CN103079730B - Argentum powder and manufacture method thereof - Google Patents
Argentum powder and manufacture method thereof Download PDFInfo
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- CN103079730B CN103079730B CN201280002704.1A CN201280002704A CN103079730B CN 103079730 B CN103079730 B CN 103079730B CN 201280002704 A CN201280002704 A CN 201280002704A CN 103079730 B CN103079730 B CN 103079730B
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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
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
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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
- B22F1/14—Treatment of metallic powder
- B22F1/148—Agglomerating
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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
- B22F1/16—Metallic particles coated with a non-metal
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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
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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
- B22F2301/00—Metallic composition of the powder or its coating
- B22F2301/25—Noble metals, i.e. Ag Au, Ir, Os, Pd, Pt, Rh, Ru
- B22F2301/255—Silver or gold
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Abstract
In order to provide and the compatibility of the solvent of silver paste agent, resin etc. and the argentum powder of excellent dispersion and manufacture method thereof, the argentum powder of the present invention forms organic coating layer on argentum powder surface, internal friction angle is less than 20 °, and be more than 100 ° with the contact angle of methanol 50 volume % aqueous solution, in the manufacture method of the argentum powder of the present invention, by Argent grain being carried out surface treatment and after surface forms organic coating layer, under the degree not damaging organic coating layer, carry out sufficient break process.
Description
Technical field
The present invention relates to argentum powder and manufacture method thereof, more specifically, relate to argentum powder and the manufacture method thereof of main constituent as silver paste agent (silverpaste), this silver paste agent is for forming the wiring layer of electronic machine, electrode etc..
The application based on June 16th, 2011 Japanese patent application No. Patent 2011-134337 in Japanese publication and CLAIM OF PRIORITY, with reference to these applications, and quoted to the application.
Background technology
Wiring layer in electronic machine, electrode etc. form the silver paste agent using resin type silver paste agent, calcinated type silver paste agent etc more.By being coated or printed on various base material by these silver paste agent, then it is heated solidifying or heating and calcining, it is possible to be formed into the conducting film of wiring layer, electrode etc..
Such as, resin type silver paste agent is made up of argentum powder, resin, firming agent, solvent etc., is printed on electric conductor circuit pattern or terminal, and being heated solidification with 100 DEG C ~ 200 DEG C makes conducting film, thus forming wiring layer, electrode.
It addition, calcinated type silver paste agent is made up of argentum powder, glass, solvent etc., being printed on electric conductor circuit pattern or terminal, heating makes conducting film to 600 DEG C ~ 800 DEG C and calcining, thus forming wiring layer, electrode.
With in the wiring layer of these silver paste agent formation, electrode, formed the current path of electrical connection by the connection of argentum powder.
The particle diameter of the argentum powder that these silver paste agent use is 0.1 μm～several μm, the thickness of the particle diameter of the argentum powder the used wiring layer because to be formed, the thickness etc. of electrode and different.It addition, by making argentum powder be evenly dispersed in silver paste agent, it is possible to form the wiring layer of even thickness, electrode in uniform thickness.
Generally, manufacture in the method for silver paste agent, in measuring each element and putting into the container of regulation, use omnipotent agitator, kneader etc. carry out mixing in advance after, carry out leading mixing with triple-roller mill etc..In mixing in advance, by each element, moistening makes it disperse fully each other is important, mixing in advance by being sufficiently carried out this, it is possible to prevent main mixing middle generation native silver, the granularity making the argentum powder in silver paste agent is rapidly decreased to targeted particle size, makes argentum powder be uniformly dispersed in silver paste agent.
Therefore, the most argentum powder accounting for weight do not required nothing more than uniform particle diameter and assembles few, also requiring that the affinity to the excipient being made up of solvent, resin etc. is good in silver paste agent, the high such characteristic of the dispersibility in silver paste agent.This characteristic not only changes along with bulk density, the character of the such powder structure aspect of particle size distribution, changes also as the slip easness of powder surface, hydrophilic, the chemical property on the such argentum powder surface of hydrophobicity.
For the argentum powder that silver paste agent uses, for instance describe in patent documentation 1: have specific bulk density and formed body density due to ball shape silver powder, thus good with the compatibility of excipient or resin.But, patent documentation 1 there is no the relevant record of surface chemical property, be only difficult to control to the compatibility of itself and excipient, resin by the parameter of this configuration aspects.It addition, for the manufacture method of argentum powder in patent documentation 1, for above-mentioned surface chemical property has the manufacture methods such as the breaking method of the argentum powder of considerable influence there is no record.
On the other hand, patent documentation 2 describes: using the ratio D50/DIA of the D50 value obtained by particle size distribution and the particle diameter DIA obtained by graphical analysis as the benchmark of powder body concentration class, if this ratio is below particular value, be then low aggregation.Really, it is believed that the quantity of the aggregation in the little then powder body of this value is few.But, patent documentation 2 is same with patent documentation 1, there is no impact when making paste to excipient, the argentum powder surface chemical property of the compatibility of resin relevant record, affect the relevant record of the manufacture method of chemical property.
For the argentum powder used in silver paste agent, as patent documentation 1, patent documentation 2, only by the character of the configuration aspects such as bulk density, formed body density, powder body concentration class, it is impossible to optimize and the compatibility of the solvent of silver paste agent, resin etc., dispersibility fully.Therefore, argentum powder is required the further lifting of the compatibility and dispersibility.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2006-097086 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2004-100013 publication
Summary of the invention
The problem that invention to solve
Thus, it is an object of the invention to, in view of above-mentioned existing situation, it is provided that a kind of with the compatibility of the solvent of silver paste agent, resin etc. with the argentum powder of excellent dispersion and manufacture method thereof.
For solving the scheme of problem
The argentum powder of the present invention realizing above-mentioned purpose is characterised by, internal friction angle is less than 20 °, and is more than 100 ° with the contact angle of methanol 50 volume % aqueous solution.
The manufacture method of the argentum powder realizing the present invention of above-mentioned purpose is characterised by, by Argent grain carrying out surface treatment and after surface forms organic coating layer, carries out sufficient break process under the degree not damaging organic coating layer.
