CN107921543A - The manufacture method of high temperature sintering type conductive paste silver powder - Google Patents
The manufacture method of high temperature sintering type conductive paste silver powder Download PDFInfo
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- CN107921543A CN107921543A CN201680047257.XA CN201680047257A CN107921543A CN 107921543 A CN107921543 A CN 107921543A CN 201680047257 A CN201680047257 A CN 201680047257A CN 107921543 A CN107921543 A CN 107921543A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
Abstract
The present invention provides a kind of manufacture method of silver powder, including：Silver salt reduction step (S2), is formed by manufacturing the reaction solution manufacturing step (S21) comprising silver ion, the 1st reaction solution of ammonia and nitric acid and the 2nd reaction solution comprising reducing agent and the precipitation step (S22) by making the 1st reaction solution and the 2nd reaction solution react to obtain silver powder；Wherein, the shrinking percentage being capable of providing by above-mentioned manufacture method in 260~400 DEG C of sections is less than 10% silver powder.
Description
Technical field
The present invention relates to a kind of manufacture method of high temperature sintering type conductive paste silver powder.
Background technology
Conductive metal slurry is a kind of painting that can be after drying with the coating characteristics and electric current that can form film
The slurry flowed in film, is that conductive filling (metal charge) is distributed to the load being made of cement and solvent
Mobility constituent in body, is widely used in the formation of electric loop or the formation of the outer electrode of ceramic capacitor etc..
After the fact that organic polymer can also make electric current flowing is found recently, people, which are actively developing, is related to electric conductivity height
The research and development activity of molecule, but because electroconductive polymer is to realize its electric conductivity by means of being conjugated dual combination structure,
Therefore in view of its strand is tetanic and crystallinity is higher and the problem of be difficult to be dissolved in solvent, it is difficult to be made into coating
The outstanding slurry of characteristic.
Conductive metal slurry practical at present passes through hardening of resin at a temperature of being included in less than 200 DEG C of sole
And make it that conductive filling is extruded and thereby ensures that the hardening of resin type of its turn-on effect, and at 500~1200 DEG C
Under hot environment by the volatilization of organic carrier constituent and conductive filling is sintered and thereby ensures that its turn-on effect
Slug type.
Wherein, slug type conductive paste is by the conductive filling centered on noble metal and glass dust (glass
Frit), organic carrier (resin and organic solvent) is formed, after the film to being coated with is dried, by using high temperature
Handled and make organic carrier roasting evaporation, so that welding occurs between metal charge and realizes the conduction of film whereby
Property.At this time, glass frit component can be sintered inside film and play the role of inorganic bond, so as to provide between substrate
Bonding force.Organic carrier can play the role of type metal powder and the organic liquid medium needed for glass dust, still
Because the organic matter inside the film of residual after the hardening can cause such as electrical resistance increase to the performance of intended applications
Harmful effect, it is therefore desirable to reduce remaining content of organics.
For the silver powder used in slug type conductive paste, in order to tackle the graph thinning trend of electrode or circuit,
It is required that in it is microgranular while the silver powder with sharp keen size distribution, therefore there is relative new technology to be taken off
Show.
For example, in patent document 1 (Japanese Laid-Open 2005-48237 publications), disclose it is a kind of by comprising
The aqueous solution of silver salt adds alkali or complexing agent and reduces the spherical silver powder of polymolecularity for the micronized for separating out less than 0.6 μm, so that
The coacervation of acquisition powder is less and with the method close to monodispersed dispersed microgranular silver powder.
In addition, in patent document 2 (Japanese Laid-Open the 2017-70793rd), disclose a kind of by mixed nitrate silver
Aqueous solution and ammonium hydroxide simultaneously bring it about reaction and obtain silver ammonia complex aqueous solution, and in the particle as crystal seed and imidization
In the presence of compound, above-mentioned silver ammonia complex aqueous solution and reducing agent aqueous solution mix and whereby separate out silver from
Son, so as to obtain, average grain diameter is less than 1 μm more than 0.1 μm, size distribution is sharp keen and the method for the spherical silver powder of polymolecularity.
