD slurry that copper powder is made, can not reach good yield, the powder characteristics of gained copper powder also has big deviation.On the other hand, when with respect to 1mol copper, when the alkali concn in the Kocide SD slurry surpassed 1.8mol, the Kocide SD pH value of slurry showed strong basicity, was difficult to be controlled to suitable pH value scope in the reduction operation.
In adjustment to this Kocide SD slurry, preferably make the solution temperature of copper ions solution reach 30 ℃～70 ℃ (more preferably 40 ℃～60 ℃), to the alkaline solution that wherein adds as nertralizer, thereby neutralization is pH3.0～pH7.0.Here, why the solution temperature with the copper ions aqueous solution is adjusted into 30 ℃～70 ℃, is because when solution temperature is lower than 30 ℃, can not dissolve above-mentioned minimum mantoquita of limiting the quantity of aptly, the solution that can't obtain having suitable copper concentration.In contrast to this, when the solution temperature of the copper ions aqueous solution surpasses 70 ℃, become the high Kocide SD of crystallinity easily.Its result, after operation 2 in the dissolution velocity of Kocide SD slack-off, it is big that the gained cuprous oxide particle becomes, and therefore, is difficult to obtain uniform copper in subsequent handling.Cause operation and quality instability.
In addition, preferably the Kocide SD pH value of slurry is controlled at 3.0～7.0 scope.When breaking away from this scope, in follow-up operation 2, be difficult to the pH value of solution value is controlled near the neutral region.This pH value zone is when the copper concentration in the above-mentioned Kocide SD slurry being adjusted into 2.2mol/l～3.0mol/l and will being adjusted into 1.4mol～1.8mol with respect to the alkali number of 1mol copper, the scope that can control.
Operation 2: in operation 2, carry out in this Kocide SD slurry adding reducing agent and first reduction that obtains the cuprous oxide slurry is handled.In copper powder manufacture method of the present invention, its maximum is characterised in that, adds as the hydrazine class of reducing agent in the lump and adjusts the ammonia spirit of agent as pH to the Kocide SD slurry in operation 2.
In operation 2, add hydrazine class (reducing agent) to above-mentioned Kocide SD slurry, thereby mainly carry out Kocide SD is reduced to cuprous oxide, generate the processing of cuprous oxide slurry.This cuprous oxide slurry is meant the slurry that contains cuprous oxide, also contains cuprous oxide constituent in addition sometimes.The cuprous oxide slurry of cleaning to operation 3 described later is like this too.In this operation, why adopt the hydrazine class as reducing agent, be because absorption to remain in the lip-deep possibility of cuprous oxide low, be difficult to become the cause of polluter.As the hydrazine class, can enumerate various materials such as hydrazine hydrate, hydrazine sulfate, anhydrous hydrazine, but hydrazine hydrate most preferably.Use can be used or mix to these hydrazine classes separately.And, preferably be supplied to reaction as solution.This is the cause that does not cause inhomogeneous reaction because can promptly diffuse in the solution of reaction system.
With respect to the copper in the Kocide SD slurry of 1mol, the addition of this hydrazine class is 0.3mol～0.5mol.When with respect to above-mentioned 1mol copper, when the addition of hydrazine class was lower than 0.3mol, the residual quantity of unreacted Kocide SD increased, thereby not preferred.In contrast to this, when with respect to above-mentioned 1mol copper, when the addition of hydrazine class surpasses 0.5mol, can not stop reduction reaction in the stage of cuprous oxide, its result causes cohesion etc. easily, is difficult to produce the copper powder with good powder characteristics.
In addition, in operation 2, above-mentioned Kocide SD slurry is reduced in the processing of cuprous oxide slurry, when adding above-mentioned hydrazine class as reducing agent, is adding the ammonia spirit of adjusting agent as pH value, thereby processing is reduced on limit control pH value variation limit.At this, why use ammonia spirit, be because use ammonia as nertralizer when considering when generating the Kocide SD slurry, can integrate the characteristic that nertralizer and pH adjust agent, discharge the xenogenesis composition as far as possible, thereby do one's utmost to avoid of the absorption of xenogenesis composition, control the cause of the purity of gained copper powder easily at particle surface.In addition, in order to make because of the acid pH value of solution value of the interpolation of hydrazine class deflection accurately is adjusted near the neutrality the characteristic of preferably utilizing ammonia to have as nertralizer.
