WO2017026722A1 - Production method for silver powder for high-temperature sintering type of electrically-conductive paste - Google Patents

Production method for silver powder for high-temperature sintering type of electrically-conductive paste Download PDF

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WO2017026722A1
WO2017026722A1 PCT/KR2016/008474 KR2016008474W WO2017026722A1 WO 2017026722 A1 WO2017026722 A1 WO 2017026722A1 KR 2016008474 W KR2016008474 W KR 2016008474W WO 2017026722 A1 WO2017026722 A1 WO 2017026722A1
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silver powder
silver
reaction solution
solution
parts
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PCT/KR2016/008474
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French (fr)
Korean (ko)
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진우민
권태현
이창근
우상덕
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엘에스니꼬동제련 주식회사
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Priority to CN201680047257.XA priority Critical patent/CN107921543A/en
Priority to JP2018527702A priority patent/JP2018523758A/en
Publication of WO2017026722A1 publication Critical patent/WO2017026722A1/en

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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
    • 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

Definitions

  • the present invention relates to a method for producing silver powder for high temperature sintered conductive paste.
  • a conductive metal paste is a paste in which electricity flows in a dried coating film having a coating ability capable of forming a coating film.
  • a conductive metal paste is a fluid composition in which a conductive filler (metal filler) is dispersed in a vehicle composed of a resin binder and a solvent. It is widely used for forming external electrodes of Recently, after the fact that the organic polymer is also known that electricity flows, research and development on the conductive polymer is actively progressed, but since the conductive polymer is obtained based on the conjugated double bond structure, the molecular chain is rigid, crystalline This has a problem that it is difficult to produce a paste having excellent coating suitability in that it is not easily dissolved by a solvent.
  • the conductive metal paste currently in practical use is a resin curable type in which a conductive filler is squeezed by curing the resin at a low temperature of 200 ° C. or lower to secure conduction, and an organic vehicle component volatilizes under a high temperature atmosphere of 500 to 1200 ° C.
  • a sintering type in which conductive fillers sinter to secure conduction.
  • the sintered conductive paste is composed of a conductive filler centered on a noble metal, a glass frit, and an organic vehicle (resin and an organic solvent), and the organic vehicle component is dried by treating the coated film at a high temperature.
  • This plastic evaporation and fusion between the metal pillars causes the sintered coating film to exhibit conductivity.
  • the glass frit component acts as an inorganic binder while being sintered in the coating film, thereby providing adhesion to the substrate.
  • the organic vehicle acts as an organic liquid medium for printing metal powder and glass frit. Organic matter remaining inside the cured coating film has an adverse effect on the performance of the application, such as increasing electrical resistance. It causes a problem of having to lower the content.
  • Patent Document 1 Japanese Patent Laid-Open No. 2005-48237
  • an alkali or a complexing agent is added to a silver salt-containing aqueous solution to reduce precipitation of finely dispersed spherical silver powder of 0.6 ⁇ m or less.
  • the method of obtaining the fine silver powder which has fine dispersibility which is fine silver powder and has a dispersibility closer to monodispersion with few aggregation of granules is proposed.
  • Patent Document 2 Japanese Patent Laid-Open No. 2010-70793 discloses an aqueous silver ammine complex solution by mixing and reacting an aqueous solution of silver nitrate with aqueous ammonia to obtain a silver ammine complex aqueous solution.
  • the method of obtaining the average particle diameter of 0.1 micrometer or more and less than 1 micrometer, the sharp particle size distribution, and the highly dispersible spherical silver powder is mixed by mixing a reducing agent aqueous solution and reducing precipitated silver particles.
  • the present invention is to solve the problems as described above, which is a silver powder that can be suitably used as the conductive metal filler of the sintered conductive paste, the heat shrinkage in the temperature range of 260 ⁇ 400 °C low, heat shrinkage of the substrate and silver powder It is to provide a method for producing silver powder that can suppress the difference in behavior.
  • the present invention is a silver powder by reacting the reaction solution preparation step (S21) and the first reaction solution and the second reaction solution to prepare a second reaction solution containing a first reaction solution and a reducing agent containing silver ions, ammonia and nitric acid It provides a silver powder manufacturing method comprising a; silver salt reduction step (S2) comprising a precipitation step (S22) to obtain.