The effect of invention
In the present invention, the internal friction angle of argentum powder is less than 20 °, and is more than 100 ° with the contact angle of methanol 50 volume % aqueous solution, thus with compatibility height, the excellent dispersion of solvent, resin etc., paste can be easily made.Thus, in the present invention, it is possible to improve quality and the productivity ratio of silver paste agent.
Accompanying drawing explanation
Fig. 1 is the model utility schematic diagram for Argent grain form and particle surface state.
Detailed description of the invention
Hereinafter, the manufacture method for the argentum powder and argentum powder that are suitable for the present invention is described in detail.It should be noted that the present invention is when being not particularly limited, it is not limited to further detail below.
Argentum powder 1 shown in Fig. 1 is included in the resin type silver paste agent being made up of firming agent, resin, solvent etc., or in the calcinated type silver paste agent being made up of glass, solvent etc..Resin type silver paste agent, calcinated type silver paste agent containing argentum powder 1 are used for forming wiring layer, electrode.Therefore, argentum powder 1 is in order to realize electrical connection, it is necessary to the compatibility with the solvent of silver paste agent, resin is good, and is uniformly dispersed in paste.Argentum powder 1 is particularly suitable for employing the silver paste agent of hydrophobic solvent.
The internal friction angle of argentum powder 1 is less than 20 °, and is more than 100 ° with the contact angle of methanol 50 volume % aqueous solution.And then, the surface SP value that argentum powder 1 is measured by acetone titration is preferably less than 18.This argentum powder 1 by being made as low hydrophilic and optimizing sliding by the chemical property of powder surface, so that good with the compatibility of the solvent of silver paste agent, the such excipient of resin.It should be noted that argentum powder 1 is except primary particle, also comprise second particle and aggregation.Herein, as shown in (A) of Fig. 1, primary particle refers to single spherical silver particles 2, and as shown in (B) of Fig. 1, the Argent grain 2 that multiple primary particles are linked by welding, adhesion etc. is called second particle.As shown in (C) of Fig. 1, these primary particles, the material that the Argent grain 2 of second particle is assembled are called aggregation.
The scope that mean diameter is 0.1 μm ~ 1.5 μm of the preferred primary particle of argentum powder 1.Owing to the mean diameter of primary particle is more than 0.1 μm, it is possible to do not produce resistance when making silver paste agent (conductive paste) and make electric conductivity good.It addition, be less than 1.5 μm by making the mean diameter of primary particle, so that dispersibility will not worsen, will not producing flake silver powder time mixing, printing also becomes good.The mean diameter of primary particle can be passed through scanning electron microscope (SEM) observation and be measured.It addition, the granularity of argentum powder 1 is preferably 0.5 μm ~ 5 μm by the D50 (volume integrating 50% footpath) using laser diffraction and scattering method to measure, more preferably 1.0 μm ~ 4.0 μm.By making D50 be this scope, as silver paste agent with being preferred, internal friction angle is able to optimization, and the dispersibility in paste is improved.
The internal friction angle of argentum powder 1 indicates that the parameter of the slip easness of powder body, it is possible to be measured by commercially available powder layer shearing force determinator.When for argentum powder 1 of silver paste agent, when internal friction angle is more than 20 °, the slip between granule (in argentum powder 1 self-existent primary particle, second particle or aggregation) is deteriorated.Its result, when making paste, solvent, resin cannot be introduced into, between the granule of argentum powder 1, being only capable of the part on the surface of moistening argentum powder 1.In this state, even if being stirred, granule is also difficult to scatter each other, the bad dispersibility of argentum powder 1.For the argentum powder 1 of bad dispersibility, it is applied not only to moistening each element when making its scattered premix refining loss each other, and the argentum powder 1 being undertaken having assembled when leading mixing by triple-roller mill etc. is grinded up, and easily produce flake silver powder.Therefore, argentum powder 1 is less than 20 ° by making internal friction angle, makes slip become good, and solvent, resin enter between granule, and the compatibility becomes good, and therefore the dispersibility in silver paste agent becomes good.
It addition, the internal friction angle after just having manufactured of argentum powder 1 is 20 ° and the following is natural, it is preferred that even if internal friction angle is also maintained at less than 20 ° after fabrication, though with solvent, mixed with resin and also reach less than 20 ° when making paste.Such as, after manufacturing argentum powder 1, for instance even if at room temperature after 1 month, the internal friction angle of argentum powder 1 is also less than 20 °.Internal friction angle is the parameter changed with the gathering of granule, even just having manufactured the powder body that rear aggregation extent is low, due to intergranular gathering time dependent advance, internal friction angle also can become big sometimes.When the change of time dependent ground and internal friction angle are more than 20 °, the various problems such as dispersibility reduction, argentum powder 1 gathering can be caused when making paste.Thus, if being able to maintain that the internal friction angle of less than 20 °, then can suppress the propelling assembled, therefore, it is possible to go wrong when preventing from making paste.
Then, the contact angle for argentum powder 1 illustrates.The contact angle of argentum powder 1 and methanol 50 volume % aqueous solution is more than 100 °.Contact angle indicates that the surface parameter relative to the moistening easness of solvent of argentum powder 1, for instance, more big relative to the contact angle of water, then more easy by hydrophobic paste wet with solvent.On the contrary, more little relative to the contact angle of water, then more there is hydrophilic, be deteriorated relative to the moistening of hydrophobic paste solvent.The contact angle of argentum powder 1 generally measures on the surface shaped, and when using aquametry, for the powder body that hydrophobicity is big, water droplet is shaping in proper sphere shape on powder surface, and water droplet can slide, thus is difficult to critically measure.Therefore, implement in water, to add the low solvent of methanol isopolarity, reduce the method that the polarity of solvent is measured.When making silver paste agent, the generally hydrophobic solvent of many uses.Therefore, when argentum powder 1 has the contact angle hydrophilic surface less than 100 °, with the poor compatibility of the solvent of paste, resin, argentum powder 1 and solvent, resin will not produce moistening, it is difficult to make paste.It addition, mixing when making paste by force, dispersion stabilization is poor, easily produces the separation of paste because reassociating.
