CN103079730A - Silver powder and method for producing same - Google Patents
Silver powder and method for producing same Download PDFInfo
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- CN103079730A CN103079730A CN2012800027041A CN201280002704A CN103079730A CN 103079730 A CN103079730 A CN 103079730A CN 2012800027041 A CN2012800027041 A CN 2012800027041A CN 201280002704 A CN201280002704 A CN 201280002704A CN 103079730 A CN103079730 A CN 103079730A
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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
- 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
- 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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- General Chemical & Material Sciences (AREA)
- Powder Metallurgy (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
In order to provide a silver powder which has excellent compatibility with a solvent, a resin, etc. in a silver paste, and excellent dispersibility, and a method for producing the same, a silver powder according to the invention has an organic coating layer formed on the surface thereof and has an internal friction angle of 20 DEG or less and a contact angle with an aqueous solution of 50 vol% methanol of 100 DEG or more, and a method for producing a silver powder according to the invention comprises performing a surface treatment of silver particles, thereby forming an organic coating layer on the surfaces thereof, and thereafter, performing a sufficient crushing treatment to such an extent that the organic coating layer is not damaged.
Description
Technical field
The present invention relates to silver powder and manufacture method thereof, more specifically, relate to silver powder and manufacture method thereof as the principal component of silver-colored paste (silver paste), this silver paste is used to form wiring layer, electrode of electronic instrument etc.
The application is based on advocating priority at the Japanese patent application No. Patent 2011-134337 of Japanese publication on June 16th, 2011, with reference to these applications, and it quoted to the application.
Background technology
The silver-colored paste of resin type silver paste, calcinated type silver paste and so on is used in the formation of the wiring layer in the electronic instrument, electrode etc. more.By these silver-colored pastes are coated with or are printed on the various base materials, then be heating and curing or heating and calcining, can form the conducting film that becomes wiring layer, electrode etc.
For example, resin type silver paste is comprised of silver powder, resin, curing agent, solvent etc., and it is printed on electric conductor circuit pattern or the terminal, is heating and curing with 100 ℃ ~ 200 ℃ and makes conducting film, thereby form wiring layer, electrode.
In addition, calcinated type silver paste is comprised of silver powder, glass, solvent etc., and it is printed on electric conductor circuit pattern or the terminal, is heated to 600 ℃ ~ 800 ℃ and calcining and makes conducting film, thereby form wiring layer, electrode.
In the wiring layer that forms with these silver-colored pastes, the electrode, form the current path of electrical connection by the connection of silver powder.
The particle diameter of the employed silver powder of these silver-colored pastes is 0.1 μ m～number μ m, and the particle diameter of employed silver powder is different because of the thickness of the wiring layer that will form, thickness of electrode etc.In addition, be evenly dispersed in the silver-colored paste by making silver powder, can form the wiring layer of even thickness, the electrode of even thickness.
Usually, make in the method for silver-colored paste, measure each inscape and put into the container of regulation, use omnipotent agitator, kneader etc. carry out pre-mixing after, lead mixing with triple-roller mill etc.In pre-mixing, wetting fully each other to make its dispersion be important with each inscape, mixing in advance by carrying out fully this, can prevent main mixing middle generation silver foil, make the granularity of the silver powder in the silver-colored paste be down to rapidly targeted particle size, silver powder is dispersed in the silver-colored paste equably.
Therefore, to the most silver powder that accounts for weight in the silver-colored paste not only require uniform particle diameter and assemble few, also require the affinity of the excipient that formed by solvent, resin etc. good, the such characteristic of dispersed height in silver-colored paste.This specific character also changes along with the chemical property on the such silver powder surface of slip easness, hydrophily, the hydrophobicity of powder surface not only along with the character of the such powder structure aspect of bulk density, size distribution and change.
For the employed silver powder of silver-colored paste, for example in patent documentation 1, put down in writing: because ball shape silver powder has specific bulk density and formed body density, thereby good with the compatibility of excipient or resin.Yet, there is no the relevant record of surface chemical property in the patent documentation 1, only the difficult parameters by this configuration aspects is to control the compatibility of itself and excipient, resin.In addition, in the patent documentation 1 for the manufacture method of silver powder, for having the manufacture methods such as breaking method of the silver powder of considerable influence to there is no record to above-mentioned surface chemical property.
On the other hand, put down in writing in the patent documentation 2: with the ratio D50/DIA of the D50 value that obtains by particle size distribution and the particle diameter DIA that obtains by the graphical analysis benchmark as the powder concentration class, if this ratio is below the particular value, then be low aggregation.Really, can think that the quantity of the aggregation in the little then powder of this value is few.Yet patent documentation 2 is same with patent documentation 1, the relevant record of the silver powder surface chemical property of when there is no impact and making paste and compatibility excipient, resin, affects the relevant record of the manufacture method of chemical property.
For the silver powder that uses in the silver-colored paste, as patent documentation 1, patent documentation 2, only by the character of the configuration aspects such as bulk density, formed body density, powder concentration class, can't optimize fully compatibility, dispersiveness with the solvent of silver-colored paste, resin etc.Therefore, silver powder is required compatibility and dispersed further lifting.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2006-097086 communique
Patent documentation 2: TOHKEMY 2004-100013 communique
Summary of the invention
The problem that invention will solve
Thereby, the object of the invention is to, in view of above-mentioned existing situation, provide a kind of compatibility of solvent, resin etc. of and silver-colored paste and silver powder and the manufacture method thereof of excellent dispersion.
For the scheme of dealing with problems
The silver powder of the present invention of realizing above-mentioned purpose is characterised in that, internal friction angle is below 20 °, and with the contact angle of the methyl alcohol 50 volume % aqueous solution be more than 100 °.
The manufacture method that realizes the silver powder of the present invention of above-mentioned purpose is characterised in that, by silver-colored particle is carried out surface treatment and after the surface forms organic coating layer, carries out sufficient break process under the degree of not damaging organic coating layer.
The effect of invention
Among the present invention, the internal friction angle of silver powder is below 20 °, and with the contact angle of the methyl alcohol 50 volume % aqueous solution be more than 100 °, thereby, excellent dispersion high with the compatibility of solvent, resin etc., can easily make paste.Thus, among the present invention, can improve quality and the productivity ratio of silver-colored paste.
Description of drawings
Fig. 1 is the model utility schematic diagram for silver-colored particle shape and particle surface state.
The specific embodiment
Below, be elaborated for the manufacture method that is suitable for silver powder of the present invention and silver powder.Need to prove, the present invention is not limited to following detailed description in the situation that be not particularly limited.