Represent to begin the pH value of solution value variable condition when the Kocide SD slurry adds the hydrazine class to operation 2 end in operation 2 with Fig. 1 here.In this Fig. 1, illustrate and with the pH value change curve of the embodiment 1 of hydrazine and ammonia spirit with use the pH value change curve of the comparative example of hydrazine separately.As can be known clear and definite from their contrast, embodiment 1 and comparative example are beginning to add the hydrazine time-like, are the oxytropism side variation sharp temporarily of Kocide SD pH value of slurry.Then, when the alcaliotropism side shifts the pH value of certain amplitude, become stable normality.There to be the prerequisite that is changed to of pH value so, following content is described.
Preferably by in the Kocide SD slurry, adding hydrazine class and ammonia spirit in the lump, thereby compare, make the pH value be controlled at 3.0～7.0 scope, make the transfer amplitude of pH value oxytropism side little with the situation of not using ammonia spirit.Its result, little to the influence of particle coacervation etc., the dispersiveness of gained copper powder is higher, can efficiently produce the copper powder of narrow particle size distribution.
For the pH value being controlled at 3.0～7.0 scope, preferably above-mentioned hydrazine class and ammonia spirit are carried out in accordance with the following methods to the interpolation of Kocide SD slurries.Promptly, preferred hydrazine class and the ammonia spirit of adding continuously, so that add when finishing, with respect to the copper in the above-mentioned Kocide SD slurry of 1mol, the ratio of hydrazine class is that the ratio of 0.3mol～0.5mol and ammonia spirit (as ammonia) is 0.2mol～0.4mol, like this pH value of slurry of adding is as long as the difference of the endpoint pH of the initial pH value when being adjusted into interpolation that reducing agent and pH adjust agent and beginning when adding end is below 3.0.In addition, preferably in the variation of the scope inner control pH of pH value 3.5～5.0 value.And about the total amount of the alkali of use in operation 1 and the operation 2, with respect to 1mol copper, preferably its alkali composition is 1.85mol～2.0mol.
Here,, change at any time, cause to surpass 3 variation from initial pH value according to the pH value of its addition solution when independent interpolation hydrazine time-like.When having the variation of pH value of solution value so, the particle diameter deviation of gained cuprous oxide particle is big, causes the size distribution variation as the copper powder particle of final products.For this reason, and with hydrazine class and ammonia spirit, by continuous interpolation they, the variation minimum of the pH value of solution when making restoring operation keeps certain pH value.
At this, when the addition of hydrazine class and ammonia spirit was lower than this lower limit, Kocide SD can not carry out well to the reduction of cuprous oxide.On the other hand, when the addition of hydrazine class and ammonia spirit surpasses this higher limit, can not stop restoring operation in the stage of cuprous oxide.In addition, when breaking away from above-mentioned interpolation scope, the pH value variation of adding solution can not be controlled between 3.0～7.0, its result can't obtain having the copper powder of good powder characteristics.
In addition, in operation 2, shown in the comparative example of Fig. 1, add the hydrazine time-like when beginning in the Kocide SD slurry, the pH value of solution is oxytropism side variation sharp temporarily.This amplitude of variation is according to addition and difference, if do not use ammonia spirit, the Kocide SD slurry that begins to add the hydrazine class becomes the pH value and is lower than 2.8 highly acid.In highly acid zone so, the powder characteristics variation of gained copper powder, the deviation of product qualified rate strengthens.Therefore, as copper powder manufacture method of the present invention, by and with adding as the hydrazine class of reducing agent and adjusting the ammonia spirit of agent as pH, shown in the embodiment 1 of Fig. 1, can make the rapid transfer that has just begun to add the pH value oxytropism side after the hydrazine class be in the state that the pH value is the alkaline side more than 2.8, by pH value change curve is generally speaking diminished to the transfer of highly acid side, thereby improve the powder characteristics of gained copper powder, obtain stable and high product qualified rate.Above-mentioned and below content in, with this rapid oxytropism side change, acid pH value when the strongest is called " minimum pH value ".