Then, the surface SP value for argentum powder 1 illustrates.The surface SP value of argentum powder 1 is less than 18.Surface SP value indicates that the parameter of the polarity on argentum powder 1 surface, more little, more has hydrophobicity, more big, more has hydrophilic.
This surface SP value can be measured with commercially available powder body wettability test instrument etc., it is also possible to being measured by acetone titration as described in " colorant, 62 (9) 524-528 " simply.In this acetone titration, water (A [ml]) adds hydrophobic powder body and makes it swim.While stir lentamente with agitator, limit measurement with test tube drip acetone until powder body moistening and settle needed for acetone dripping quantity (B [ml]).The SP value of water is 23.43, the SP value of acetone is 9.75, passes through the volume of water that uses and the volume of acetone that uses calculates the SP value of the acetone soln settled according to following formula 1, using this value surface SP value as argentum powder 1.
[mathematical expression 1]
When the surface SP value of argentum powder 1 is more than 18, hydrophilic is excessive, and with the compatibility poor of the solvent of paste, resin, argentum powder 1 and solvent, resin will not produce moistening, it becomes difficult to make paste.Even if it addition, mixing paste of making by force, dispersion stabilization is also poor, becomes easily to produce the separation of paste because reassociating.On the other hand, being less than 18 by making the surface SP value of argentum powder 1, the hydrophilic of argentum powder 1 will not become excessive, and the compatibility with solvent, resin becomes good, excellent dispersion, thus can be easily made paste.
For argentum powder 1; by the Argent grain 2 using wet-type reduction method to obtain is carried out surface treatment; organic coating layer 3 is formed as shown in Figure 1 on the surface of primary particle or second particle; can make above-mentioned internal friction angle is less than 20 °; and can to make the contact angle of argentum powder and methanol 50 volume % aqueous solution be more than 100 °, and then can also to make the surface SP value measured by acetone titration be less than 18.This organic coating layer 3 can be formed by surfactant or surfactant and dispersant.
Organic coating layer 3 is formed preferably by surfactant and dispersant.In argentum powder 1, by making SURFACTANT ADSORPTION in Argent grain 2 under ionized state, it is possible to suppress to assemble, when only suppressing to assemble with surfactant, addition can become too much.Therefore, even if silver paste agent is obtained in that good dispersity, sometimes wiring layer, electrode electric conductivity also insufficient.Thus, in order to suppress the gathering of argentum powder 1 and make wiring layer, electrode keep sufficient electric conductivity, combination to use surfactant and dispersant to be effective.
Particularly preferably organic coating layer 3 is formed as follows: by adding dispersant when Argent grain 2 absorption surface activating agent or after absorption surface activating agent, makes the surfactant being adsorbed in Argent grain 2 adsorb dispersant further and is formed.By making the surface of Argent grain 2 form organic coating layer 3 via SURFACTANT ADSORPTION dispersant, organic coating layer 3 can be made to be firmly adhered to the surface of Argent grain 2, it addition, become good with the compatibility of solvent, resin.Thus, even if argentum powder 1 and solvent, the mixed with resin of organic coating layer 3 will be identically formed with substantially with the surface of Argent grain 2, it is also possible to suppress the stripping of organic coating layer 3.
Such as, when argentum powder 1 being initiation material with silver chloride, as surfactant, it is preferred to use cation system surfactant.Cation system surfactant is not owing to being ionized as cation by the impact of pH, thus can obtain the effect improving the adsorptivity to argentum powder 1.
Cation system surfactant is not particularly limited, it is preferable that selected from the alkyl monoamine salt form being representative with monoalkyl amine salt；The alkyl diamine salt form being representative with N-alkyl (C14 ~ C18) propane diamine two oleate；The alkyl trimethyl ammonium salt type being representative with alkyl trimethyl ammonium chloride；The alkyl dimethyl benzyl ammonium salt type being representative with cocoalkyl dimethyl benzyl ammonium chloride；The quaternary being representative with alkyl two polyoxy ethylene methyl ammonium chloride；The tertiary amine-type being representative with alkyl pyridine salt form, stearyl dimethyl amine；The polyoxyethylene alkyl amine type being representative with polyoxypropylene polyoxyethylene alkylamine；With N, N ', N '-three (2-ethoxy)-N-alkyl (C14 ~ 18) 1,3-diaminopropanes is at least one in the oxygen ethylidene add-on type of the diamidogen of representative, more preferably quaternary, tertiary amine salt form any one or its mixture.
Cation system surfactant preferably have at least 1 be representative with methyl, butyl, cetyl, stearyl, Adeps Bovis seu Bubali, solidification Adeps Bovis seu Bubali, department of botany's stearyl, the alkyl of the carbon number with C4 ~ C36.It addition, as alkyl, it is preferable that addition has at least one in polyoxyethylene, polyoxypropylene, polyoxyethylene polyoxypropylene, polyacrylic acid, polycarboxylic acid.These alkyl are strong with the absorption of the fatty acid used as dispersant, thus when making Argent grain 2 via SURFACTANT ADSORPTION dispersant, it is possible to firmly absorbing fats acid.
Cation system surfactant is not particularly limited, it is preferred at least one in fluoride, bromide, iodide, chloride, sulfate, nitrate, phosphate.They contain usually used as the main constituent of surfactant, it is easy to obtain, thus preferably.
As dispersant, for instance the protecting colloids such as fatty acid, organic metal, gelatin can be used, if but consider not worry being mixed into impurity and with surfactant adsorption, then fatty acid or its salt are preferably used.It should be noted that fatty acid or its salt can also add in the form of an emulsion.
Fatty acid as dispersant is not particularly limited, it is preferred at least one in stearic acid, oleic acid, myristic acid, Palmic acid, linoleic acid, lauric acid, linolenic acid.This is because the boiling point of these fatty acids is relatively low, the harmful effect of the wiring layer using silver paste agent to be formed, electrode is few.It is believed that: fatty acid is originally used for hydrophobicity, by making the surface of Argent grain 2 via SURFACTANT ADSORPTION dispersant, and makes fatty acid be present in the exterior side of organic coating layer 3 in a large number, so that argentum powder 1 becomes have hydrophobicity.Especially, by select to be easily adsorbed at Argent grain 2, such as ionization be the surfactant with the electric charge of the electric charge reflexive on Argent grain 2 surface, it is possible to adsorb dispersant via surfactant fully, make argentum powder 1 show sufficient hydrophobicity.