But the tendency that percent thermal shrinkage becomes larger can be showed when silver powder tends to micronized, and when at 400~800 DEG C
At a high temperature of thermal contraction degree difference between the metal charge and substrate of the slug type conductive paste that sinter it is larger
When, phenomena such as stripping between substrate and metal deposit, bending, deformation, crackle can be caused.
The content of the invention
Technical task
It is an object of the invention to solve above-mentioned existing issue and providing a kind of can be effective as slug type conduction
In the silver powder that the conductive metal filler of property slurry is used, because the thermal contraction in 260~400 DEG C of temperature ranges
Rate is relatively low and can effectively suppress the manufacture method of the silver powder of the thermal contraction degree difference between substrate and silver powder.
But the purpose of the present invention is not limited to purpose mentioned above, the practitioner of relevant industries can lead to
Cross following records and be further expressly understood that silent other purposes.
Solve problem method
The present invention provides a kind of manufacture method of silver powder, including：Silver salt reduction step S2, by manufacture comprising silver ion,
The reaction solution manufacturing step S21 of 1st reaction solution of ammonia and nitric acid and the 2nd reaction solution comprising reducing agent and by making the 1st
The precipitation step S22 that reaction solution and the 2nd reaction solution react and obtain silver powder is formed.
In addition, it is a feature of the present invention that above-mentioned ammonia includes 250 to 600 weights relative to the above-mentioned silver ion of 100 parts by weight
Measure part.
In addition, it is a feature of the present invention that above-mentioned nitric acid includes 20 to 230 weights relative to the above-mentioned silver ion of 100 parts by weight
Measure part.
In addition, it is a feature of the present invention that above-mentioned reducing agent being included in above-mentioned 1st reaction solution relative to 100 parts by weight
Silver ion include 50 to 60 parts by weight.In addition, it is a feature of the present invention that above-mentioned reaction solution manufacturing step S21 is by molten
Agent addition silver ion, ammonia spirit and aqueous solution of nitric acid simultaneously carry out stirring and dissolving and manufacture the 1st reaction solution, and above-mentioned reaction solution
Manufacturing step S21 is by adding reducing agent to solvent and carrying out the step of stirring and dissolving is to manufacture 2 reaction solution.
In addition, it is a feature of the present invention that above-mentioned precipitation step S22 is in the state being stirred to above-mentioned 1st reaction solution
Under the step of being slowly added dropwise or disposably adding above-mentioned 2nd reaction solution and bring it about reaction.
In addition, it is a feature of the present invention that above-mentioned precipitation step S22 be further addition from by aliphatic acid, soap,
Selected in the group that surfactant, organic metal, chelating agent and protecting colloid are formed more than one and bring it about reaction
The step of.
In addition, it is a feature of the present invention that above-mentioned reducing agent be from by hydroquinone, ascorbic acid, alkanolamine, hydrazine with
And formalin form group in select more than one.
In addition, the present invention provides a kind of silver powder, in crystallization average diameter is 1.5 μm to 3 μm of silver powder, will utilize
The film of above-mentioned silver powder manufacture in atmosphere with 3 DEG C/min of programming rate from room temperature rise to 260 DEG C and keep 2 it is small when, so
Afterwards with 3 DEG C/min of programming rate from 260 DEG C be warming up to 400 DEG C and keep 2 it is small when so that it is in 260~400 DEG C of sections
Interior shrinking percentage is less than 10%.
Invention effect
The present invention relates to a kind of manufacture method of high temperature sintering type conductive paste silver powder, change can not only be passed through
The usage amount of ammonia and nitric acid and produce uniform silver powder, additionally it is possible to by being less than its shrinking percentage in 260~400 DEG C
10% and suppress the thermal contraction degree difference between substrate and silver powder so that excellent reliability after providing high temperature sintering
High temperature sintering type conductive paste.
In addition, because the shrinking percentage in 260~400 DEG C can be suppressed, therefore enable in particular to be effective as cascade type pottery
Conductive filling used in the slug type conductive paste of porcelain condenser is used.
Brief description of the drawings
The heat treatment temperature curve of silver powder is shown in Fig. 1.