In addition, the solution temperature of operation 2 preferably adopts 40 ℃～60 ℃ scope.When being lower than 40 ℃, reduction reaction speed is slow, can not satisfy industrial productivity.On the other hand, when surpassing 60 ℃, reduction reaction is too fast, causes uneven reduction reaction, therefore, and the powder characteristics variation of gained copper powder.Usually in the said temperature scope, when the particle diameter of wishing gained cuprous oxide is particulate, preferably keep constant at low temperatures,, preferably under high temperature, keep constant when the particle diameter of wishing gained cuprous oxide when being big.
Operation 3: in operation 3, leave standstill this cuprous oxide slurry and precipitate cuprous oxide particle, remove supernatant after, by adding water cuprous oxide is washed, the cuprous oxide slurry that obtains cleaning by reduce processing to this cuprous oxide slurry of cleaning interpolation, obtains copper powder.
In operation 3, leave standstill above-mentioned cuprous oxide slurry and precipitate cuprous oxide particle.PH value of solution value in this step is about about 3.9.In addition, after removing its supernatant, add water, cuprous oxide particle is washed.Washing methods to this moment is not done special qualification, can adopt all washing methods, but preferably adopt following dispersion washing (リ パ Le プ cleans), the washing grade is managed with the pH value of the cuprous oxide slurry in the washing (following said " the cuprous oxide slurry of cleaning ").At this, when carrying out this washing, fill with washings after the discarded supernatant, and should operate repeatedly and carry out, and the slurry form of having injected washings when carrying out this operation repeatedly is called clean cuprous oxide slurry.
In disperseing washing, preferably wash repeatedly, become any constant pH value between 4.1～6.0 until the cuprous oxide pH value of slurry of cleaning.When the cuprous oxide pH value of slurry of cleaning is lower than 4.1, when obtaining copper powder further adding reducing agent the cohesion of copper powder strong, powder characteristics variation such as bad dispersibility.On the other hand, when the pH value of the cuprous oxide of cleaning surpasses 6.0, cause the electron transfer reaction (reaction of giving and accepting thereby ionic weight is few, acidichromism) variation, when obtaining copper powder further adding reducing agent, the generation cohesion causes the uniformity reduction of particle etc., and its powder characteristics is variation also, and reduction efficiency is poor.That is, we can say that the pH value is to be beneficial to the scope of condensing avoided between 4.1～6.0.
In addition, more preferably washing to the cuprous oxide pH value of slurry of cleaning becomes any constant pH value between 4.3～4.7.Be adjusted into 4.3～4.7 by the cuprous oxide pH value of slurry that will clean, not only can suppress cohesion, also reduce coarse grain, can obtain particulate and the few good copper powder of deviation with low cost, be positioned at this scope, then the stability for the operation that obtains particulate and polymolecularity is the most excellent.
Then, in the cuprous oxide slurry of cleaning that obtains as mentioned above, add reducing agent.PH value when at this moment, interpolation being finished is adjusted into 7.0～9.0 and gets final product.That is, if the hydrazine class, when add finishing, with respect to the copper in the clean cuprous oxide slurry of being contained in of 1mol, the reduction dosage that is added is preferably 0.4mol～0.7mol.More preferably, the total amount of the hydrazine class of being added in operation 2 and the operation 3 is 0.85mol～1.2mol with respect to 1mol copper.When this pH value greater than 9.0 the time, become the many states of reducing agent, be easy to generate particulate and be easy to generate cohesion.On the other hand, when the pH value less than 7.0 the time, the coarse grain increase causes being easy to generate cohesion, dispersed variation.Therefore, if add the scope of the pH value disengaging 7.0～9.0 when finishing, the obvious variation of the powder characteristics of gained copper powder shows wide size distribution.
The temperature of preferred reducing agent remains between 40 ℃～55 ℃ to a certain degree.When the temperature of reducing agent was lower than 40 ℃, reduction reaction was slow, can not satisfy the productivity ratio of industrial hope.On the other hand, when surpassing 55 ℃, reduction rate is too fast, and particle diameter is uneven easily.In addition, as the reducing agent of operation 3, preferably adopt the hydrazine class of using in the above-mentioned operation 2.Its reason is, the reducing power that has as the hydrazine class of reducing agent is fit to obtain the good copper powder of powder characteristics.In addition, by adopt with operation 2 in the identical reducing agent of reducing agent of use, can reduce the xenogenesis composition relevant as much as possible with the reduction of copper powder, reduce the adhesion amount of pollutant component on the particle surface of copper powder thus.