The addition of surfactant is preferably with respect to the scope that Argent grain 2 is 0.002 mass % ~ 1.000 mass %.Surfactant is substantially all is adsorbed in Argent grain 2, and therefore the addition of surfactant is of substantially equal with adsorbance.When the addition of surfactant is less than 0.002 mass %, the effect sometimes cannot obtain the gathering suppressing Argent grain 2, improving the adsorptivity of dispersant.On the other hand, when addition is more than 1.000 mass %, use the wiring layer of silver paste agent formation, the electric conductivity of electrode reduces, thus not preferred.
The addition of dispersant is preferably with respect to the scope that Argent grain 2 is 0.01 mass % ~ 3.00 mass %, more preferably 0.01 mass % ~ 1.00 mass %.Dispersant adsorption is different because of the kind of dispersant in the amount of Argent grain 2, and when addition is less than 0.01 mass %, Argent grain 2 cannot adsorb the dispersant of the amount that can fully obtain the effect suppressing Argent grain 2 to assemble sometimes.On the other hand, when the addition of dispersant is more than 3.00 mass %, the dispersant being adsorbed in Argent grain 2 becomes many, sometimes uses the wiring layer of silver paste agent formation, electrode cannot obtain sufficient electric conductivity.
Argentum powder 1 is by using cation system surfactant, and makes surfactant that the adsorptivity of Argent grain 2 to be greatly improved, thus surfactant can be made firmly to be adsorbed in argentum powder 1.It may further be preferable that by making the surfactant being adsorbed in Argent grain 2 stably adsorb, it is possible to obtain suppress the argentum powder 1 of gathering and the excellent dispersion in paste further.
Then, for the manufacture method of the argentum powder 1 of the present invention, operation break-down illustrates.
For the manufacture method of argentum powder 1, for instance, as follows during using silver chloride as initiation material.First, carry out being generated the operation of Argent grain slurry by wet-type reduction method, described wet-type reduction method is: utilizes the silver complex solution that chelating agent dissolves the silver complex that silver chloride obtains to mix with reductant solution by comprising, is reduced by silver complex, make Argent grain 2 precipitate out.Generate in the operation of this Argent grain slurry, the process device of nitric acid system nitrogen in the past required using silver nitrate as the method for the initiation material retracting device of nitrous acid gas, waste water need not be set, and operation is also little on the impact of environment, the reduction of manufacturing cost therefore can be realized.
Specifically, generating in the operation of Argent grain slurry, first, use chelating agent to dissolve silver chloride, preparation comprises the silver complex solution of silver complex.Chelating agent is not particularly limited, it is preferred to use easy and silver chloride forms complex and the ammonia without the composition remained with the form of impurity.It addition, silver chloride is preferably used highly purified silver chloride.As this silver chloride, the industrial high-purity silver chloride stably manufacturing purity 99.9999 mass %.
Dissolving method as silver chloride, for instance when using ammonia as chelating agent, it is possible to the slurry first making silver chloride adds ammonia again, but improves productivity ratio to improve complex concentration, it is preferable that adds silver chloride in ammonia and dissolves.Can be industrial normally used ammonia for dissolving the ammonia of silver chloride, in order to prevent being mixed into of impurity, it is preferable that the ammonia that purity is high as far as possible.
Then, the preparation reductant solution for mixing with silver complex solution.As reducing agent, it is possible to use common hydrazine, formalin etc..The reduction of ascorbic acid is slow, makes the crystal grain in Argent grain 2 be prone to grow, thus particularly preferably.Hydrazine, formalin reducing power strong, therefore the crystal in Argent grain 2 easily diminishes.It addition, for the homogeneity or the response speed that control reaction, it is also possible to use after reducing agent pure water etc. being dissolved or diluting and make the aqueous solution that concentration is adjusted.
When carrying out reduction reaction, it is preferable that add water soluble polymer.The water soluble polymer added is not particularly limited, it is preferred at least one in Pluronic F-127, Polyethylene Glycol, polyvinyl alcohol or polyvinylpyrrolidone.Water soluble polymer makes Argent grain 2 be adsorbed in the surface of Argent grain 2 when precipitating out at reduction silver complex, plays the effect making the scattered dispersant of Argent grain 2 so that primary particle or the second particle of silver will not excessively be assembled.During without water soluble polymer, the core, the nucleus growth that sometimes produce because of the reduction of silver complex and excessive gathering can be there is in the Argent grain 2 that formed, cause bad dispersibility.When without water soluble polymer, although by reducing condition, the granularity of argentum powder 1 can be adjusted to the degree being preferred for silver paste agent, but by adding water soluble polymer, it is possible to adjust to the preferred granularity for silver paste agent.The addition of water soluble polymer suitably selects with the particle diameter of the argentum powder 1 to obtain according to the kind of water soluble polymer, it is preferable that relative to the scope that the silver contained in silver complex solution is 1 mass % ~ 10 mass %.By making the content of water soluble polymer be 1 mass % ~ 10 mass %; primary particle or the second particle that can make silver will not produce excessive gathering; and while adjusting the granularity of argentum powder 1, subsequent handling is properly formed on the surface of Argent grain 2 organic coating layer 3.