Embodiment
It should be understood that term used in the present specification is only applicable in before the present invention will be described in detail
Described in specific embodiment, be not intended to make the scope of the present invention restriction, the scope of the present invention should be by institute
The scope of attached claims makes restriction.Unless otherwise stated, all technology arts used in the present specification
The technical implication of language and scientific terminology is identical with the normally understood implication of personnel institute for grasping general technology.
Unless otherwise stated, include used in this specification and all the elements of claims
(comprise, comprises, comprising) term refer to include mentioned object, step or a series of object with
And step, but do not imply that a series of presence for excluding any other objects, step or objects or series of steps.
In addition, being recorded unless otherwise clearly opposite, each embodiment for being otherwise applicable in the present invention can also be with other realities
Apply example and combine and implement.Especially, being designated as some preferable or favourable feature can also be with being appointed as preferable or favourable it
Outer some other feature and multiple features combine.In the following, will be with reference to attached drawing to being applicable in the embodiment of the present invention and its effect
It is described in detail.
Being applicable in the manufacture method of the high temperature sintering type conductive paste silver powder of one of present invention embodiment includes：Silver salt
Manufacturing step S1；Silver salt reduction step S2；The purification step S3 such as filtering and washing；And surface treatment step S4.It is applicable in this hair
The manufacture method of bright silver powder must include silver salt reduction step S2, other steps then can be omitted.
1. silver salt manufacturing step S1
The silver salt manufacturing step S1 for being applicable in one of present invention embodiment be by ingot, bar shaped, particle shape silver
The step of (silver, Ag) carries out acid adding processing and produce silver salt (silver salt) solution, can be direct by this step
Produce silver salt solution and further manufacture silver powder, can also use silver nitrate, silver salt complex compound or silver from market purchase
Midbody solution performs follow-up step.
2. silver salt reduction step S2
The silver-colored reduction step S2 for being applicable in one of present invention embodiment be by silver salt solution add reducing agent and ammonia and
The step of reducing silver ion and separating out silver particles (silver particle) whereby, including：Manufacture includes silver ion, ammonia and nitre
1st reaction solution of acid and the reaction solution manufacturing step S21 of the 2nd reaction solution comprising reducing agent and by making the 1st reaction solution
React with the 2nd reaction solution and obtain the precipitation step S22 of silver powder.
The reaction solution manufacturing step S21 for being applicable in one of present invention embodiment is by adding to the silver salt solution comprising silver ion
Ammonification and nitric acid simultaneously carry out stirring and dissolving and produce the 1st reaction solution.
As long as the form of the silver-colored cation of above-mentioned silver ion is not just any way limited.As an example, nitre can be used
Sour silver, silver salt complex compound or silver-colored intermediate.The concentration of silver ion is not so limited, but in the range of 6g/L to 40g/L
It is advisable.When less than 6g/L can because yield is relatively low and the problem of cause economy to decline, and can cause powder when higher than 40g/L
The problem of end cohesion.
The present invention can reduce by 260~400 DEG C of contractions burnt till in section by adding ammonia and nitric acid to the 1st reaction solution
Rate.It would generally be shunk using the ceramic wafer of high temperature sintering conductive paste more than 600 DEG C, such as the silver powder in Fig. 1
Heat treatment temperature curve shown in, when in 260 DEG C~400 DEG C of maintenance section more contraction occurs for silver powder, can lead
Ceramic wafer is caused to deform or the problem of crackle.Therefore, it is necessary to be dropped by reducing the shrinking percentage in 260 DEG C to 400 DEG C sections
The low influence caused by ceramic wafer, generally it can be thought that when shrinking percentage of the silver powder in 260~400 DEG C of sections is less than 10%
Hardly ceramic wafer is impacted.
Present invention estimation can be by adding ammonia and nitric acid to silver salt solution so that by nitrate and ammonium ion with reference to and
Into ammonium nitrate be comprised in the silver powder of manufactured (precipitation), so as to increase its firing temperature, and substituted using ammonium nitrate
Also identical effect can be realized when nitric acid and ammonia.