  • ammonia is characterized in that it comprises 250 to 600 parts by weight based on 100 parts by weight of the silver ions.
  • the nitric acid is characterized in that it comprises 20 to 230 parts by weight based on 100 parts by weight of the silver ions.
  • the reducing agent is characterized in that it comprises 50 to 60 parts by weight based on 100 parts by weight of silver ions contained in the first reaction solution.
  • the reaction solution production step (S21) is a silver ions, ammonia aqueous solution and nitric acid solution to the solvent and stirred to prepare a first reaction solution by dissolving
  • the reaction solution production step (S21) is to add a reducing agent to the solvent It is characterized in that the stirring to dissolve to prepare a second reaction solution.
  • the precipitation step (S22) is characterized in that the step of reacting by dropwise addition or batch addition of the second reaction solution in the state of stirring the first reaction solution.
  • the precipitation step (S22) is characterized in that the step of reacting by further adding any one or more selected from the group consisting of fatty acids, fatty acid salts, surfactants, organometallic, chelate forming agents and protective colloids.
  • the reducing agent is characterized in that at least one member selected from the group consisting of hydroquinone, ascorbic acid, alkanolamine, hydrazine and formalin.
  • the present invention is a silver powder having a crystallite average diameter of 1.5um to 3um, the film prepared using the silver powder is maintained at a temperature increase rate of 3 °C / min in air at room temperature to 260 °C 2 hours, temperature rising rate 3 After the temperature was raised from 260 ° C. to 400 ° C. at 2 ° C./min.
  • the present invention is a method for producing a silver powder for high-temperature sintered conductive paste, which can produce a uniform silver powder by varying the amount of ammonia and nitric acid, as well as a substrate and silver powder with a shrinkage of 260-400 ° C. of less than 10%. It is possible to provide a high-temperature sintered conductive paste having excellent reliability after high-temperature sintering by suppressing the difference in heat shrinkage behavior.
  • shrinkage rate in 260-400 degreeC can be suppressed, it can use suitably as an electrically conductive filler used especially for the sintering type electrically conductive paste for laminated ceramic capacitors.
  • Method for producing a silver powder for high temperature sintered conductive paste is a silver salt manufacturing step (S1); Silver salt reduction step (S2); Purification step such as filtration and washing (S3); And a surface treatment step (S4).
  • the production method of silver powder according to the present invention necessarily includes a silver salt reduction step (S2), other steps can be omitted.
  • Silver salt preparation step (S1) is a silver salt solution containing silver ions (Ag + ) by acid treatment of silver (Ag + ) in the form of ingots, ribs, granules
  • the silver salt solution may be prepared by directly preparing a silver salt solution through this step, but commercially available silver nitrate may be performed afterwards using a silver salt complex or a silver intermediate solution.
  • Silver salt reduction step (S2) is a step of depositing silver particles by reducing the silver ions by adding a reducing agent and ammonia to the silver salt solution, silver ions, ammonia and nitric acid It includes a reaction solution manufacturing step (S21) for producing a second reaction solution containing a first reaction solution and a reducing agent including and a precipitation step (S22) of reacting the first reaction solution and the second reaction solution to obtain a silver powder. .
  • reaction solution preparation step (S21) ammonia and nitric acid are added to the silver salt solution containing silver ions, stirred, and dissolved to prepare a first reaction solution.
  • the silver ions are not limited as long as they are in the form of silver cations.
  • silver nitrate may be a silver salt complex or silver intermediate.
  • concentration of silver ions is not limited but may be in the range of 6 g / L to 40 g / L. If it is less than 6g / L yield is low economic problem, and if more than 40g / L there is a problem that causes the aggregation of the powder.
  • the present invention is believed to increase the firing temperature by adding ammonia and nitric acid to the silver salt solution to include silver powder in which ammonium nitrate combined with nitrate and ammonium ions is produced (precipitated), thereby increasing the firing temperature.
  • ammonia and nitric acid added to the silver salt solution to include silver powder in which ammonium nitrate combined with nitrate and ammonium ions is produced (precipitated), thereby increasing the firing temperature.
  • ammonia and nitric acid to the silver salt solution to include silver powder in which ammonium nitrate combined with nitrate and ammonium ions is produced (precipitated), thereby increasing the firing temperature.