In addition, preferably handling under the slurry form of ending phase to the reduction of copper powder, adopt fluid polishing (thread mill etc.), laminar flow mixing method (T.K.Filmix etc.), aggregated particle is bumped against in carrying out the mobile slurry of high speed centrifugation each other, thereby destroying state of aggregation makes it approach primary particle, implement to be used to carry out the level and smooth grain of separating of particle surface simultaneously and handle, improve the particle dispersiveness thus.
The copper powder that obtains as mentioned above through the common operation of filtration, washing, drying etc., thereby is able to commercialization as copper powder.And, in order to improve acid resistance, preferably this copper powder is implemented surface treatment as required with the aliphatic acid or the amine of oleic acid, stearic acid etc.In addition, even under the state of this drying copper powder, also can be as required, implement to separate grain with the device that can carry out the conflict processing between the aggregated particle of grading plant, powder compounding machine (Ha イ Block リ イ ザ-), air classifier (-ボ Network ラ シ Off ァ イ ア) etc. and handle, thereby improve the particle dispersiveness.
As mentioned above, according to copper powder manufacture method of the present invention, particulate can be produced stably and deviation is few, the uniform copper powder of powder characteristics.In addition, owing to can suppress of the absorption of xenogenesis element to particle surface, the gaseous volatilization in the time of therefore can suppressing to burn till, the internal flaw that can as far as possible avoid burning till film can produce the good copper powder of conductance thus.
Below, specifically describe the present invention with embodiment and comparative example.In addition, the present invention is not limited to following embodiment.And for the ease of understanding creating conditions of copper powder in following embodiment and the comparative example, simple record is created conditions in table 2.
Table 2
Figure A200780007353D00121
(note): copper sulphate: copper sulfate pentahydrate
Ammonia: the ammonia spirit of 25wt% concentration
Reducing agent: hydrazine monohydrate
PH adjusts agent: the ammonia spirit of 25wt% concentration
Embodiment 1
Operation 1: in 6.5 liters 50 ℃ pure water, add the copper sulfate pentahydrate of 6000g (24.0mol), prepare to contain the copper ions aqueous solution of bivalent cupric ion.Then, to this copper ions aqueous solution that remains on 50 ℃, add the ammonia spirit (concentration 25wt%) of 2500ml (36.7mol) and neutralize with times of 30 minutes, thereby obtain the Kocide SD slurry.Then, adding pure water to this Kocide SD slurry, is that 2mol/L, pH value are 6.3 thereby be adjusted into copper concentration.
Operation 2:, add as the hydrazine monohydrate of reducing agent and the ammonia spirit of adjusting agent as pH to above-mentioned Kocide SD slurry in order to control the variation of pH value.Promptly, the liquid temperature that with the pH value is 6.3 above-mentioned Kocide SD slurry remains on 50 ℃, with the continuous ammonia spirit (concentration 25wt%) that adds 450g (9.0mol) hydrazine monohydrate and 590ml (8.7mol) of 30 minutes times, thereby make the pH value of adding when finishing be adjusted into 3.9.In the variation of this said pH value, initial pH value 6.3, endpoint pH 3.9, minimum pH value 3.5, initial pH value and endpoint pH difference are 2.4.For reduction reaction is carried out fully, further continue to stir 30 minutes.
Then, disperse washing.That is, add pure water and leave standstill after being adjusted to 18 liters in the slurry of operation 2 operation that is through with, remove 14 liters of supernatants after leaving standstill, the pH value that this dispersions washing operation is proceeded to after disperseing to wash repeatedly reaches 4.7, thus the cuprous oxide slurry that obtains cleaning.
Operation 3: then, add water, the liquid temperature is remained on 50 ℃, make copper concentration be adjusted into 2mol/L to above-mentioned clean cuprous oxide slurry.Then, with the hydrazine monohydrate that added 600g (12.0mol) in 30 minutes.The pH value of adding when finishing is 8.2.Further, carry out 60 minutes stirring, reduction reaction is carried out fully, thereby copper powder (second reduction is handled) is separated out in reduction.