Water soluble polymer can add in silver complex solution and reductant solution or in any one.For adding water soluble polymer in silver complex solution and reductant solution or in any one, can be added in advance in the solution adding object before carrying out reduction treatment, it is also possible to add when being used for the mixing containing silver complex solution and reductant solution carrying out reduction treatment.More preferably mixing water soluble macromolecular in reductant solution in advance.This is authenticated by experiment result, it is believed that by being pre-mixed reductant solution and water soluble polymer, core produces or nucleus growth place exists water soluble polymer, water soluble polymer is promptly adsorbed on the core generated or the surface of Argent grain 2, such that it is able to suppress excessive gathering.It addition, the concentration of water soluble polymer is for more than 3 mass % and below 10 mass % when more preferably making mixing water soluble macromolecular in silver complex solution.Being added in advance by water soluble polymer containing time in silver complex solution, core produces or nucleus growth place is difficult to supply water soluble polymer, it is possible to the surface of Argent grain 2 cannot be made moderately to adsorb water soluble polymer, and therefore addition is more than 3 mass %.
When adding water soluble polymer, sometimes can foam during reduction reaction, therefore can add defoamer in silver complex solution or reducing agent mixed liquor.Defoamer is not particularly limited, the defoamer used during for generally reducing.Wherein, in order to not interfere with reduction reaction, the addition of defoamer is preferably set to be obtained in that the degree of the irreducible minimum of defoaming effect.
It should be noted that for the water used when preparing silver complex solution and reductant solution, in order to prevent being mixed into of impurity, it is preferred to use eliminate the water of impurity, it is particularly preferred to use pure water.
In the operation generating Argent grain slurry, the above-mentioned silver complex solution prepared is mixed with reductant solution, silver complex is reduced, makes Argent grain 2 be precipitated out by wet-type reduction method.This reduction reaction can use batch process to carry out, it is possible to use the continuous reduction of tubular reactor method (tubereactormethod), press over system (overflowmethod) etc carries out.It addition, the particle diameter of Argent grain 2 can be controlled by the reduction rate of silver complex solution with the mixing velocity of reductant solution, silver complex, it is possible to easily control as target grain size.It addition, with filter etc. by gained Argent grain slurries filtration, by Argent grain 2 solid-liquid separation.
In this operation, the surface adsorption of the Argent grain 2 of gained has substantial amounts of chloride ion and remaining water soluble polymer.Therefore, in order to the electric conductivity of the wiring layer of use silver paste agent formation, electrode is abundant, it is necessary to washed in ensuing washing procedure by the slurry of gained Argent grain 2, these surface adsorption things are removed by washing.
Washing methods is not particularly limited, it is common to use following method: the Argent grain 2 solid-liquid separation from slurry obtained is put in cleaning mixture, after using blender or ultrasonic washer stirring, again carries out solid-liquid separation, thus reclaiming Argent grain 2.It addition, in order to remove surface adsorption thing fully, it is preferable that repeat following operation aptly: put in cleaning mixture, agitator treating and solid-liquid separation.
Cleaning mixture can use water, in order to remove chlorine efficiently, it is possible to use the aqueous solution of alkali.Aqueous slkali is not particularly limited, it is preferred to use the sodium hydrate aqueous solution that the impurity of residual is few and cheap.When using sodium hydrate aqueous solution as cleaning mixture, it is generally desirable to, after washing with sodium hydrate aqueous solution, in order to remove sodium, Argent grain 2 or its slurry are washed with water further.
The concentration of the sodium hydrate aqueous solution for washing is preferably 0.01mol/l ~ 1mol/l.When the concentration of sodium hydrate aqueous solution is less than 0.01mol/l, clean result is insufficient, and during more than 1mol/l, Argent grain 2 can remain the sodium of more than allowance sometimes.It should be noted that the water for cleaning mixture is preferably the water not containing the impurity element that Argent grain 2 is harmful, it is particularly preferred to for pure water.
And then, carry out being formed the surface treatment procedure of organic coating layer 3 on the surface of Argent grain 2.In the surface treatment procedure to Argent grain 2, Argent grain 2 is processed with surfactant, process more preferably with surfactant and dispersant.As long as this surface treatment is before Argent grain 2 is dry, then can carry out in either phase, but when chlorine and water soluble polymer are removed completely, sometimes Argent grain 2 can be assembled, it is difficult in the surface treatment after removing chlorine and water soluble polymer and the surface of Argent grain 2 is carried out identical surface treatment, it is therefore preferable that while reduction or carry out after just reduction surface treatment, from Argent grain slurry by Argent grain 2 solid-liquid separation after carry out surface treatment or while washing procedure, carry out surface treatment before washing procedure.
In surface treatment procedure, for instance by from Argent grain slurry by Argent grain 2 solid-liquid separation after carry out surface treatment, it is possible to prevent the residual organic matter that caused by reducing agent etc. from suppressing the absorption of surfactant, dispersant, it is possible to be effectively taking place surface treatment.Thus, sufficient organic coating layer 3 is formed, it is ensured that the compatibility with solvent, resin etc. and dispersibility.
Additionally, when repeatedly repeating to wash, surface treatment can be carried out when arbitrary washing, preferably, surface treatment is carried out, for instance after carrying out more than 1 time washing, carry out surface treatment when the chlorine and remaining water soluble polymer that residue in Argent grain 2 being removed and not advancing to the gathering of the degree that surface treatment will not be impacted, Argent grain 2.
Such as, as the concrete grammar using the preferred surface of surfactant and dispersant to process, during surface treatment before washing, the Argent grain 2 solid-liquid separation from Argent grain slurry obtained is put in the water being added with surfactant and dispersant and stirs；Or it is added with in the water of surfactant and after stirring Argent grain 2 is put into, adds dispersant further and also stir.It addition, by adding surfactant and dispersant in cleaning mixture or adding dispersant again after adding surfactant simultaneously, it is possible to carry out washing and surface treatment simultaneously.In order to improve surfactant and the dispersant adsorptivity to Argent grain 2, it is preferable that after putting into Argent grain 2 in the water being added with surfactant or cleaning mixture and stirring, add dispersant further and stir.
It should be noted that the device that washing and the device that uses of surface treatment are usual washing, surface treatment to be used, for instance the reactive tank etc. with blender can be used.
Then, carry out reclaiming the recovery process of the Argent grain 2 that surface defines organic coating layer 3.This recovery process, after having carried out surface treatment and washing, carries out solid-liquid separation cash register granule 2 back and forth.The device that solid-liquid separation uses is normally used device, for instance can use centrifuge, suction filtration machine, pressure filter etc..