Ammonia can be used in the form of aqueous solution, and the usage amount of ammonia spirit is the silver relative to 100 parts by weight
Ion, which adds 250 to 600 parts by weight, to be advisable.It can cause percent thermal shrinkage minimizing effect when the ammonia added is less than 250 parts by weight
The problem of insufficient, and the size (size) of manufactured silver powder can be caused when the ammonia added is more than 600 parts by weight
The problem of significantly reducing.When using 25% ammonia spirit, 60 to 150 weight are added relative to the silver ion of 100 parts by weight
Part is advisable.Above-mentioned ammonia includes its derivative.
The usage amount of nitric acid is to add 20 to 230 parts by weight relative to the silver ion of 100 parts by weight to be advisable.When what is added
The problem of nitric acid can cause shrinking percentage minimizing effect insufficient when being less than 20 parts by weight, and work as added nitric acid and be more than 230 weights
The problem of when measuring part the size (size) of manufactured silver powder and the content of organic matter being caused to be significantly increased.Above-mentioned nitric acid
Include its derivative.
The 1st reaction solution comprising silver ion, ammonia and nitric acid, can by water equal solvent add silver ion, ammonia spirit,
Aqueous solution of nitric acid simultaneously carries out stirring and dissolving and is manufactured into aqueous solution state, or is manufactured into suspension form.
In the reaction solution manufacturing step S21 of one of present invention embodiment is applicable in, also 2nd reaction of the manufacture comprising reducing agent
Liquid.
Above-mentioned reducing agent can be from the group being made of ascorbic acid, alkanolamine, hydroquinone, hydrazine and formalin
Middle selection more than one, especially therefrom selection hydroquinone be advisable.The content of reducing agent is the bag relative to 100 parts by weight
The silver ion being contained in the 1st reaction solution, which includes 50 to 60 parts by weight, to be advisable.Nothing is may result in when below using 50 parts by weight
The problem of method reduces all silver particles, and more than using 60 parts by weight when may result in the content increase of organic matter.
The 2nd reaction solution comprising reducing agent, can be made by adding reducing agent to water equal solvent and carrying out stirring and dissolving
Cause aqueous solution state.
The precipitation step S22 for being applicable in one of present invention embodiment is by making the 1st reaction solution and the 2nd reaction solution react
And the step of obtaining silver powder, the shape that can be stirred in the 1st reaction solution to being produced by reaction solution manufacturing step S21
Under state slowly land price or the 2nd reaction solution of disposable addition and bring it about reaction.It is preferred that the method disposably added can be
Disposably reduction reaction is completed in the shorter time and is prevented the cohesion between particle and is lifted its dispersiveness.
In addition, in one embodiment of the invention is applicable in, in order to lift the dispersiveness of silver particles and prevent it from agglomerating
And further add the scheme that above-mentioned dispersant is reacted and be not also excluded outside right.As dispersant
Example, can be aliphatic acid, soap, surfactant, organic metal, chelating agent and protecting colloid etc..
But the problem of may result in the content increase of residual organic matter when adding above-mentioned dispersant, therefore not
The diameter of the particle diameter of silver powder, the content of residual organic matter and crystallization, which is controlled, in the case of addition dispersant is advisable.
3. purification step S3
Being applicable in the purification step S3 of one of present invention embodiment includes：Silver particles are completed by silver salt reduction step S2
After evolution reaction, using the silver powder being dispersed in aqueous solution or suspension is separated and washed such as modes such as filterings
Step S31.Specifically, the supernatant of dispersion liquid, Ran Houli are removed after the silver particles sedimentation in silver powder dispersion liquid is made
Filtered with centrifugal separator and filter medium is cleaned using clear water., it is necessary to go completely during cleaning is performed
Except the washings washed to powder can be completed.Therefore, it is necessary to moisture content is reduced to less than 10%.Alternatively,
The cohesion of silver powder can be prevented by adding dispersant mentioned above to the solution for completing reaction before filtration.
In addition, the purification step S3 for being applicable in one of present invention embodiment can also include the drying after washing and crush
Step S34.