Silver powder 1 shown in Figure 1 is included in the resin type silver paste that is made of curing agent, resin, solvent etc., or in the calcinated type silver paste that is consisted of by glass, solvent etc.The resin type silver paste, the calcinated type silver paste that contain silver powder 1 are used to form wiring layer, electrode.Therefore, silver powder 1 is electrically connected in order to realize, need to be good with the compatibility of the solvent of silver-colored paste, resin, and be dispersed in the paste equably.Silver powder 1 has been particularly suitable for using the silver-colored paste of hydrophobic solvent.
The internal friction angle of silver powder 1 is below 20 °, and with the contact angle of the methyl alcohol 50 volume % aqueous solution be more than 100 °.And then the surperficial SP value that silver powder 1 is measured by acetone titration is preferably below 18.This silver powder 1 is made as low hydrophily and optimizes sliding by the chemical property with powder surface, thereby makes with the compatibility of the such excipient of solvent, the resin of silver-colored paste good.Need to prove, silver powder 1 also comprises second particle and aggregation except primary particle.Herein, like that, primary particle refers to single spherical silver particles 2 shown in Fig. 1 (A), and like that, a plurality of primary particles are called second particle by the silver-colored particle 2 that welding, adhesion etc. links shown in Fig. 1 (B).Like that, the silver-colored particle 2 of these primary particles, second particle is assembled the material that forms and is called aggregation shown in Fig. 1 (C).
The average grain diameter of silver powder 1 preferred primary particle is the scope of 0.1 μ m ~ 1.5 μ m.Because the average grain diameter of primary particle is more than the 0.1 μ m, can when making silver-colored paste (conductive paste), have a resistance and make electric conductivity good.In addition, be below the 1.5 μ m by the average grain diameter that makes primary particle, thereby dispersiveness can not worsened, can not produce flake silver powder when mixing, it is good that printing also becomes.The average grain diameter of primary particle can be observed by scanning electron microscope (SEM) and be measured.In addition, the granularity of silver powder 1 is preferably 0.5 μ m ~ 5 μ m, more preferably 1.0 μ m ~ 4.0 μ m by the D50 that uses the laser diffraction and scattering method to measure (volume integrating 50% footpath).Be this scope by making D50, with being preferred, internal friction angle is able to optimization as silver-colored paste, and the dispersiveness in the paste is improved.
The internal friction angle of silver powder 1 is the parameter of the slip easness of expression powder, can measure by commercially available powder layer shearing force determinator.In the situation of the silver powder 1 that is used for silver-colored paste, when internal friction angle surpasses 20 °, the slip variation between particle (self-existent primary particle, second particle or aggregation in the silver powder 1).Its result, when making paste, solvent, resin can't enter between the particle of silver powder 1, the part on surface that only can wetting silver powder 1.In this state, even stir, particle also is difficult to scatter the bad dispersibility of silver powder 1 each other.For the silver powder 1 of bad dispersibility, not only be used for wetting each inscape and make each other the pre-mixing consuming time of its dispersion, and lead the silver powder 1 of having assembled when mixing by triple-roller mill etc. and pulverized, and easily produce flake silver powder.Therefore, silver powder 1 is below 20 ° by making internal friction angle, and making slides becomes good, and solvent, resin enter between the particle, and compatibility becomes well, and therefore the dispersiveness in the silver-colored paste becomes good.
In addition, the internal friction angle after the firm manufacturing of silver powder 1 is finished is to be natural below 20 °, preferably, even also maintain below 20 ° in internal friction angle after the manufacturing, even with solvent, mixed with resin and also reach below 20 ° when making paste.For example, after making silver powder 1, even for example at room temperature through after 1 month, the internal friction angle of silver powder 1 also is below 20 °.Internal friction angle is Varying parameters with the gathering of particle, even the low powder of aggregation extent after just manufacturing has been finished, because intergranular gathering time dependent ground advances, it is large that internal friction angle also can become sometimes.Time dependent ground changes and internal friction angle when surpassing 20 °, can cause the variety of issues such as dispersed reduction, silver powder 1 gathering when making paste.Thereby if can keep internal friction angle below 20 °, the propelling that then can suppress to assemble goes wrong in the time of therefore can preventing from making paste.
Then, the contact angle for silver powder 1 describes.Silver powder 1 is more than 100 ° with the contact angle of the methyl alcohol 50 volume % aqueous solution.Contact angle is to represent the surface of silver powder 1 with respect to the parameter of the wetting easness of solvent, and is for example larger with respect to the contact angle of water, then easier of hydrophobic paste wet with solvent.On the contrary, less with respect to the contact angle of water, then more have hydrophily, with respect to the wetting variation of hydrophobic paste solvent.The contact angle of silver powder 1 is measured on the surface that has been shaped usually, and when using aquametry, for the large powder of hydrophobicity, water droplet is proper sphere shape at the shaping powder surface, and water droplet can slide, thereby is difficult to critically measure.Therefore, the polarity that implement to add the low solvent of methyl alcohol isopolarity in water, reduces solvent is carried out method for measuring.When making silver-colored paste, usually use hydrophobic solvent more.Therefore, silver powder 1 has hydrophilic when surface of 100 ° of contact angle less thaies, and is poor with the compatibility of the solvent of paste, resin, and it is wetting that silver powder 1 and solvent, resin can not produce, and is difficult to make paste.In addition, mixing when making paste by force, dispersion stabilization is poor, easily produces the separation of paste because reassociating.
Then, the surperficial SP value for silver powder 1 describes.The surperficial SP value of silver powder 1 is below 18.Surface SP value is the parameter that represents the polarity on silver powder 1 surface, littlely then more has a hydrophobicity, then more has a hydrophily greatlyr.
The enough commercially available powder wettability test instrument of this surface SP value energy etc. are measured, and the acetone titration that passes through that also can put down in writing such as " colorant, 62 (9) 524-528 " is simply measured.In this acetone titration, in water (A[ml]), add hydrophobic powder and it is swum.Stir lentamente with agitator on the limit, the limit instrumentation drips acetone with test tube until the acetone dripping quantity that powder is wetting and sedimentation is required (B[ml]).The SP value of water is 23.43, the SP value of acetone is 9.75, and the volume by employed water and the volume of employed acetone calculate the SP value of the acetone soln of sedimentation according to following formula 1, with the surperficial SP value of this value as silver powder 1.
[mathematical expression 1]
The surperficial SP value of silver powder 1 was greater than 18 o'clock, and hydrophily is excessive, and with the solvent of paste, the compatibility variation of resin, silver powder 1 and solvent, resin can not produce wetting, and becoming is difficult to make paste.In addition, even the mixing paste of making by force, dispersion stabilization is also poor, becomes and easily produces the separation of paste because reassociating.On the other hand, be below 18 by the surperficial SP value that makes silver powder 1, it is excessive that the hydrophily of silver powder 1 can not become, become well with the compatibility of solvent, resin, excellent dispersion, thereby be easy to make paste.