The copper powder that so obtains is filtered and collected.Then, in this copper powder, add 5 liters of methanol solutions that are dissolved with the 1.5g lauryl amine, thereby carry out surface treatment, and carry out 30 minutes stirring, carry out 80 ℃ * 5 hours heat drying, thereby obtain powder.
For the powder characteristics of verifying the copper powder that is obtained by embodiment 1 and the deviation of yield, in 10 groups of copper powders that obtained by the foregoing description 1 every group carries out D 10, D 50, D 90, standard deviation (SD), D 90/ D 10, specific area, jolt ramming packed density mensuration, and each powder characteristics calculated mean value, each data of standard deviation of 10 groups, The above results is shown in Table 3.In addition, will be expressed as SD, will be expressed as σ, distinguish both thus the standard deviation of 10 groups of data to every group standard deviation.
The powder characteristics of copper powder: 10 cell means of the copper powder powder characteristics that the above-mentioned operation of process obtains are D 10=0.77 μ m, D 50=1.75 μ m, D 90=3.68 μ m, standard deviation (SD)=1.14 μ m, D 90/ D 10=4.77, specific area (SSA)=0.54m 2/ g, jolt ramming packed density (TD)=4.7g/cc.
Calculate the yield of every group of copper powder, its result is more than 97%, and its yield deviations is 0.8, can access stable yield.In addition, yield is with the actual copper powder amount that obtains the theoretic copper powder amount of calculating from employed mantoquita amount to be calculated.
Table 3
Figure A200780007353D00141
Embodiment 2
Operation 1: adopt method similarly to Example 1, obtain the Kocide SD slurry.
Operation 2:, add as the hydrazine monohydrate of reducing agent and the ammonia spirit of adjusting agent as pH to above-mentioned Kocide SD slurry in order to control the variation of pH value.Promptly, the liquid temperature that with the pH value is 6.3 above-mentioned Kocide SD slurry remains on 40 ℃, with the continuous ammonia spirit (concentration 25wt%) that adds 450g (9.0mol) hydrazine monohydrate and 350ml (5.1mol) of 15 minutes times, thereby make the pH value of adding when finishing be adjusted into 4.8.In the variation of this said pH value, initial pH value 6.3, endpoint pH 4.8, minimum pH value 3.8, initial pH value and endpoint pH difference are 1.5.For reduction reaction is carried out fully, further continue to stir 30 minutes.Then, disperse washing similarly to Example 1, the cuprous oxide slurry that obtains cleaning.
Operation 3: then, the liquid temperature of the reaction paste during with reduction remains on beyond 45 ℃, operates equally with the operation 3 of embodiment 1, thereby the copper powder reduction is separated out.
The copper powder that obtains is as mentioned above carried out similarly to Example 1 post processing, thereby obtain powder.
10 groups of copper powders to being obtained by embodiment 2 similarly to Example 1, carry out D to every group 10, D 50, D 90, standard deviation (SD), D 90/ D 10, specific area, jolt ramming packed density mensuration, and each powder characteristics calculated mean value, each data of standard deviation of 10 groups, The above results is shown in Table 4.
The powder characteristics of copper powder: 10 cell means of the copper powder powder characteristics that the above-mentioned operation of process obtains are D 10=0.63 μ m, D 50=1.49 μ m, D 90=3.08 μ m, standard deviation (SD)=0.91 μ m, D 90/ D 10=4.89, specific area=0.62m 2/ g, jolt ramming packed density=4.1g/cc.In addition, calculate the yield of every group of copper powder, its result is more than 97%, and its yield deviations is 0.9, can access stable yield.
Table 4
Figure A200780007353D00151
Embodiment 3
In embodiment 3, except the liquid temperature with when reduction in the operation 3 changes to 45 ℃, adopt method similarly to Example 1, obtain copper powder.In addition, the pH value in operation 2 changes, and its initial pH value 6.3, endpoint pH 3.9, minimum pH value 3.5, initial pH value and endpoint pH difference are 2.4.
10 groups of copper powders to being obtained by embodiment 3 similarly to Example 1, carry out D to every group 10, D 50, D 90, standard deviation (SD), D 90/ D 10, specific area, jolt ramming packed density mensuration, and each powder characteristics calculated mean value, each data of standard deviation of 10 groups, The above results is shown in Table 5.Calculate the yield of every group of copper powder, its result is more than 97%, and its yield deviations is 0.9, can access stable yield.