4. surface treatment step S4
The surface treatment step S4 for being applicable in one of present invention embodiment is to carry out hydrophobization to the water-wetted surface of silver powder
Step, optionally performs.Specifically, can will filter after obtained wet cake (wet cake) moisture content
Adjust to after less than 10%, surface conditioning agent is added to be surface-treated to silver powder and adjusts moisture content and is arrived
70%~85%.Next, silver powder can be obtained by drying, crushing process.Because it is surface-treated to silver powder
When only have powder to be dispersed throughout the decline that can effectively realize and can cause dispersion efficiency when surface treatment and relatively low moisture content,
Therefore carrying out surface treatment in the case where ensuring certain moisture content is advisable.
For the silver powder produced according to one embodiment of the invention is applicable in, scanning electron microscope (SEM) is being utilized
Each diameters of 100 powder is measured the mean size calculated afterwards (size) value 1.5 μm to 3 μm scope it
It is interior, TGA analyses are performed to 500 DEG C of scope to room temperature with 10 DEG C/min of programming rate in atmosphere and are determined whereby
The content of organic matter is less than 1.0 weight %.
In addition, for utilizing according to the film test piece for being applicable in the silver powder manufacture that one embodiment of the invention produces,
In air with 3 DEG C/min of programming rate from room temperature rise to 260 DEG C and keep 260 DEG C state 2 it is small when, then with 3 DEG C/minute
The programming rate of clock be warming up to 400 DEG C and keep 400 DEG C state 2 it is small when, the shrinking percentage in 260~400 DEG C of sections is small at this time
In 10%.
Embodiment and comparative example
<Embodiment 1>
To pure water input 64g silver nitrate solutions, 58g ammonia solutions (concentration 25%) and the 11g nitric acid of 880g room temperature
Solution (concentration 60%), and the 1st reaction solution is prepared by stirring and dissolving.In addition, put into the pure water of 1000g room temperature
10g hydroquinones, and the 2nd reaction solution is prepared by stirring and dissolving.
Next, the 2nd reaction solution is disposably added to above-mentioned 1st reaction solution under the lasting reaction of stirring the 1st liquid status
In, and be stirred for after the addition was complete 5 minutes, so that the particle growth in mixed liquor.Next stop stirring and make to mix
The particle precipitation in liquid is closed, the supernatant of mixed liquor is then removed and mixed liquor is filtered using centrifugal separator, afterwards
Filter medium is cleaned using clear water, silver powder is obtained finally by dry.
<Embodiment 2>
To pure water input 64g silver nitrate solutions, 87g ammonia solutions (concentration 25%) and the 17g nitric acid of 850g room temperature
Solution (concentration 60%), and the 1st reaction solution is prepared by stirring and dissolving.In addition, put into the pure water of 1000g room temperature
10g hydroquinones, and the 2nd reaction solution is prepared by stirring and dissolving.
Next, the 2nd reaction solution is disposably added to above-mentioned 1st reaction solution under the lasting reaction of stirring the 1st liquid status
In, and be stirred for after the addition was complete 5 minutes, so that the particle growth in mixed liquor.Next stop stirring and make to mix
The particle precipitation in liquid is closed, the supernatant of mixed liquor is then removed and mixed liquor is filtered using centrifugal separator, afterwards
Filter medium is cleaned using clear water, silver powder is obtained finally by dry.
<Embodiment 3>
To pure water input 64g silver nitrate solutions, 87g ammonia solutions (concentration 25%) and the 41g nitric acid of 830g room temperature
Solution, and the 1st reaction solution is prepared by stirring and dissolving.In addition, 10g hydroquinones are put into the pure water of 1000g room temperature, and
2nd reaction solution is prepared by stirring and dissolving.
Next, the 2nd reaction solution is disposably added to above-mentioned 1st reaction solution under the lasting reaction of stirring the 1st liquid status
In, and be stirred for after the addition was complete 5 minutes, so that the particle growth in mixed liquor.Next stop stirring and make to mix
The particle precipitation in liquid is closed, the supernatant of mixed liquor is then removed and mixed liquor is filtered using centrifugal separator, afterwards
Filter medium is cleaned using clear water, silver powder is obtained finally by dry.