Then, washing and after surface treatment terminates, carry out making solid-liquid separation and drying process that the moisture of Argent grain 2 that obtains evaporates and dries.As drying means, for instance, the Argent grain 2 reclaimed after washing and surface treatment being terminated is placed on rustless steel pad, uses the drying device that dried-air drier or vacuum drier etc. are commercially available, is heated with the temperature of 40 DEG C ~ 80 DEG C.
Then, with will not the degree of organic coating layer 3 that formed of injured surface, very weak energy dried Argent grain 2 is crushed to the preferred size for silver paste agent, carry out for staged care broken-classification operation, it is hereby achieved that argentum powder 1.As long as breaking method is the degree not damaging organic coating layer 3, just it is not particularly limited, it is preferred to use the device that the crushing force such as airflow milling, homogenizer is weak.The device that crushing force is strong not only can damage organic coating layer 3, and argentum powder 1 also can be made to deform, thus not preferred.Grading plant is not particularly limited, it is possible to use airflow classification machine, sieve etc..
Break process is to instigate the operation of state that dried gathering powder is shattered into the primary particle before surface treatment or second particle.As broken means, it is possible to use various broken means such as ball mill, conflict formula airflow destructor, impact type destructor, cartridge type homogenizers.When broken energy is crossed weak, it is impossible to scatter aggregation fully that generate in wet processed, in dry run, it is impossible to making internal friction angle is less than 20 °.On the other hand, when broken energy is crossed strong, organic coating layer 3 on the surface of argentum powder 1 can be damaged, or make the part that the primary particle in second particle is bonded to each other be damaged, thus because the new dough of argent is exposed on the surface of argentum powder 1 again, the surface SP value cause big and methanol 50 volume % aqueous solution the contact angle of hydrophilic change on surface to become less than 100 °, utilizing acetone titration to measure is more than 18.And then, there is also the new surface exposed becomes avtive spot and reassociates in keeping, becomes big possibility with making internal friction angle time dependent.
Therefore, when no matter using any breaking treatment machine, it is required for limit and confirms that the such parameter limit of internal friction angle, contact angle, surface SP value adjusts broken condition, and the break process of the degree of organic coating layer 3 on argentum powder 1 surface while being applied to the destruction of joint portion suppressing primary particle to be bonded to each other, will not be damaged, organic coating layer 3 namely will not be made to peel off and expose the break process of Argent grain 2.The broken condition state etc. according to the size of breaker, made argentum powder 1, suitably determines the rotating speed of breaker, broken time, temperature etc..
Such as, when using homogenizer, broken condition is different because of the capacity of blender, the input amount according to Argent grain 2, adjusts peripheral speed and the mixing time etc. of blender in the way of not damaging organic coating layer 3.As broken condition when employing homogenizer, for instance be preferably: peripheral speed is 10m/ second ~ 40m/ second, the broken time is 10 minutes ~ about 60 minutes.
It should be noted that after break process, in order to remove the block argentum powder aggregation generating in Argent grain slurry generation process, broken-classification operation or being mixed into, it is preferable that carry out the staged care of air-flowing type or sieve formula etc..
In the manufacture method of above-mentioned argentum powder 1, after the surface of the Argent grain 2 obtained by Argent grain slurry generation process forms organic coating layer 3, broken by what carry out Argent grain 2 suppressing the new dough of argent to regenerate, can obtain internal friction angle is less than 20 °, and with the low hydrophilic argentum powder 1 that contact angle is more than 100 ° of methanol 50 volume % aqueous solution.And then, the surface SP value measured by acetone titration of this argentum powder 1 is less than 18.Thus, in this manufacture method, owing to the internal friction angle of argentum powder 1 is less than 20 °, and be more than 100 ° with the contact angle of methanol 50 volume % aqueous solution, excellent with the wettability of the solvent of silver paste agent, resin etc., thus favorable dispersibility, it is possible to it is easily made paste, makes silver paste agent.
Additionally, the argentum powder 1 manufactured by this manufacture method is owing to having carried out sufficient surface treatment, even if therefore not only mix with the resin of silver paste agent, solvent after just having manufactured, its internal friction angle is also less than 20 °, thus, even if when manufactured mix with solvent more in a moment, the compatibility with solvent, resin etc. is also good, excellent dispersion, therefore can be easily made paste.
Therefore, above-mentioned argentum powder 1 owing to disperseing equably in silver paste agent, thus electrical connection can be made to become good when forming wiring layer, electrode with silver paste agent.
Embodiment
Hereinafter, illustrate for the specific embodiment being suitable for the present invention, but the present invention is not limited to these embodiments.
< embodiment 1 >
In embodiment 1, first, in the 25 mass % ammonia 36L remained in the temperature bath of 38 DEG C by temperature of liquid 36 DEG C, put into 2490g silver chloride (Sumitomo Metal Mining Co., Ltd's system) while stirring, make silver complex solution, in temperature is bathed, remain 36 DEG C.
On the other hand, the ascorbic acid 1318g (Kanto Kagaku K. K.'s system, reagent) as reducing agent is dissolved in the pure water 10L of 36 DEG C, makes reductant solution.
Then, it is taken as the polyvinyl alcohol 187.5g (KurarayCo. for water soluble polymer, Ltd. system, PVA205, be 10.0 mass % relative to Argent grain), be dissolved in the pure water 4.6L of 36 DEG C and make solution, this solution is mixed in above-mentioned reductant solution.
Then, use Mono pump (mono-pump) (Hyoao Equipment Co., Ltd.'s system) above-mentioned silver complex solution and reductant solution to be inputted to groove with the speed of 2.44L/ minute and 0.90L/ minute respectively, silver complex is reduced.Reduction rate now is calculated as 127g/ minute with silver amount.It should be noted that above-mentioned groove employs the vinyl chloride rider of internal diameter 25mm and length 725mm.The slurry comprising the Argent grain obtained by the reduction of silver complex is accommodated in holding tank while stirring.After storage terminates, persistently stir 60 minutes in holding tank.Above-mentioned Argent grain slurry after utilizing pressure filter that stirring is terminated is filtered, by Argent grain solid-liquid separation.