For silver powder 1; by the silver-colored particle 2 that uses the wet type reducing process to obtain is carried out surface treatment; form as shown in Figure 1 organic coating layer 3 on the surface of primary particle or second particle; can make above-mentioned internal friction angle is below 20 °; and can make the contact angle of silver powder and the methyl alcohol 50 volume % aqueous solution is more than 100 °, and then can also to make the surperficial SP value of measuring by acetone titration be below 18.This organic coating layer 3 can form by surfactant or surfactant and dispersant.
Organic coating layer 3 preferably forms by surfactant and dispersant.In the silver powder 1, by making SURFACTANT ADSORPTION in silver-colored particle 2 under ionized state, can suppress to assemble, when only suppressing to assemble with surfactant, it is too much that addition can become.Therefore, namely allow to obtain good dispersity in the silver-colored paste, the electric conductivity of wiring layer, electrode is also insufficient sometimes.Thereby for the gathering that suppresses silver powder 1 and make wiring layer, electrode keep sufficient electric conductivity, it is effective being used in combination surfactant and dispersant.
Particularly preferably organic coating layer 3 following formation: by when the silver-colored particle 2 absorption surface activating agent or after the absorption surface activating agent, adding dispersant, make the surfactant that is adsorbed in silver-colored particle 2 further adsorb dispersant and form.Being situated between by the surface that makes silver-colored particle 2 forms organic coating layer 3 by the SURFACTANT ADSORPTION dispersant, can make organic coating layer 3 firmly be attached to the surface of silver-colored particle 2, in addition, becomes good with the compatibility of solvent, resin.Thus, even will substantially similarly be formed with the surface of silver-colored particle 2 silver powder 1 and solvent, mixed with resin of organic coating layer 3, also can suppress peeling off of organic coating layer 3.
For example, in the situation of the silver powder 1 take silver chlorate as initiation material, as surfactant, preferably using cation is surfactant.Cation is surfactant owing to not being subjected to the impact ground ionization of pH to be cation, thereby can be improved to the effect of the adsorptivity of silver powder 1.
Cation is that surfactant is not particularly limited, and is preferably selected from the alkyl monoamine salt type take the monoalkyl amine salt as representative; (propane diamine two oleates of C14 ~ C18) are as the alkyl diamine salt type of representative take the N-alkyl; Alkyl trimethyl ammonium salt type take alkyl trimethyl ammonium chloride as representative; Alkyl dimethyl benzyl ammonium salt type take the coconut zephiran as representative; Quaternary take alkyl two polyoxy ethene ammonio methacrylates as representative; Tertiary amine-type take Fixanol type, stearyl dimethyl amine as representative; Polyoxyethylene alkyl amine type take polyoxypropylene-polyoxyethylene alkyl amine as representative; With N, N ', N '-three (2-ethoxy)-N-alkyl (C14 ~ 18) 1,3-diaminopropanes are at least a kind in the oxygen ethylidene add-on type of diamines of representative, more preferably any or its mixture of quaternary, tertiary ammonium salt type.
Cation is that surfactant preferably has at least 1 alkyl take methyl, butyl, cetyl, stearyl, tallow, curing tallow, department of botany's stearyl as carbon number representative, that have C4 ~ C36.In addition, as alkyl, preferred addition has at least a kind that is selected from polyoxyethylene, polyoxypropylene, polyoxyethylene polyoxypropylene, polyacrylic acid, the polycarboxylic acid.These alkyl are strong with the absorption of the aliphatic acid that uses as dispersant, thereby when making silver-colored particle 2 be situated between by the SURFACTANT ADSORPTION dispersant, firmly absorbing fats acid.
Cation is that surfactant is not particularly limited, and is preferably at least a kind that is selected from fluoride, bromide, iodide, chloride, sulfate, nitrate, the phosphate.They contain as the principal component of surfactant usually, easily obtain, thereby preferred.
As dispersant, such as can using the protecting colloids such as aliphatic acid, organic metal, gelatin, if but consider not worry to sneak into impurity and with the adsorptivity of surfactant, then preferably use aliphatic acid or its salt.Need to prove, aliphatic acid or its salt can also add with the form of emulsion.
Aliphatic acid as dispersant is not particularly limited, and is preferably at least a kind that is selected from stearic acid, oleic acid, myristic acid, palmitic acid, linoleic acid, laurate, the leukotrienes.This is because the boiling point of these aliphatic acid is lower, and is few to the harmful effect of the wiring layer that uses silver-colored paste to form, electrode.Can think: aliphatic acid is hydrophobicity originally, is situated between by the SURFACTANT ADSORPTION dispersant by the surface that makes silver-colored particle 2, and makes aliphatic acid be present in a large number the exterior side of organic coating layer 3, has hydrophobicity thereby silver powder 1 is become.Especially, by select easily to be adsorbed in silver-colored particle 2, for example ionization for the surfactant of the electric charge of the electric charge reflexive on silver-colored particle 2 surfaces, can be situated between and adsorb fully dispersant by surfactant, make silver powder 1 show sufficient hydrophobicity.
The scope that the addition of surfactant is 0.002 quality % ~ 1.000 quality % with respect to silver-colored particle 2 preferably.Surfactant is substantially gone up and all is adsorbed in silver-colored particle 2, so the addition of surfactant equates substantially with adsorbance.During the addition less than 0.002 quality % of surfactant, sometimes can't obtain to suppress silver-colored particle 2 gathering, improve the effect of the adsorptivity of dispersant.On the other hand, when addition surpasses 1.000 quality %, use the wiring layer of silver-colored paste formation, the electric conductivity of electrode to reduce, thus not preferred.
The scope that the addition of dispersant is 0.01 quality % ~ 3.00 quality % with respect to silver-colored particle 2 preferably, more preferably 0.01 quality % ~ 1.00 quality %.Dispersant adsorption is different because of the kind of dispersant in the amount of silver-colored particle 2, and during addition less than 0.01 quality %, silver-colored particle 2 can't adsorb the dispersant of the amount that can fully obtain to suppress the effect that silver-colored particle 2 assembles sometimes.On the other hand, when the addition of dispersant surpassed 3.00 quality %, the dispersant that is adsorbed in silver-colored particle 2 became many, and the wiring layer, the electrode that sometimes use silver-colored paste to form can't obtain sufficient electric conductivity.
Silver powder 1 is surfactant by using cation, and surfactant is significantly improved the adsorptivity of silver-colored particle 2, thereby can make surfactant firmly be adsorbed in silver powder 1.Further preferably, stably adsorb by making the surfactant that is adsorbed in silver-colored particle 2, can obtain further to suppress the silver powder 1 of gathering and the excellent dispersion in paste.
Then, for the manufacture method of silver powder 1 of the present invention, operation break-down describes.