  • ammonium nitrate combined with nitrate and ammonium ions is produced (precipitated)
  • Ammonia may be used in the form of an aqueous solution, and the amount of the aqueous ammonia solution may be added in an amount of 250 to 600 parts by weight based on 100 parts by weight of silver ions.
  • the amount of the aqueous ammonia solution may be added in an amount of 250 to 600 parts by weight based on 100 parts by weight of silver ions.
  • ammonia is added below 250 parts by weight, the effect of reducing heat shrinkage is insignificant, and when ammonia is added in excess of 600 parts by weight, there is a problem in that the size of the silver powder produced is greatly reduced.
  • a 25% aqueous solution of ammonia it is preferable to add 60 to 150 parts by weight based on 100 parts by weight of silver ions.
  • the ammonia includes its derivatives.
  • the amount of nitric acid used is preferably added in an amount of 20 to 230 parts by weight based on 100 parts by weight of silver ions.
  • the nitric acid includes its derivatives.
  • the first reaction solution containing silver ions, ammonia and nitric acid may be prepared in the form of a slurry by adding silver ions, aqueous ammonia and nitric acid to a solvent such as water, stirring and dissolving the solution. .
  • Reaction liquid preparation step (S21) according to an embodiment of the present invention also prepares a second reaction liquid containing a reducing agent.
  • the reducing agent may be at least one selected from the group consisting of ascorbic acid, alkanolamine, hydroquinone, hydrazine and formalin, and among these, hydroquinone may be preferably selected.
  • the amount of the reducing agent is preferably included in an amount of 50 to 60 parts by weight based on 100 parts by weight of silver ions contained in the first reaction solution. When using less than 50 parts by weight, all of the silver ions may not be reduced, and when used in excess of 60 parts by weight may increase the organic content may be a problem.
  • the second reaction solution containing a reducing agent may be prepared in an aqueous solution state by adding a reducing agent to a solvent such as water and stirring the solution.
  • Precipitation step (S22) is a step of obtaining a silver powder by reacting the first reaction solution and the second reaction solution, stirring the first reaction solution prepared by the reaction solution preparation step (S21)
  • the second reaction liquid can be slowly added dropwise or added in a batch to react.
  • the batch reaction may be completed in a short time to collectively add the bulk to prevent aggregation of the particles and to improve dispersibility.
  • dispersant examples include fatty acids, fatty acid salts, surfactants, organometallics, chelate formers and protective colloids.
  • the remaining organic matter content may be increased, so it is desirable to control the particle size, the remaining organic matter content, and the crystallite diameter of the silver powder without adding the dispersant.
  • Purification step (S3) is a silver salt reduction step (S2) after completing the silver particle precipitation reaction to remove and wash the silver powder dispersed in an aqueous solution or slurry using filtration and the like Step S31 is included. More specifically, after the silver particles in the silver powder dispersion are precipitated, the supernatant of the dispersion is discarded and filtered using a centrifuge, and the filter medium is washed with pure water. The washing process must be done by completely removing the wash water from which the powder has been washed. Therefore, the water content is reduced to less than 10%. It is also possible to optionally add the aforementioned dispersants to the reaction complete solution prior to filtration to prevent aggregation of the silver powder.
  • the purification step (S3) may further comprise a drying and disintegration step (S34) after washing.
  • Surface treatment step (S4) is a step of hydrophobizing the hydrophilic surface of the silver powder, it may be made selectively. More specifically, after controlling the moisture content of the wet cake (wet cake) obtained after filtration to less than 10% can be added to the surface treatment agent for the surface treatment of the silver powder and the moisture content can be adjusted to 70% to 85%. Thereafter, silver powder can be obtained through drying and pulverization. When surface treatment of silver powder, the powder should be well dispersed, and the surface treatment is sufficient. If the water content is low, the dispersion efficiency is poor, so it is better to surface-treat a certain amount with water content.
  • Silver powder prepared according to an embodiment of the present invention by measuring the diameter size of each of the 100 powders using a scanning electron microscope (SEM) and the average size is measured in the range of 1.5um to 3um, in the air
  • SEM scanning electron microscope
  • the organic matter content measured by TGA analysis in the range from normal temperature to 500 degreeC at the temperature increase rate of 10 degreeC / min is 1.0 weight% or less.