Then, the Argent grain of solid-liquid separation is carried out surface treatment.As surface conditioning agent, the polyoxyethylene addition quaternary ammonium salt 0.90g that belongs to cation system surfactant by commercially available (CrodaJapanK.K. system, trade name Silasol, be 0.048 mass % relative to Argent grain) and belong in the stearic acid late 16.87g (Zhong jing oils and fats Co., Ltd. system, SELOSOL920, be 0.90 mass % relative to Argent grain) of the dispersant pure water putting into 20L, it is stirred, thus the surface of Argent grain is carried out surface treatment.Hereafter, add NaOH until concentration reaches 0.05mol/L, stir 15 minutes and wash, being then filtered with pressure filter, reclaim Argent grain.
Then, before the Argent grain of recovery is dried, Argent grain is put in the NaOH aqueous solution of 0.05mol/L, stir 15 minutes and wash, be then filtered with pressure filter and reclaim.Thereafter, by this washing operation with based on the solid-liquid separation operation repetition filtered 3 times.
The Argent grain of solid-liquid separation is put in the pure water of 20L, stir and after filtering, Argent grain be transferred on rustless steel pad, drying 10 hours with 60 DEG C with vacuum drier.
After drying, broken and classification are carried out.Crush and be carried out as follows: take the dried Argent grain of 1.5kg, put into the homogenizer (NIPPONCOKE&ENGINEERINGCO. of 5L, LTD. FM5C/I processed) in, make rotating vane rotate 30 minutes with the peripheral speed of 15m/ second, carry out break process.And then, use airflow classification machine (Nippon Mining Co., Ltd.'s EJ-3 type), with the classification point of 7 μm, the Argent grain staged care after broken is obtained argentum powder.The mean diameter of the primary particle that gained argentum powder is observed by SEM and obtained is 0.98 μm, and using the granularity (D50) that laser diffraction and scattering method measures is 2.35 μm.
Operate as above, obtain the argentum powder of embodiment 1.Measure the internal friction angle of gained argentum powder, contact angle, surface SP value.
The mensuration of internal friction angle uses powder layer shearing force determinator (NanoseedsCorporation NS-S300 type).At normal temperatures, after 18g argentum powder is filled into the SUS cell of internal diameter 15mm, the setting value collapsing load is set to 20N, and applies load with the speed that collapses of 0.2mm/ second.Arrive after setting load, started to slide laterally with the speed of 10 μm/second after 100 seconds.It should be noted that sampling frequency is 10Hz.Value that load obtains is collapsed divided by the sectional area of cell as vertical stress σ (N/cm when sliding laterally using starting2), the value obtained divided by the sectional area of cell by the maximum of the shearing force measured after sliding laterally is as shear stress τ (N/cm2)。
Then, the setting value collapsing load is set as 40N, similarly measures vertical stress σ and shear stress τ.And then, the setting value collapsing load is set as 60N, similarly measures vertical stress σ and shear stress τ.The vertical stress σ obtained when with above three is transverse axis, marks and draws with shear stress τ for the longitudinal axis, and the slope (degree) of the near linear using method of least square to obtain is set to internal friction angle.
It it is 7.1 ° by the internal friction angle of the argentum powder of the embodiment 1 of above method mensuration.After this argentum powder at room temperature places 1 month, carrying out the mensuration of internal friction angle by method similar to the above, result is 7.8 °.
Contact angle determination device (consonance interface science Co., Ltd. CA-X150) is used to carry out with the mensuration of the contact angle of methanol 50 volume % aqueous solution.At normal temperatures, with the load of about 1MPa by argentum powder press molding, the tabular test body that argentum powder is filled by densification is obtained.Measure the contact angle that this test body is formed with methanol 50 volume % aqueous solution.It it is 110 ° with the contact angle of the argentum powder of the embodiment 1 of the method mensuration.
Being determined as follows of surface SP value based on acetone titration carries out.In 0.5g argentum powder add 50ml water, while be slowly stirred, while drip acetone in the water be added with argentum powder continuously, with swim in the water surface Argent grain disperse and solution bleach turbid time for terminal.Using the surface SP value surface SP as argentum powder adding the aqueous acetone solution that volume calculates of acetone time thus.It is 16.7 by the surface SP value of the Argent grain of the embodiment 1 of the method mensuration.
Then, use gained argentum powder is made paste to be evaluated.About the evaluation making paste, first, in the capsule of stainless steel, weigh the excipient 0.8g that weight ratio is 1:7 of 9.2g argentum powder, epoxy resin (Mitsubishi chemical Co., Ltd's system, JER819) and terpineol.Now, the surface of argentum powder because of excipient rapid moistening be can be observed.Then, when using metallicity scraper to be mixed, mixing, dispersion easily advance, it is possible to make paste-like.And then, use mixing for this paste 5 minutes from revolution type mixing roll (THINKYCORPORATION ARE-250 type) with the speed of 2000rpm, obtain homogeneous silver paste agent.Using fineness gauge to evaluate the dispersibility of gained silver paste agent, maximum particle diameter Dmax is little of 7 μm, the dispersibility that display is excellent.
< embodiment 2 >
In embodiment 2, the amount of polyvinyl alcohol is set to 75g (being 4.00 mass % relative to Argent grain), the rotating vane making homogenizer rotates with the peripheral speed of 28m/ second, in addition, obtains argentum powder by method similarly to Example 1 and is evaluated.The mean diameter of the primary particle of gained argentum powder is 1.01 μm, and granularity (D50) is 2.73 μm.
The internal friction angle of the argentum powder of embodiment 2 is 10.4 °, and the internal friction angle after at room temperature placing 1 month is 10.6 °.It addition, the contact angle of the argentum powder of embodiment 2 is 109 °, surface SP value is 17.4.
Then, gained argentum powder is used to carry out the evaluation making paste similarly to Example 1.The surface of argentum powder because of excipient promptly moistening be can be observed.When using metallicity scraper to be mixed, mixing, dispersion easily advance, it is possible to make paste-like.And then, by this paste similarly to Example 1 with mixing from revolution type mixing roll, obtain homogeneous silver paste agent.Using fineness gauge to evaluate the dispersibility of gained silver paste agent, maximum particle diameter Dmax is little of 6 μm, the dispersibility that display is excellent.