For the manufacture method of silver powder 1, for example, as follows during as initiation material with silver chlorate.At first, carry out generating by the wet type reducing process operation of silver-colored particle slurry, described wet type reducing process is: will comprise and utilize the silver complex solution of the silver complex that complexing agent dissolving silver chlorate obtains to mix with reductant solution, silver complex is reduced, silver-colored particle 2 is separated out.Generate in the operation of this silver particle slurry, not needing to arrange in the past with the retracting device of nitrous acid gas required in the method for silver nitrate as initiation material, nitric acid in the waste water is the treating apparatus of nitrogen, and operation is also little on the impact of environment, therefore can realize the reduction of manufacturing cost.
Particularly, generate in the operation of silver-colored particle slurry, at first, use complexing agent dissolving silver chlorate, preparation comprises the silver complex solution of silver complex.Complexing agent is not particularly limited, and preferred use easily with silver chlorate formation complex compound and does not contain ammoniacal liquor with the residual composition of the form of impurity.In addition, silver chlorate preferably uses highly purified silver chlorate.As this silver chlorate, the industrial high-purity chlorination silver of stably making purity 99.9999 quality %.
As the dissolving method of silver chlorate, when for example using ammoniacal liquor as complexing agent, the slurry that can make first silver chlorate adds ammoniacal liquor again, but boosts productivity in order to improve complex concentration, preferably adds silver chlorate and dissolving in ammoniacal liquor.The ammoniacal liquor that is used for the dissolving silver chlorate can be industrial normally used ammoniacal liquor, in order to prevent sneaking into of impurity, the preferred high as far as possible ammoniacal liquor of purity.
Then, for the preparation of the reductant solution that mixes with silver complex solution.As reducing agent, can use common hydrazine, formalin etc.The reduction of ascorbic acid is slow, makes the crystal grain in the silver-colored particle 2 be easy to growth, thereby particularly preferably.The reducing power of hydrazine, formalin is strong, and therefore the crystal in the silver-colored particle 2 easily diminishes.In addition, for homogeneity or the reaction speed of controlling reaction, also reducing agent can be used after making the aqueous solution of concentration through adjusting with the dissolving such as pure water or dilution.
When carrying out reduction reaction, preferably add water soluble polymer.The water soluble polymer that adds is not particularly limited, and is preferably at least a kind in Pluronic F-127, polyethylene glycol, polyvinyl alcohol or the polyvinylpyrrolidone.Water soluble polymer is adsorbed in the surface of silver-colored particle 2 when the reduction silver complex is separated out silver-colored particle 2, play the effect of the dispersant that makes silver-colored particle 2 dispersions, so that primary particle or the second particle of silver can excessively not assembled.When not adding water soluble polymer, the silver-colored particle 2 that nuclear, the nucleus growth that sometimes produces because of the reduction of silver complex forms can occur excessively to assemble, and causes bad dispersibility.In the situation that do not add water soluble polymer, although can the granularity of silver powder 1 be adjusted to the degree that is preferred for silver-colored paste by reducing condition, by adding water soluble polymer, can be adjusted to the preferred granularity for silver-colored paste.The addition of water soluble polymer is suitably selected to get final product with the particle diameter of the silver powder 1 that will obtain according to the kind of water soluble polymer, preferably is the scope of 1 quality % ~ 10 quality % with respect to the silver that contains in the silver complex solution.Be 1 quality % ~ 10 quality % by the content that makes water soluble polymer; can make primary particle or the second particle of silver can not produce excessive gathering; and in the granularity of adjusting silver powder 1, in subsequent handling, suitably form organic coating layer 3 on the surface of silver-colored particle 2.
Water soluble polymer can add in silver complex solution and the reductant solution or in any one.For in silver complex solution and reductant solution or in any one, adding water soluble polymer, can in advance it be added in the solution that adds object before processing reducing, also can when being used for reducing the mixing of the argentiferous complex solution processed and reductant solution, add.More preferably mixing water soluble macromolecular in reductant solution in advance.This is the result who verified by experiment, can think, by being pre-mixed reductant solution and water soluble polymer, nuclear produces or there is water soluble polymer in nucleus growth place, the surface of the nuclear that generates or silver-colored particle 2 is the adsorbed water soluble macromolecular promptly, thereby can suppress excessive gathering.The concentration of water soluble polymer is for surpassing 3 quality % and below the 10 quality % when in addition, more preferably making mixing water soluble macromolecular in the silver complex solution.When adding in advance water soluble polymer in the argentiferous complex solution, nuclear produces or nucleus growth place is difficult to supply with water soluble polymer, and the surface that possibly can't make silver-colored particle 2 is the adsorbed water soluble macromolecular moderately, so addition is greater than 3 quality %.
When adding water soluble polymer, sometimes can foam during reduction reaction, therefore can in silver complex solution or reducing agent mixed liquor, add defoamer.Defoamer is not particularly limited, and the defoamer that uses during for common reduction gets final product.Wherein, in order not hinder reduction reaction, the addition of defoamer preferably is made as the degree of the irreducible minimum that can obtain defoaming effect.
Need to prove, employed water during for preparation silver complex solution and reductant solution, in order to prevent sneaking into of impurity, the preferred water of having removed impurity that uses particularly preferably uses pure water.
In the operation that generates silver-colored particle slurry, above-mentioned such silver complex solution for preparing is mixed with reductant solution, with the silver complex reduction, silver-colored particle 2 is separated out by the wet type reducing process.This reduction reaction can use batch process to carry out, and also can use the continuous reduction of tubular reactor method (tube reactor method), press over system (overflow method) and so on to carry out.In addition, the particle diameter of silver-colored particle 2 can be controlled by the mixing velocity of silver complex solution and reductant solution, the reduction rate of silver complex, can easily be controlled to be target grain size.In addition, with filter etc. gained silver particle slurry is filtered, with silver-colored particle 2 Separation of Solid and Liquid.
The adsorption of the silver-colored particle 2 of gained has a large amount of chlorions and remaining water soluble polymer in this operation.Therefore, for the wiring layer that uses silver-colored paste to form, the electric conductivity of electrode are fully, the slurry of gained silver particle 2 need to be washed in ensuing washing procedure, remove these adsorption things by washing.
Washing methods is not particularly limited, and usually makes with the following method: will be from slurry Separation of Solid and Liquid and silver-colored particle 2 put in the cleaning solution, use mixer or ultrasonic washer to stir after, again carry out Separation of Solid and Liquid, thereby reclaim silver-colored particle 2.In addition, in order to remove fully the adsorption thing, preferably repeat aptly following operation: put in the cleaning solution, agitator treating and Separation of Solid and Liquid.