  • the film specimen prepared using the silver powder prepared according to an embodiment of the present invention is maintained at 260 °C, 260 °C 2 hours at room temperature at a heating rate of 3 °C / min in air, 400 °C at a heating rate of 3 °C / min To maintain the temperature at 400 °C for 2 hours until the shrinkage of 260 ⁇ 400 °C section is 10% or less.
  • the 1st reaction liquid was made to stir, the 2nd reaction liquid was added to this 1st reaction liquid collectively, and further stirred for 5 minutes after completion
  • stirring was stopped the particles in the mixed solution were allowed to settle, the supernatant of the mixed solution was discarded, the mixed solution was filtered using a centrifugal separator, the media was washed with pure water, dried, and silver powder was obtained.
  • the 1st reaction liquid was made to stir, the 2nd reaction liquid was added to this 1st reaction liquid collectively, and further stirred for 5 minutes after completion
  • stirring was stopped the particles in the mixed solution were allowed to settle, the supernatant of the mixed solution was discarded, the mixed solution was filtered using a centrifugal separator, the media was washed with pure water, dried, and silver powder was obtained.
  • the 1st reaction liquid was made to stir, the 2nd reaction liquid was added to this 1st reaction liquid collectively, and further stirred for 5 minutes after completion
  • stirring was stopped the particles in the mixed solution were allowed to settle, the supernatant of the mixed solution was discarded, the mixed solution was filtered using a centrifugal separator, the media was washed with pure water, dried, and silver powder was obtained.
  • the 1st reaction liquid was made to stir, the 2nd reaction liquid was added to this 1st reaction liquid collectively, and further stirred for 5 minutes after completion
  • stirring was stopped the particles in the mixed solution were allowed to settle, the supernatant of the mixed solution was discarded, the mixed solution was filtered using a centrifugal separator, the media was washed with pure water, dried, and silver powder was obtained.
  • the 1st reaction liquid was made to stir, the 2nd reaction liquid was added to this 1st reaction liquid collectively, and further stirred for 5 minutes after completion
  • stirring was stopped the particles in the mixed solution were allowed to settle, the supernatant of the mixed solution was discarded, the mixed solution was filtered using a centrifugal separator, the media was washed with pure water, dried, and silver powder was obtained.
  • the 1st reaction liquid was made to stir, the 2nd reaction liquid was added to this 1st reaction liquid collectively, and further stirred for 5 minutes after completion
  • stirring was stopped the particles in the mixed solution were allowed to settle, the supernatant of the mixed solution was discarded, the mixed solution was filtered using a centrifugal separator, the media was washed with pure water, dried, and silver powder was obtained.
  • the 1st reaction liquid was made to stir, the 2nd reaction liquid was added to this 1st reaction liquid collectively, and further stirred for 5 minutes after completion
  • stirring was stopped the particles in the mixed solution were allowed to settle, the supernatant of the mixed solution was discarded, the mixed solution was filtered using a centrifugal separator, the media was washed with pure water, dried, and silver powder was obtained.
  • the 1st reaction liquid was made to stir, the 2nd reaction liquid was added to this 1st reaction liquid collectively, and further stirred for 5 minutes after completion
  • stirring was stopped the particles in the mixed solution were allowed to settle, the supernatant of the mixed solution was discarded, the mixed solution was filtered using a centrifugal separator, the media was washed with pure water, dried, and silver powder was obtained.
  • the silver powders prepared according to the Examples and Comparative Examples of the present invention were measured by averaging the diameters of 100 powders using a scanning electron microscope manufactured by JEOL.
  • Example 1 1.54 0.22 7.8
  • Example 2 1.67 0.40 6.3
  • Example 3 1.61 0.68 7.5
  • Example 4 1.82 0.21 7.5
  • Example 5 1.95 0.10 6.0
  • Example 6 1.61 0.10 3.7 Comparative Example 1 1.43 0.49 16.2 Comparative Example 2 1.29 0.10 14.6

Abstract

The present invention relates to a production method for a silver powder, the method comprising: a silver salt reducing step (S2) including a reaction-fluid production step (S21) involving the production of a first reaction fluid comprising silver ions, ammonia and nitric acid, and a second reaction fluid comprising a reducing agent; and a precipitation step (S22) in which a silver powder is obtained by reacting the first reaction fluid and the second reaction fluid. The production method makes it possible to produce a silver powder having a shrinkage ratio of no more than 10% in the 260-400°C interval.