< comparative example 1 >
In comparative example 1, except making the rotating vane of homogenizer rotate with the peripheral speed of 42m/ second, obtain argentum powder by method similarly to Example 1 and be evaluated.The mean diameter of the primary particle of gained argentum powder is 0.99 μm, and granularity (D50) is 1.82 μm.It addition, the internal friction angle of the argentum powder of comparative example 1 is 20.8 °, than embodiment high a lot.It addition, the contact angle of the argentum powder of comparative example 1 is 85 °, surface SP value is 18.7.
Then, gained argentum powder is used to carry out the evaluation making paste similarly to Example 1.Substantially do not observe surface moistening because of excipient of argentum powder.It addition, when using metallicity scraper that it is stirred, only become big argillaceous, it is impossible to make paste-like.And then, by this paste similarly to Example 1 with mixing from revolution type mixing roll, make paste-like.Use fineness gauge evaluate gained silver paste agent dispersibility, maximum particle diameter Dmax greatly to 20 μm, bad dispersibility.
< comparative example 2 >
In comparative example 2, except making the rotating vane of homogenizer rotate with the peripheral speed of 7m/ second, obtain argentum powder by method similarly to Example 2 and be evaluated.The mean diameter of the primary particle of gained argentum powder is 1.00 μm, and granularity (D50) is 3.52 μm.It addition, the internal friction angle of the argentum powder of comparative example 2 is 25.8 °, than embodiment high a lot.It addition, the contact angle of the argentum powder of comparative example 2 is 110 °, surface SP value is 17.4 °.
Then, gained argentum powder is used to carry out the evaluation making paste similarly to Example 1.Substantially do not observe surface moistening because of excipient of argentum powder.It addition, when using metallicity scraper that it is stirred, only become the argillaceous of bulk, it is impossible to make paste-like.And then, by this paste similarly to Example 1 with mixing from revolution type mixing roll, make paste-like.Use fineness gauge evaluate gained silver paste agent dispersibility, maximum particle diameter Dmax greatly to 18 μm, bad dispersibility.
Based on above embodiments and comparative example, even by the argentum powder that same procedure makes, compared with comparative example, the degree of the overlay film that the surface will not damage argentum powder is formed has been sufficiently carried out in broken embodiment 1 and embodiment 2, internal friction angle is less than 20 °, and be more than 100 ° with the contact angle of methanol 50 volume % aqueous solution, the compatibility with excipient is good, it is possible to obtain the argentum powder of excellent dispersion.It addition, in embodiment 1 and embodiment 2, the surface SP value measured by acetone titration further is less than 18.And then, embodiment 1 and in embodiment 2, even if after at room temperature argentum powder is placed 1 month, internal friction angle is also less than 20 °, and gathering is suppressed.
On the other hand, in comparative example 1, broken condition is excessively strong, and organic coating layer that the surface of argentum powder is formed is impaired, and internal friction angle is more than 20 °, and contact angle is again smaller than 100 °.And then, surface SP value is also greater than 18.It addition, in comparative example 2, broken condition is weak, it is impossible to aggregation is scattered fully, thus internal friction angle is 25.8 °, becomes very large.Thus, comparative example 1 and in comparative example 2, with the poor compatibility of excipient, the bad dispersibility of argentum powder.
Claims (4)
1. an argentum powder, it is characterized in that, internal friction angle is less than 20 °, and be more than 100 ° with the contact angle of methanol 50 volume % aqueous solution, wherein said argentum powder has the organic coating layer formed by surfactant and dispersant, wherein said surfactant is cation system surfactant, and described dispersant is fatty acid or its salt.
2. argentum powder according to claim 1, it is characterised in that its surface SP value measured by acetone titration is less than 18.
3. the argentum powder according to claim 1 or claim 2, it is characterised in that described internal friction angle when mixing with the solvent of silver slurry is less than 20 °.
4. the manufacture method of an argentum powder, it is characterized in that, with surfactant, the Argent grain using the synthesis of wet-type reduction method is carried out surface treatment, and carry out surface treatment with dispersant while surfactants based surface treatment or after processing, after Argent grain surface forms organic coating layer, use homogenizer, break process is carried out when the peripheral speed of stirring vane is more than 10m/ second and less than 40m/ second, manufacturing internal friction angle is less than 20 ° and the argentum powder that contact angle is more than 100 ° with methanol 50 volume % aqueous solution, wherein said surfactant is cation system surfactant, described dispersant is fatty acid or its salt.
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| PCT/JP2012/065411 WO2012173245A1 (en) | 2011-06-16 | 2012-06-15 | Silver powder and method for producing same |
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| JP6404553B2 (en) * | 2013-10-03 | 2018-10-10 | 住友金属鉱山株式会社 | Silver solution management method and silver powder production method |
| JP6404554B2 (en) * | 2013-10-03 | 2018-10-10 | 住友金属鉱山株式会社 | Silver powder manufacturing method |
| JP6201875B2 (en) * | 2014-04-22 | 2017-09-27 | 住友金属鉱山株式会社 | Silver powder and method for producing the same |
| CN104128616B (en) * | 2014-08-12 | 2016-03-23 | 苏州思美特表面材料科技有限公司 | A kind of preparation method of metal dust |
| JP2016108649A (en) * | 2014-11-26 | 2016-06-20 | 住友金属鉱山株式会社 | Silver-coated copper powder and method of producing the same |
| CN112296351B (en) * | 2020-09-29 | 2022-12-20 | 湖南中伟新银材料科技有限公司 | Preparation method of high-tap-density ultrafine silver powder |
| CN114226745B (en) * | 2021-12-10 | 2024-03-22 | 江西贝特利新材料有限公司 | Method for cleaning micron-sized flake silver powder |
| CN115519129B (en) * | 2022-08-05 | 2023-04-18 | 南通领跑者新材料科技有限公司 | Preparation method of silver powder for conductive paste |
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