<Embodiment 4>
It is molten to the pure water input 64g silver nitrate solutions, 29g ammonia solutions (concentration 25%) and 7g nitric acid of 920g room temperature
Liquid, 10g ammonium nitrate solutions, and the 1st reaction solution is prepared by stirring and dissolving.In addition, put into the pure water of 1000g room temperature
10g hydroquinones, and the 2nd reaction solution is prepared by stirring and dissolving.
Next, the 2nd reaction solution is disposably added to above-mentioned 1st reaction solution under the lasting reaction of stirring the 1st liquid status
In, and be stirred for after the addition was complete 5 minutes, so that the particle growth in mixed liquor.Next stop stirring and make to mix
The particle precipitation in liquid is closed, the supernatant of mixed liquor is then removed and mixed liquor is filtered using centrifugal separator, afterwards
Filter medium is cleaned using clear water, silver powder is obtained finally by dry.
<Embodiment 5>
It is molten to the pure water input 64g silver nitrate solutions, 29g ammonia solutions (concentration 25%) and 7g nitric acid of 920g room temperature
Liquid, 33g ammonium nitrate solutions, and the 1st reaction solution is prepared by stirring and dissolving.In addition, put into the pure water of 1000g room temperature
10g hydroquinones, and the 2nd reaction solution is prepared by stirring and dissolving.
Next, the 2nd reaction solution is disposably added to above-mentioned 1st reaction solution under the lasting reaction of stirring the 1st liquid status
In, and be stirred for after the addition was complete 5 minutes, so that the particle growth in mixed liquor.Next stop stirring and make to mix
The particle precipitation in liquid is closed, the supernatant of mixed liquor is then removed and mixed liquor is filtered using centrifugal separator, afterwards
Filter medium is cleaned using clear water, silver powder is obtained finally by dry.
<Embodiment 6>
It is molten to the pure water input 64g silver nitrate solutions, 29g ammonia solutions (concentration 25%) and 7g nitric acid of 920g room temperature
Liquid, 50g ammonium nitrate solutions, and the 1st reaction solution is prepared by stirring and dissolving.In addition, put into the pure water of 1000g room temperature
10g hydroquinones, and the 2nd reaction solution is prepared by stirring and dissolving.
Next, the 2nd reaction solution is disposably added to above-mentioned 1st reaction solution under the lasting reaction of stirring the 1st liquid status
In, and be stirred for after the addition was complete 5 minutes, so that the particle growth in mixed liquor.Next stop stirring and make to mix
The particle precipitation in liquid is closed, the supernatant of mixed liquor is then removed and mixed liquor is filtered using centrifugal separator, afterwards
Filter medium is cleaned using clear water, silver powder is obtained finally by dry.
<Comparative example 1>
64g silver nitrate solutions and 30g ammonia solutions (concentration 25%) are put into the pure water of 930g room temperature, and by stirring
Mix dissolving and prepare the 1st reaction solution.In addition, putting into 10g hydroquinones to the pure water of 1000g room temperature, and pass through stirring and dissolving
Prepare the 2nd reaction solution.
Next, the 2nd reaction solution is disposably added to above-mentioned 1st reaction solution under the lasting reaction of stirring the 1st liquid status
In, and be stirred for after the addition was complete 5 minutes, so that the particle growth in mixed liquor.Next stop stirring and make to mix
The particle precipitation in liquid is closed, the supernatant of mixed liquor is then removed and mixed liquor is filtered using centrifugal separator, afterwards
Filter medium is cleaned using clear water, silver powder is obtained finally by dry.
<Comparative example 2>
It is molten to the pure water input 64g silver nitrate solutions, 29g ammonia solutions (concentration 25%) and 8g nitric acid of 930g room temperature
Liquid, 42g potassium nitrate solutions, 28g ammonium sulfate, and the 1st reaction solution is prepared by stirring and dissolving.In addition, to the pure of 1000g room temperature
Water purification puts into 10g hydroquinones, and prepares the 2nd reaction solution by stirring and dissolving.