The powder characteristics of copper powder: 10 cell means of the copper powder powder characteristics that the above-mentioned operation of process obtains are D 10=0.85 μ m, D 50=1.99 μ m, D 90=4.05 μ m, standard deviation (SD)=1.20 μ m, D 90/ D 10=4.79, specific area=0.46m 2/ g, jolt ramming packed density=5.0g/cc.
Table 5
Figure A200780007353D00161
Comparative example
In comparative example, do not use the ammonia spirit in the operation 2 as pH adjustment agent, this point is different with embodiment.Therefore, operation is in addition omitted its explanation.
Operation 2: the liquid temperature of above-mentioned Kocide SD slurry is remained on 50 ℃, only add 450g (9.0mol) hydrazine monohydrate continuously with 30 minutes times.The pH value that its minimum pH value is 2.4, add when finishing is 3.2.That is, because the pH after the Kocide SD slurry adjustment operation is 6.3, therefore, initial pH value and endpoint pH difference are 3.1.Then, carry out fully, further continue to stir 30 minutes in order to make reduction reaction.
Then, disperse washing.That is, in the slurry of the operation 2 that is through with, add pure water and leave standstill after being adjusted to 18 liters, remove 14 liters of supernatants after leaving standstill, this dispersions washing operation is proceeded to pH after disperseing to wash repeatedly to reaching 4.5, thus the cuprous oxide slurry that obtains cleaning.At this moment, with respect to cyclic washing number of times (average 2 times) in the above-described embodiments, the cyclic washing number of times in this comparative example is for when the number of times that disperses washing is 4 times, and the pH value is 4.5, and hence one can see that, and the washing cost improves.
10 groups of copper powders to being obtained by comparative example similarly to Example 1, carry out D to every group 10, D 50, D 90, standard deviation (SD), D 90/ D 10, specific area, jolt ramming packed density mensuration, and each powder characteristics calculated mean value, each data of standard deviation of 10 groups, The above results is shown in Table 6.By this result as can be known, the mean value of yield is 84.5% low value.
Table 6
Figure A200780007353D00171
The powder characteristics of copper powder: 10 cell means of the copper powder powder characteristics that is obtained by comparative example are D 10=0.63 μ m, D 50=1.71 μ m, D 90=5.13 μ m, standard deviation (SD)=1.52 μ m, D 90/ D 10=8.63, specific area (SSA)=1.51m 2/ g, jolt ramming packed density (TD)=3.0g/cc.
At this, the evaluation method and the evaluating apparatus of each characteristic in this specification is illustrated.Volume accumulation particle diameter and size distribution (D 10, D 50, D 90, SD) mensuration, the 0.1g copper powder is mixed with 0.1% aqueous solution (manufacturing of sannopco company) of SN デ ィ ス パ-サ Application ト 5468, adopt ultrasonic homogenizer (US-300T, the smart mechanism of Japan is done manufacturing) disperse after 5 minutes, adopt laser diffraction formula particle size distribution device at random Micro Trac HRA 9320-X100 type (manufacturing of Leeds+Northrup company) and carry out.In addition, the mensuration of " jolt ramming packed density " is to measure with パ ウ ダ-ス -PT-E (manufacturing of Hosokawa Micron company).Specific area be to the 2.00g sample after the degassing of carrying out under 75 ℃ 10 minutes is handled, with モ ノ ソ-Block (manufacturings of Quantachrome company), and employing BET1 point method is measured.
The contrast of embodiment and comparative example
Below, with reference to recording the mean value of embodiment and comparative example and Fig. 7 of standard deviation, embodiment and comparative example are compared at each assessment item.
Table 7
Figure A200780007353D00181
Volume accumulation particle diameter and size distribution: in size distribution, the D of comparative example 90Big a little, cohesion is strong as can be seen, but the mean value of size distribution does not have big difference.But when the standard deviation interval of considering size distribution, than comparative example, the standard deviation of embodiment 1～embodiment 3 is little.That is, than comparative example, embodiment 1～embodiment 3 has good size distribution, can be understood as to have narrow powder characteristics.