Description

고온 소결형 도전성 페이스트용 은 분말의 제조방법Manufacturing method of silver powder for high temperature sintered conductive paste
본 발명은 고온 소결형 도전성 페이스트용 은 분말의 제조방법에 관한 것이다.The present invention relates to a method for producing silver powder for high temperature sintered conductive paste.
도전성 금속 페이스트는 도막 형성이 가능한 도포 적성을 갖고 건조된 도막에 전기가 흐르는 페이스트로서, 수지계 바인더와 용매로 이루어지는 비히클 중에 도전성 필러(금속 필러)를 분산시킨 유동성 조성물이며, 전기 회로의 형성이나 세라믹 콘덴서의 외부 전극의 형성 등에 널리 사용되고 있다. 최근 유기 고분자에도 전기가 흐른다라는 사실이 알려 진 후, 전도성 고분자에 대한 연구 개발이 활발히 진행되고 있지만, 전도성 고분자는 공액 이중 결합 구조를 기본으로 전도성을 얻고 있기 때문에, 분자 사슬이 강직하고, 결정성이 높아 용제에 의해 잘 용해되지 못한다라는 점에서 도포 적성이 우수한 페이스트로 제조하기에는 어렵다는 문제점을 가지고 있다.A conductive metal paste is a paste in which electricity flows in a dried coating film having a coating ability capable of forming a coating film. A conductive metal paste is a fluid composition in which a conductive filler (metal filler) is dispersed in a vehicle composed of a resin binder and a solvent. It is widely used for forming external electrodes of Recently, after the fact that the organic polymer is also known that electricity flows, research and development on the conductive polymer is actively progressed, but since the conductive polymer is obtained based on the conjugated double bond structure, the molecular chain is rigid, crystalline This has a problem that it is difficult to produce a paste having excellent coating suitability in that it is not easily dissolved by a solvent.
현재 실용화되고 있는 도전성 금속 페이스트는 200℃ 이하의 낮은 온도에서 수지의 경화에 의하여 도전성 필러가 압착되어 도통(導通)을 확보하는 수지 경화형과, 500~1200℃의 고온 분위기 하에서 유기 비히클 성분이 휘발하여 도전성 필러가 소결해서 도통을 확보하는 소결형이 있다.The conductive metal paste currently in practical use is a resin curable type in which a conductive filler is squeezed by curing the resin at a low temperature of 200 ° C. or lower to secure conduction, and an organic vehicle component volatilizes under a high temperature atmosphere of 500 to 1200 ° C. There is a sintering type in which conductive fillers sinter to secure conduction.
이 중, 소결형 도전성 페이스트는 귀금속을 중심으로 하는 도전성 필러와 글라스 프릿(glass frit), 유기 비히클(수지와 유기 용제)로 구성되며, 도포된 도막을 건조한 후, 고온에서 처리함에 따라 유기 비히클 성분이 소성 증발되고, 금속 필러들 사이에 융착이 일어나 소결된 도막은 전도성을 발현하게 된다. 이 때 글라스 플릿 성분은 도막 내에서 소결된 채 무기 바인더로써의 역할을 하게 되어 기판과의 접착력을 부여한다. 유기 비히클은 금속 분말 및 유리 프리트를 인쇄 가능하게 하기 위한 유기 액체 매체로서 작용하는데, 경화된 도막 내부에 잔존하는 유기물은 전기적 저항을 증가시키는 등 어플리케이션의 성능에 좋지 않은 영향을 미치므로, 잔존 유기물의 함량을 낮추어야 하는 문제를 야기한다. Among these, the sintered conductive paste is composed of a conductive filler centered on a noble metal, a glass frit, and an organic vehicle (resin and an organic solvent), and the organic vehicle component is dried by treating the coated film at a high temperature. This plastic evaporation and fusion between the metal pillars causes the sintered coating film to exhibit conductivity. At this time, the glass frit component acts as an inorganic binder while being sintered in the coating film, thereby providing adhesion to the substrate. The organic vehicle acts as an organic liquid medium for printing metal powder and glass frit. Organic matter remaining inside the cured coating film has an adverse effect on the performance of the application, such as increasing electrical resistance. It causes a problem of having to lower the content.