Cleaning solution can make water, in order to remove efficiently chlorine, can use the aqueous solution of alkali.Aqueous slkali is not particularly limited, and preferably uses the few and cheap sodium hydrate aqueous solution of residual impurity.When using sodium hydrate aqueous solution as cleaning solution, it is desirable to, after washing with aqueous sodium hydroxide washes, in order to remove sodium, silver-colored particle 2 or its slurry are further washed with water.
The concentration that is used for the sodium hydrate aqueous solution of washing is preferably 0.01mol/l ~ 1mol/l.During the not enough 0.01mol/l of the concentration of sodium hydrate aqueous solution, clean result is insufficient, and when surpassing 1mol/l, silver-colored particle 2 can the above sodium of residual tolerance sometimes.Need to prove, the water that is used for cleaning solution is preferably the water that does not contain the impurity element that silver-colored particle 2 is harmful to, and is particularly preferably pure water.
And then, carry out forming on the surface of silver-colored particle 2 surface treatment procedure of organic coating layer 3.In the surface treatment procedure to silver-colored particle 2, silver-colored particle 2 usefulness surfactants are processed, more preferably process with surfactant and dispersant.This surface treatment is so long as before silver-colored particle 2 dryings, then can carry out by one-phase in office, but when chlorine and water soluble polymer are removed fully, sometimes silver-colored particle 2 can be assembled, be difficult in the surface treatment after removing chlorine and water soluble polymer identical surface treatment be carried out on the surface of silver-colored particle 2, it is therefore preferable that in reduction or just reduction after carry out surface treatment, from silver-colored particle slurry, carrying out surface treatment or in washing procedure, carrying out surface treatment before with washing procedure after silver-colored particle 2 Separation of Solid and Liquid.
In the surface treatment procedure, for example by from silver-colored particle slurry, will carrying out surface treatment after silver-colored particle 2 Separation of Solid and Liquid, the inhibition surfactants such as residual organic matter that caused by reducing agent, the absorption of dispersant can be prevented, surface treatment can be effectively carried out.Thus, form sufficient organic coating layer 3, guarantee compatibility and dispersiveness with solvent, resin etc.
In addition, when repeatedly repeating to wash, can when arbitrary washing, carry out surface treatment, preferably, be removed to not under the state that the gathering of can effects on surface processing the degree that impacts, silver-colored particle 2 do not advance at the chlorine that will residue in silver-colored particle 2 and remaining water soluble polymer and carry out surface treatment, for example carrying out carrying out surface treatment after the washing more than 1 time.
For example, concrete grammar as the preferred surface processing of using surfactant and dispersant, during surface treatment before washing, will be from silver-colored particle slurry Separation of Solid and Liquid and silver-colored particle 2 put in the water that is added with surfactant and dispersant and stir and get final product; Perhaps silver-colored particle 2 is being put in the water that is added with surfactant and after stirring, further added dispersant and stirring getting final product.In addition, by in cleaning solution, adding simultaneously surfactant and dispersant or after adding surfactant, adding again dispersant, can wash simultaneously and surface treatment.In order to improve surfactant and dispersant to the adsorptivity of silver-colored particle 2, preferably in the water that is added with surfactant or cleaning solution, after the silver-colored particle 2 of input and the stirring, further add dispersant and stirring.
Need to prove, washing and the employed device of surface treatment be common wash, the employed device of surface treatment gets final product, such as using with the reactive tank of mixer etc.
Then, reclaim the recovery process that the surface has formed the silver-colored particle 2 of organic coating layer 3.This recovery process carries out back and forth cash register particle 2 of Separation of Solid and Liquid after having carried out surface treatment and washing.The employed device of Separation of Solid and Liquid is that normally used device gets final product, such as using centrifuge, suction filtration machine, filter press etc.
Then, after washing and surface treatment finish, make Separation of Solid and Liquid and the moisture evaporation of silver-colored particle 2 and the drying process of drying.As drying means, for example, the silver-colored particle 2 that reclaims after washing and surface treatment finished is placed on the stainless steel pad, and the commercially available drying devices such as use dried-air drier or vacuum drier heat with 40 ℃ ~ 80 ℃ temperature and to get final product.
Then, with the degree of the organic coating layer 3 that can not injured surface forms, very weak energy is crushed to preferred size for silver-colored paste with dried silver-colored particle 2, carry out the fragmentation processed for classification-classification operation, thereby can obtain silver powder 1.Breaking method preferably uses the weak device of the crushing forces such as airflow milling, homogenizer as long as for not damaging the degree of organic coating layer 3, just be not particularly limited.The device that crushing force is strong not only can damage organic coating layer 3, also can make silver powder 1 distortion, thereby not preferred.Grading plant is not particularly limited, and can use airflow classification machine, sieve etc.
Break process is to instigate dried gathering powder to be shattered into the operation of the state of the front primary particle of surface treatment or second particle.As the means of fragmentation, can use the various broken means such as ball mill, conflict formula airflow grinder, impact type grinder, cartridge type homogenizer.Broken energy is crossed when weak, and in the wet processed of can't scattering fully, the aggregation that generates in the dry run, can't make internal friction angle is below 20 °.On the other hand, broken energy is crossed when strong, can damage organic coating layer 3 on the surface of silver powder 1, the part that primary particle in the second particle is bonded to each other is damaged, thereby the newborn face that again exposes argent because of the surface of silver powder 1 causes the hydrophily on surface to become large, becomes 100 ° of less thaies with the contact angle of the methyl alcohol 50 volume % aqueous solution, utilizes surperficial SP value that acetone titration measures greater than 18.And then, also exist the new surface expose to become avtive spot and in keeping, reassociate, make large possible of internal friction angle time dependent ground change.
Therefore, when no matter using any breaking treatment machine, all need the limit to confirm internal friction angle, contact angle, the such parameter limit adjustment broken condition of surperficial SP value, and can not damage the break process of degree of organic coating layer 3 on silver powder 1 surface when being applied to the destruction of suppressing the joint portion that primary particle is bonded to each other, organic coating layer 3 is peeled off and expose the break process of silver-colored particle 2.Broken condition suitably determines the rotating speed of breaker, broken time, temperature etc. according to the state of the silver powder 1 of the size of breaker, made etc.
For example, when using homogenizer, broken condition is different because of the capacity of mixer, according to the input amount of silver-colored particle 2, adjusts the peripheral speed of mixer and mixing time etc. in the mode of not damaging organic coating layer 3.Broken condition when having used homogenizer for example is preferably: peripheral speed is that second in 10m/ second ~ 40m/, broken time are about 10 minutes ~ 60 minutes.
Need to prove, after the break process, generate the silver powder aggregation of the bulk that generates in operation, the fragmentation-classification operation or sneak in order to remove silver-colored particle slurry, preferably carry out the classification of air-flowing type or sieve formula etc. and process.