Next, the 2nd reaction solution is disposably added to above-mentioned 1st reaction solution under the lasting reaction of stirring the 1st liquid status
In, and be stirred for after the addition was complete 5 minutes, so that the particle growth in mixed liquor.Next stop stirring and make to mix
The particle precipitation in liquid is closed, the supernatant of mixed liquor is then removed and mixed liquor is filtered using centrifugal separator, afterwards
Filter medium is cleaned using clear water, silver powder is obtained finally by dry.
[table 1]
Test example
(1) SEM dimension measurements
For the silver powder produced according to the embodiment of the present invention and comparative example is applicable in, Japan Electronics strain formula is being utilized
The scanning electron microscope of commercial firm (JEOL) manufacture has calculated average after being measured to each diameter of 100 powder
Value.
(2) content of organics measures
For the silver powder produced according to the embodiment of the present invention and comparative example is applicable in, Seiko instrument (Seiko is utilized
Instruments) manufacture TG/DTA EXART6600, in atmosphere with 10 DEG C/min of programming rate to room temperature to 500 DEG C
Scope perform TGA and analyze and determined the content of organic matter whereby.
(3) percent thermal shrinkage measures
For the silver powder produced according to the embodiment of the present invention and comparative example is applicable in, TA instruments (TA is utilized
Instruments) the TMA Q400 of manufacture, rise to 260 DEG C from room temperature with 3 DEG C/min of programming rate in atmosphere and keep
When 260 DEG C of state 2 is small, then with 3 DEG C/min of programming rate be warming up to 400 DEG C and keep 400 DEG C state 2 it is small when, it is right
Shrinking percentage in 260~400 DEG C of sections is determined.
[table 2]
As shown in table 2, it can be found that shrinking percentage when using ammonia and nitric acid in 260 to 400 DEG C of sections is less than 10%.
In addition it is also found that in addition to using only the situation of ammonia solution and salpeter solution (embodiment 1 to embodiment 3), use
When ammonium nitrate provides ammonium ion and nitrate ion, the shrinking percentage minimizing effect more than equal can be showed, and pass through and compare
Example 2 can not realize contraction it can be found that during using the potassium nitrate and ammonium sulfate that are capable of providing ammonium ion and nitrate ion
Rate minimizing effect.
For the feature described in each embodiment as described above, structure, effect etc., there is neck belonging to embodiment
The personnel of the general knowledge in domain can be combined by other embodiment or deformation implementation.Therefore, as described above combination or
Deform relevant content and should be interpreted that and be included within the scope of the present invention.
Claims (9)
- A kind of 1. manufacture method of silver powder, it is characterised in that including：Silver salt reduction step (S2), by manufacture comprising silver ion, the 1st reaction solution of ammonia and nitric acid and comprising reducing agent the 2nd The reaction solution manufacturing step (S21) of reaction solution andIt is made up of the precipitation step (S22) for making the 1st reaction solution and the 2nd reaction solution react to obtain silver powder.
- 2. the manufacture method of silver powder according to claim 1, it is characterised in that：Above-mentioned ammonia includes 250 to 600 parts by weight relative to the above-mentioned silver ion of 100 parts by weight.
- 3. the manufacture method of silver powder according to claim 2, it is characterised in that：Above-mentioned nitric acid includes 20 to 230 parts by weight relative to the above-mentioned silver ion of 100 parts by weight.
- 4. the manufacture method of silver powder according to claim 3, it is characterised in that：Above-mentioned reducing agent includes 50 to 60 parts by weight relative to the silver ion being included in above-mentioned 1st reaction solution of 100 parts by weight.
- 5. the manufacture method of silver powder according to claim 1, it is characterised in that：Above-mentioned reaction solution manufacturing step (S21) is gone forward side by side by adding silver ion, ammonia spirit and aqueous solution of nitric acid to solvent Row stirring and dissolving and manufacture the 1st reaction solution,And above-mentioned reaction solution manufacturing step (S21) is by adding reducing agent to solvent and to carry out stirring and dissolving anti-to manufacture the 2nd The step of answering liquid.
- 6. the manufacture method of silver powder according to claim 5, it is characterised in that：Above-mentioned precipitation step (S22) is slowly added dropwise or disposably adds in the state of being stirred to above-mentioned 1st reaction solution Above-mentioned 2nd reaction solution and the step of bring it about reaction.