Jolt ramming packed density (TD): as known from Table 7, the jolt ramming packed density of embodiment 1～embodiment 3 is obviously than comparative example height.Therefore, form conductor when the copper powder of embodiment is implemented slurryization and the copper powder of comparative example is implemented slurryization and conductor density when forming conductor when comparing, the conductor density height of embodiment can be thought to form low-resistance conductor.
Specific area (SSA): the specific area of embodiment 1～embodiment 3 is littler than comparative example, when the granularity of primary particle during at ad eundem, can think the flatness that can improve particle surface.
Every group result of implementation: about the standard deviation of each characteristic, embodiment 1～embodiment 3 is all little than comparative example, and copper powder that we can say embodiment 1～embodiment 3 is the little uniform copper powder of the deviation ratio comparative example of powder characteristics.Particularly, about yield, than comparative example, embodiment 1～embodiment 3 can change little stable productivity ratio with high yield and yield and make, and its result can think to realize the manufacture method of copper powder cheaply.
In sum, in the operation 2 of embodiment, by adding hydrazine class and ammonia spirit in the lump, can be in the variation of prescribed limit inner control pH value, suppress cohesion that the variation because of the pH value causes etc. thus, thereby can produce the copper powder of the few and narrow particle size distribution of the stable deviation of manufacturing process with good yield.In contrast to this, the copper powder of comparative example, the deviation of powder characteristics is big, and not only yield is low, and the stability of yield is also poor.Think that its reason is the adding method of the reducing agent of operation 2.
Industrial applicibility
According to copper powder manufacture method of the present invention, can improve the productivity ratio of the good copper powder of powder characteristics. Its result can offer market at an easy rate with high-quality copper powder. In addition, copper powder of the present invention manufacturing side Method had not both been used special additive, did not more need special manufacturing installation, therefore, can seek existing Effective utilization of equipment is arranged, do not need equipment investment, therefore have very big advantage at cost.
In addition, in the manufacture method of the present invention since in operation 3, can adopt with operation 2 in use The identical reducing agent of reducing agent, can reduce thus the xenogenesis composition relevant with the reduction of copper powder. Its knot Really, can produce the few copper powder of adsorbance of pollutant component on the particle surface of gained copper powder, can carry For high conductive high-quality fine-particle copper powders, be conducive to the utilization in fine wiring.

Claims (7)

1. the manufacture method of a copper powder, it carries out the copper powder manufacturing by the wet type reduction, promptly, the copper ions aqueous solution and alkaline solution are reacted and obtain the Kocide SD slurry, add reducing agent and carry out the first reduction processing to this Kocide SD slurry, obtain the cuprous oxide slurry, leave standstill this cuprous oxide slurry, thereby make the cuprous oxide particle precipitation, remove after the supernatant and cuprous oxide particle is washed the cuprous oxide slurry that obtains cleaning, in this cuprous oxide slurry of cleaning, add reducing agent and carry out second reduction and handle, thereby obtain copper powder by adding water, it is characterized in that
During first reduction is handled, add in the lump as the hydrazine class of reducing agent with as the ammonia spirit of pH value adjustment agent to the Kocide SD slurry.
2. as the manufacture method of the copper powder of claim 1 record, it is characterized in that, in described first reduction is handled, adjust the ammonia spirit of agent by adding in the lump to the Kocide SD slurry, thereby the variation of pH value is controlled at the scope of pH3.0～pH7.0 as the hydrazine class of reducing agent with as the pH value.
3. the manufacture method of copper powder as claimed in claim 1 or 2 is characterized in that, the variation of described pH value control is that the difference of initial pH value when the interpolation that reducing agent and pH value are adjusted agent the is begun endpoint pH during with the interpolation end is controlled at below 3.0.
4. as the manufacture method of any described copper powder in the claim 1～3, it is characterized in that, in described first reduction is handled, adjust the ammonia spirit of agent by adding in the lump to the Kocide SD slurry, the minimum pH value of the pH value of change is controlled at more than 2.8 as the hydrazine class of reducing agent with as the pH value.
5. as the manufacture method of any described copper powder in the claim 1～4, it is characterized in that described alkaline solution is an ammonia spirit.
6. as the manufacture method of any described copper powder in the claim 1～5, it is characterized in that described clean cuprous oxide pH value of slurry is 4.1～6.0.
7. a copper powder is characterized in that, the manufacture method by any described copper powder in the claim 1～6 obtains.
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