In the manufacture method of above-mentioned silver powder 1, after the surface of the silver-colored particle 2 that obtains by silver-colored particle slurry generation operation forms organic coating layer 3, the fragmentation that regenerates by the newborn face that silver-colored particle 2 is suppressed argent, can obtain internal friction angle is below 20 °, and with the contact angle of the methyl alcohol 50 volume % aqueous solution be low hydrophilic silver powder 1 more than 100 °.And then the surperficial SP value of passing through acetone titration mensuration of this silver powder 1 is below 18.Thus, in this manufacture method, because the internal friction angle of silver powder 1 is below 20 °, and with the contact angle of the methyl alcohol 50 volume % aqueous solution be more than 100 °, excellent with the wetability of the solvent of silver-colored paste, resin etc., thereby favorable dispersibility, can easily make paste, make silver-colored paste.
In addition, silver powder 1 by this manufacture method manufacturing is owing to having carried out sufficient surface treatment, even therefore not only just make finish after during with the resin of silver-colored paste, solvent, its internal friction angle also is below 20 °, thereby, even in the situation that made in a moment again and solvent, also good with the compatibility of solvent, resin etc., therefore excellent dispersion can easily make paste.
Therefore, above-mentioned silver powder 1 is owing to disperseing equably in silver-colored paste, thereby can make electrical connection become good when forming wiring layer, electrode with silver-colored paste.
Embodiment
Below, describe for applicable specific embodiment of the present invention, but the present invention is not limited to these embodiment.
＜embodiment 1＞
Among the embodiment 1, at first, drop into while stirring 2490g silver chlorate (Sumitomo Metal Mining Co., Ltd's system) to fluid temperature being remained among 36 ℃ the 25 quality % ammoniacal liquor 36L in 38 ℃ temperature is bathed, make silver complex solution, in temperature is bathed, remain 36 ℃.
On the other hand, will be dissolved in as the ascorbic acid 1318g (Kanto Kagaku K. K.'s system, reagent) of reducing agent among 36 ℃ the pure water 10L, make reductant solution.
Then, get polyvinyl alcohol 187.5g as water soluble polymer (Kuraray Co., Ltd. system, PVA205, be 10.0 quality % with respect to silver-colored particle), be dissolved among 36 ℃ the pure water 4.6L and make solution, this solution is mixed in above-mentioned reductant solution.
Then, use Mono pump (mono-pump) (Hyoao Equipment Co., Ltd.'s system) with the 2.44L/ minute speed with 0.90L/ minute above-mentioned silver complex solution and reductant solution to be inputed in the groove respectively, silver complex is reduced.The reduction rate of this moment is counted 127g/ minute with the silver amount.Need to prove, above-mentioned groove has used the vinyl chloride rider of internal diameter 25mm and length 725mm.The slurry that will comprise the silver-colored particle that the reduction by silver complex gets is accommodated in the holding tank while stirring.After taking in end, continue stirring 60 minutes in the holding tank.Utilize filter press that the above-mentioned silver-colored particle slurry that stirs after finishing is filtered, with silver-colored particle Separation of Solid and Liquid.
Then, the silver-colored particle of Separation of Solid and Liquid is carried out surface treatment.As surface conditioning agent, the commercially available stearic acid late 16.87g that belongs to the polyoxyethylene addition quaternary ammonium salt 0.90g that cation is surfactant (Croda Japan K.K. system, trade name Silasol, be 0.048 quality % with respect to silver-colored particle) and belong to dispersant (Zhong jing grease Co., Ltd. system, SELOSOL920, be 0.90 quality % with respect to silver-colored particle) is put in the pure water of 20L, stir, thereby surface treatment is carried out on the surface of silver-colored particle.After this, add NaOH until concentration reaches 0.05mol/L, stirred 15 minutes and washing, then filter with filter press, reclaim silver-colored particle.
Then, before the silver-colored particle drying that will reclaim, silver-colored particle is put in the NaOH aqueous solution of 0.05mol/L, stirred 15 minutes and washing, then filter and reclaim with filter press.With this washing operation with based on the Separation of Solid and Liquid operation of filtering repeat 3 time thereafter.
The silver-colored particle of Separation of Solid and Liquid is put in the pure water of 20L, after stirring and filtering, with silver-colored transfer of granules to the stainless steel pad, with vacuum drier with 60 ℃ of dryings 10 hours.
After the drying, carry out fragmentation and classification.Broken following carrying out: get the dried silver-colored particle of 1.5kg, put into homogenizer (the NIPPON COKE ﹠amp of 5L; ENGINEERING CO., LTD. FM5C/I processed) in, makes rotating vane with the peripheral speed rotation in 15m/ second 30 minutes, carry out break process.And then, use airflow classification machine (EJ-3 of Nippon Mining Co., Ltd. type) to process and obtain silver powder with name a person for a particular job silver-colored gradation after the fragmentation of the classification of 7 μ m.Gained silver powder is 0.98 μ m by the average grain diameter that SEM observes the primary particle that obtains, and the granularity (D50) of using the laser diffraction and scattering method to measure is 2.35 μ m.
As above operate like that, obtain the silver powder of embodiment 1.Measure internal friction angle, contact angle, the surperficial SP value of gained silver powder.
The mensuration of internal friction angle is used powder layer shearing force determinator (Nanoseeds Corporation NS-S300 type processed).At normal temperatures, 18g silver powder is filled into the SUS cell processed of internal diameter 15mm after, the setting value that will press fall into load is made as 20N, and falls into speed with the pressure in 0.2mm/ second and apply load.After arrive setting load, the speed with 10 μ m/ seconds after 100 seconds begins horizontal slip.Need to prove, sampling frequency is 10Hz.The value that the sunken load of pressure when beginning is laterally slided gets divided by the sectional area of cell is as vertical stress σ (N/cm
2), the value that the maximum of the shearing force of measuring afterwards laterally sliding gets divided by the sectional area of cell is as shear stress τ (N/cm
2).
Then, with pressing the setting value that falls into load to be set as 40N, similarly measure vertical stress σ and shear stress τ.And then, with pressing the setting value that falls into load to be set as 60N, similarly measure vertical stress σ and shear stress τ.The vertical stress σ that obtains under above-mentioned three conditions marks and draws take shear stress τ as the longitudinal axis as transverse axis, and the slope (degree) of the near linear that uses least square method to obtain is made as internal friction angle.
The internal friction angle of the silver powder of the embodiment 1 that measures in order to upper method is 7.1 °.After this silver powder is at room temperature placed 1 month, use the mensuration of carrying out internal friction angle with above-mentioned same method, the result is 7.8 °.
Use contact angle determination device (the consonance interface science CA-X150 processed of Co., Ltd.) to carry out with the mensuration of the contact angle of the methyl alcohol 50 volume % aqueous solution.At normal temperatures, with the silver powder press molding, obtain the tabular test body that silver powder is filled by densification with the load of about 1MPa.Measure the contact angle that this test body and the methyl alcohol 50 volume % aqueous solution form.The contact angle of the silver powder of the embodiment 1 that measures with the method is 110 °.