- 7. the manufacture method of silver powder according to claim 6, it is characterised in that：Above-mentioned precipitation step (S22) is further addition from by aliphatic acid, soap, surfactant, organic metal, chelating Selected in the group that agent and protecting colloid are formed more than one and the step of bring it about reaction.
- 8. the manufacture method of silver powder according to claim 4, it is characterised in that：Above-mentioned reducing agent is selected from the group being made of hydroquinone, ascorbic acid, alkanolamine, hydrazine and formalin More than one.
- A kind of 9. silver powder, it is characterised in that：In crystallization average diameter is 1.5 μm to 3 μm of silver powder,The film manufactured using above-mentioned silver powder is risen to 260 DEG C from room temperature with 3 DEG C/min of programming rate in atmosphere and is protected Hold 2 it is small when, then with 3 DEG C/min of programming rate from 260 DEG C be warming up to 400 DEG C and keep 2 it is small when so that its 260~ Shrinking percentage in 400 DEG C of sections is less than 10%.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2015-0113932 | 2015-08-12 | ||
| KR1020150113932A KR101733165B1 (en) | 2015-08-12 | 2015-08-12 | The manufacturing method of silver powder for high temperature sintering conductive paste |
| PCT/KR2016/008474 WO2017026722A1 (en) | 2015-08-12 | 2016-08-01 | Production method for silver powder for high-temperature sintering type of electrically-conductive paste |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107921543A true CN107921543A (en) | 2018-04-17 |
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| CN201680047257.XA Pending CN107921543A (en) | 2015-08-12 | 2016-08-01 | The manufacture method of high temperature sintering type conductive paste silver powder |
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| JP (1) | JP2018523758A (en) |
| KR (1) | KR101733165B1 (en) |
| CN (1) | CN107921543A (en) |
| WO (1) | WO2017026722A1 (en) |
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| CN108941609A (en) * | 2018-09-10 | 2018-12-07 | 河南金渠银通金属材料有限公司 | Solar cell conductive silver paste high performance spherical super fine silver powder and preparation method thereof |
| CN109637693A (en) * | 2018-12-17 | 2019-04-16 | 中国计量大学 | A kind of conductive silver paste and preparation method thereof based on from the silver-colored frame of sintering |
| CN113365767A (en) * | 2018-11-30 | 2021-09-07 | LS-Nikko铜制炼株式会社 | Method for manufacturing silver powder with adjustable shrinkage rate |
| CN115335163A (en) * | 2020-03-25 | 2022-11-11 | Ls-日光铜制炼株式会社 | Silver powder for conductive paste with improved viscosity stability and method for producing same |
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| KR102007856B1 (en) * | 2017-10-13 | 2019-08-06 | 엘에스니꼬동제련 주식회사 | The manufacturing method of silver powder with improved dispersibility |
| KR102061719B1 (en) * | 2017-10-30 | 2020-01-02 | 엘에스니꼬동제련 주식회사 | Silver powder and method for manufacturing the same |
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| KR102197542B1 (en) * | 2018-11-30 | 2020-12-31 | 엘에스니꼬동제련 주식회사 | The manufacturing method of silver powder with improved washability |
| CN115464147A (en) * | 2022-09-16 | 2022-12-13 | 北京曙光航空电气有限责任公司 | Silver powder manufacturing method |
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| CN113365767A (en) * | 2018-11-30 | 2021-09-07 | LS-Nikko铜制炼株式会社 | Method for manufacturing silver powder with adjustable shrinkage rate |
| CN109637693A (en) * | 2018-12-17 | 2019-04-16 | 中国计量大学 | A kind of conductive silver paste and preparation method thereof based on from the silver-colored frame of sintering |
| CN115335163A (en) * | 2020-03-25 | 2022-11-11 | Ls-日光铜制炼株式会社 | Silver powder for conductive paste with improved viscosity stability and method for producing same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2018523758A (en) | 2018-08-23 |
| KR101733165B1 (en) | 2017-05-08 |
| KR20170019727A (en) | 2017-02-22 |
| WO2017026722A1 (en) | 2017-02-16 |
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