Being determined as follows of surperficial SP value based on acetone titration carried out.Add 50ml water in 0.5g silver powder, slowly stir on the limit, and the limit drips acetone continuously in the water that is added with silver powder, take swim in the silver-colored particle of the water surface disperse and during the solution becomes gonorrhoea as terminal point.The surperficial SP value of the aqueous acetone solution that the interpolation volume of the acetone with thus the time is calculated is as the surperficial SP of silver powder.The surperficial SP value of the silver-colored particle of the embodiment 1 that measures with the method is 16.7.
Then, to using gained silver powder to make paste evaluation.About making the evaluation of paste, at first, weighing 9.2g silver powder, epoxy resin (Mitsubishi chemical Co., Ltd's system, JER819) are the excipient 0.8g of 1:7 with the weight ratio of terpinol in the capsule of stainless steel.At this moment, can be observed the surface of silver powder wetting rapidly because of excipient.Then, when using the metallicity scraper that it is mixed, mix, disperse easily to advance, can make paste-like.And then, use from revolution type mixing roll (THINKY CORPORATION ARE-250 type processed) with the speed of 2000rpm mixing 5 minutes of this paste, obtain the silver-colored paste of homogeneous.Use fineness gauge to estimate the dispersiveness of gained silver paste, maximum particle diameter Dmax is little of 7 μ m, shows excellent dispersiveness.
＜embodiment 2＞
Among the embodiment 2, the amount of polyvinyl alcohol is made as 75g (be 4.00 quality %s with respect to silver-colored particle), makes the rotating vane of homogenizer with the 28m/ peripheral speed rotation in second, in addition, obtain silver powder and estimate with similarly to Example 1 method.The average grain diameter of the primary particle of gained silver powder is 1.01 μ m, and granularity (D50) is 2.73 μ m.
The internal friction angle of the silver powder of embodiment 2 is 10.4 °, and the internal friction angle of at room temperature placing after 1 month is 10.6 °.In addition, the contact angle of the silver powder of embodiment 2 is 109 °, and surperficial SP value is 17.4.
Then, use gained silver powder carries out the evaluation of making paste similarly to Example 1.The surface that can be observed silver powder is promptly wetting because of excipient.When using the metallicity scraper that it is mixed, mix, disperse easily to advance, can make paste-like.And then, this paste is used similarly to Example 1 from revolution type mixing roll mixing, obtain the silver-colored paste of homogeneous.Use fineness gauge to estimate the dispersiveness of gained silver paste, maximum particle diameter Dmax is little of 6 μ m, shows excellent dispersiveness.
＜comparative example 1＞
In the comparative example 1, except the rotating vane that makes homogenizer with the 42m/ peripheral speed rotation in second, obtain silver powder and estimate with similarly to Example 1 method.The average grain diameter of the primary particle of gained silver powder is 0.99 μ m, and granularity (D50) is 1.82 μ m.In addition, the internal friction angle of the silver powder of comparative example 1 is 20.8 °, and is high more a lot of than embodiment.In addition, the contact angle of the silver powder of comparative example 1 is 85 °, and surperficial SP value is 18.7.
Then, use gained silver powder carries out the evaluation of making paste similarly to Example 1.Basically the surface that does not observe silver powder is wetting because of excipient.In addition, when using the metallicity scraper that it is stirred, only become large argillaceous, can't make paste-like.And then, this paste is used similarly to Example 1 from revolution type mixing roll mixing, make paste-like.Use fineness gauge to estimate the dispersiveness of gained silver paste, maximum particle diameter Dmax is greatly to 20 μ m, bad dispersibility.
＜comparative example 2＞
In the comparative example 2, except the rotating vane that makes homogenizer with the 7m/ peripheral speed rotation in second, obtain silver powder and estimate with similarly to Example 2 method.The average grain diameter of the primary particle of gained silver powder is 1.00 μ m, and granularity (D50) is 3.52 μ m.In addition, the internal friction angle of the silver powder of comparative example 2 is 25.8 °, and is high more a lot of than embodiment.In addition, the contact angle of the silver powder of comparative example 2 is 110 °, and surperficial SP value is 17.4 °.
Then, use gained silver powder carries out the evaluation of making paste similarly to Example 1.Basically the surface that does not observe silver powder is wetting because of excipient.In addition, when using the metallicity scraper that it is stirred, only become the argillaceous of bulk, can't make paste-like.And then, this paste is used similarly to Example 1 from revolution type mixing roll mixing, make paste-like.Use fineness gauge to estimate the dispersiveness of gained silver paste, maximum particle diameter Dmax is greatly to 18 μ m, bad dispersibility.
Based on above embodiment and comparative example, even the silver powder by the same procedure making, compare with comparative example, the degree of the overlay film that forms with the surface that can not damage silver powder has been carried out among broken embodiment 1 and the embodiment 2 fully, internal friction angle is below 20 °, and with the contact angle of the methyl alcohol 50 volume % aqueous solution be more than 100 °, good with the compatibility of excipient, can obtain the silver powder of excellent dispersion.In addition, among embodiment 1 and the embodiment 2, the surperficial SP value of further measuring by acetone titration is below 18.And then, among embodiment 1 and the embodiment 2, even after silver powder at room temperature placed 1 month, internal friction angle also was that gathering is suppressed below 20 °.
On the other hand, in the comparative example 1, broken condition is excessively strong, and organic coating layer that the surface of silver powder forms is impaired, and internal friction angle is greater than 20 °, and contact angle is also less than 100 °.And then surperficial SP value is also greater than 18.In addition, in the comparative example 2, a little less than the broken condition, aggregation can't be scattered fully, thereby internal friction angle is 25.8 °, becomes very large.Thus, poor with the compatibility of excipient in comparative example 1 and the comparative example 2, the bad dispersibility of silver powder.
Claims (5)
1. a silver powder is characterized in that, internal friction angle is below 20 °, and with the contact angle of the methyl alcohol 50 volume % aqueous solution be more than 100 °.
2. silver powder according to claim 1 is characterized in that, its surperficial SP value of measuring by acetone titration is below 18.
3. according to claim 1 or silver powder claimed in claim 2, it is characterized in that, the described internal friction angle during with the solvent of silver-colored paste is below 20 °.
4. the manufacture method of a silver powder, it is characterized in that, by to using the synthetic silver-colored particle of wet type reducing process to carry out surface treatment after the surface forms organic coating layer, under the degree of not damaging described organic coating layer, carry out sufficient break process, make internal friction angle and be below 20 ° and with the contact angle of the methyl alcohol 50 volume % aqueous solution be silver powder more than 100 °.
5. the manufacture method of silver powder according to claim 4 is characterized in that, the method for described break process is used homogenizer, and its condition is that the peripheral speed of stirring vane is above and 40m/ below second in 10m/ second.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011134337 | 2011-06-16 | ||
| JP2011-134337 | 2011-06-16 | ||
| PCT/JP2012/065411 WO2012173245A1 (en) | 2011-06-16 | 2012-06-15 | Silver powder and method for producing same |
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| Publication Number | Publication Date |
|---|---|
| CN103079730A true CN103079730A (en) | 2013-05-01 |
| CN103079730B CN103079730B (en) | 2016-06-29 |
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| CN201280002704.1A Expired - Fee Related CN103079730B (en) | 2011-06-16 | 2012-06-15 | Argentum powder and manufacture method thereof |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JP5344099B2 (en) |
| KR (2) | KR20140024829A (en) |
| CN (1) | CN103079730B (en) |
| MY (1) | MY156843A (en) |
| TW (1) | TWI579073B (en) |
| WO (1) | WO2012173245A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112296351A (en) * | 2020-09-29 | 2021-02-02 | 湖南诺尔得材料科技有限公司 | Preparation method of high-tap-density ultrafine silver powder |
| CN114226745A (en) * | 2021-12-10 | 2022-03-25 | 江西贝特利新材料有限公司 | Method for cleaning micron-sized flake silver powder |
| CN115519129A (en) * | 2022-08-05 | 2022-12-27 | 南通领跑者新材料科技有限公司 | Preparation method of silver powder for conductive paste |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN115780797A (en) * | 2022-11-15 | 2023-03-14 | 长沙族兴新材料股份有限公司 | Imitation electroplating aluminum paste and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1548260A (en) * | 2003-05-12 | 2004-11-24 | 贵研铂业股份有限公司 | Surface processing method of superfine silver powder |
| CN101462164A (en) * | 2009-01-09 | 2009-06-24 | 贵阳晶华电子材料有限公司 | High-tap density micro aluminum powder and method for producing the same |
| CN101716685A (en) * | 2009-12-14 | 2010-06-02 | 昆明理工大学 | Method for preparing spherical superfine silver powder by using chemical reduction method |
| JP2010180471A (en) * | 2009-02-09 | 2010-08-19 | Dowa Electronics Materials Co Ltd | Flaky silver powder and method for producing the same, and conductive paste |
| CN101856726A (en) * | 2010-06-17 | 2010-10-13 | 哈尔滨得意药业有限责任公司 | Method for preparing multifunctional nano silver solution |
| JP2010229480A (en) * | 2009-03-26 | 2010-10-14 | Mitsubishi Materials Corp | Silver particle and method of producing the same |
| JP2011001581A (en) * | 2009-06-17 | 2011-01-06 | Sumitomo Metal Mining Co Ltd | Silver powder and method for producing the same |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3381240B2 (en) * | 1992-08-10 | 2003-02-24 | 旭化成株式会社 | How to collect foam particles |
| JP4732645B2 (en) * | 1999-06-15 | 2011-07-27 | 丸山 稔 | Method for producing metal composite ultrafine particles |
| JP4569727B2 (en) * | 2000-09-08 | 2010-10-27 | Ｄｏｗａエレクトロニクス株式会社 | Silver powder and method for producing the same |
| JP2006156426A (en) * | 2004-11-25 | 2006-06-15 | Seiko Epson Corp | Method of forming conductive pattern |
| WO2008013274A1 (en) * | 2006-07-28 | 2008-01-31 | Mitsubishi Materials Corporation | Silver fine particles and processes and equipment for the production thereof |
| KR101651915B1 (en) * | 2009-09-14 | 2016-08-29 | 한화케미칼 주식회사 | A method for preparing water-soluble nanoparticles and their dispersions |
| JP5556561B2 (en) * | 2010-10-06 | 2014-07-23 | 住友金属鉱山株式会社 | Silver powder and method for producing the same |
-
2012
- 2012-06-15 KR KR1020137005227A patent/KR20140024829A/en active Application Filing
- 2012-06-15 KR KR1020187016842A patent/KR20180069930A/en not_active Application Discontinuation
- 2012-06-15 WO PCT/JP2012/065411 patent/WO2012173245A1/en active Application Filing
- 2012-06-15 JP JP2012548249A patent/JP5344099B2/en not_active Expired - Fee Related
- 2012-06-15 MY MYPI2013701718A patent/MY156843A/en unknown
- 2012-06-15 CN CN201280002704.1A patent/CN103079730B/en not_active Expired - Fee Related
- 2012-06-18 TW TW101121743A patent/TWI579073B/en not_active IP Right Cessation
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1548260A (en) * | 2003-05-12 | 2004-11-24 | 贵研铂业股份有限公司 | Surface processing method of superfine silver powder |
| CN101462164A (en) * | 2009-01-09 | 2009-06-24 | 贵阳晶华电子材料有限公司 | High-tap density micro aluminum powder and method for producing the same |
| JP2010180471A (en) * | 2009-02-09 | 2010-08-19 | Dowa Electronics Materials Co Ltd | Flaky silver powder and method for producing the same, and conductive paste |
| JP2010229480A (en) * | 2009-03-26 | 2010-10-14 | Mitsubishi Materials Corp | Silver particle and method of producing the same |
| JP2011001581A (en) * | 2009-06-17 | 2011-01-06 | Sumitomo Metal Mining Co Ltd | Silver powder and method for producing the same |
| CN101716685A (en) * | 2009-12-14 | 2010-06-02 | 昆明理工大学 | Method for preparing spherical superfine silver powder by using chemical reduction method |
| CN101856726A (en) * | 2010-06-17 | 2010-10-13 | 哈尔滨得意药业有限责任公司 | Method for preparing multifunctional nano silver solution |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112296351A (en) * | 2020-09-29 | 2021-02-02 | 湖南诺尔得材料科技有限公司 | Preparation method of high-tap-density ultrafine silver powder |
| CN114226745A (en) * | 2021-12-10 | 2022-03-25 | 江西贝特利新材料有限公司 | Method for cleaning micron-sized flake 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 |
| CN115519129A (en) * | 2022-08-05 | 2022-12-27 | 南通领跑者新材料科技有限公司 | Preparation method of silver powder for conductive paste |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2012173245A1 (en) | 2012-12-20 |
| JPWO2012173245A1 (en) | 2015-02-23 |
| MY156843A (en) | 2016-03-31 |
| KR20140024829A (en) | 2014-03-03 |
| CN103079730B (en) | 2016-06-29 |
| JP5344099B2 (en) | 2013-11-20 |
| TWI579073B (en) | 2017-04-21 |
| TW201306967A (en) | 2013-02-16 |
| KR20180069930A (en) | 2018-06-25 |
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