소결형 도전성 페이스트에 사용되는 은분에 대해서는 전극이나 회로의 파인라인화 추세에 대응하기 위하여, 미립이며 또한 샤프한 입도 분포를 갖는 은분이 요구되기 때문에, 그에 대응한 새로운 기술이 제안되어 오고 있다.For silver powder used in the sintered conductive paste, in order to cope with the tendency of fine lines of electrodes and circuits, silver powder having fine and sharp particle size distribution is required, and therefore, a new technique corresponding thereto has been proposed.
예를 들면, 특허문헌 1(일본국 특개2005-48237호 공보)에 있어서, 은염 함유 수용액에, 알칼리 또는 착화제를 첨가하여, 0.6㎛ 이하의 미립자화한 고분산성의 구상의 은분을 환원 석출시킴에 의해, 미립의 은분이며, 또한 분립의 응집이 적은 단분산에 보다 가까운 분산성을 구비하는 미립 은분을 얻는 방법이 제안되어 있다.For example, in Patent Document 1 (Japanese Patent Laid-Open No. 2005-48237), an alkali or a complexing agent is added to a silver salt-containing aqueous solution to reduce precipitation of finely dispersed spherical silver powder of 0.6 µm or less. By this, the method of obtaining the fine silver powder which has fine dispersibility which is fine silver powder and has a dispersibility closer to monodispersion with few aggregation of granules is proposed.
또한, 특허문헌 2(일본국 특개2010-70793호 공보)에는, 질산은 수용액과 암모니아수를 혼합하여 반응시켜서 은 암민 착체 수용액을 얻고, 시드가 되는 입자 및 이민 화합물의 존재 하에 있어서, 당해 은 암민 착체 수용액과 환원제 수용액을 혼합하여, 은 입자를 환원 석출시킴으로써, 평균 입경이 0.1㎛ 이상, 1㎛ 미만이며, 입도 분포가 샤프하고 또한 고분산성의 구상 은분을 얻는 방법이 제안되어 있다.In addition, Patent Document 2 (Japanese Patent Laid-Open No. 2010-70793) discloses an aqueous silver ammine complex solution by mixing and reacting an aqueous solution of silver nitrate with aqueous ammonia to obtain a silver ammine complex aqueous solution. The method of obtaining the average particle diameter of 0.1 micrometer or more and less than 1 micrometer, the sharp particle size distribution, and the highly dispersible spherical silver powder is mixed by mixing a reducing agent aqueous solution and reducing precipitated silver particles.
그러나 은분말이 미립화될수록 열수축률이 커지는 경향이 있는데, 400~800℃ 의 고온에서 소결되는 소결형 도전성 페이스트의 금속 필러와 기판과의 열수축 거동의 차이가 크면 기판과 금속 도막 사이의 박리, 휨, 변형, 크랙 등이 발생하는 문제가 있다. However, as the silver powder is atomized, the thermal shrinkage tends to increase. If the difference in the heat shrinkage behavior between the metal filler and the substrate of the sintered conductive paste sintered at a high temperature of 400 to 800 ° C. is large, peeling, warping and deformation between the substrate and the metal coating film There is a problem that cracks occur.
본 발명은 상기와 같은 문제점을 해결하기 위한 것으로 소결형 도전성 페이스트의 도전성 금속 필러로서 호적하게 사용될 수 있는 은 분말로서, 260~400℃의 온도범위에서의 열수축율이 낮아, 기판과 은분말의 열수축 거동의 차를 억제할 수 있는 은 분말의 제조방법을 제공하는 것이다. The present invention is to solve the problems as described above, which is a silver powder that can be suitably used as the conductive metal filler of the sintered conductive paste, the heat shrinkage in the temperature range of 260 ~ 400 ℃ low, heat shrinkage of the substrate and silver powder It is to provide a method for producing silver powder that can suppress the difference in behavior.
그러나 본 발명의 목적들은 상기에 언급된 목적으로 제한되지 않으며, 언급되지 않은 또 다른 목적들은 아래의 기재로부터 당업자에게 명확하게 이해될 수 있을 것이다.However, the objects of the present invention are not limited to the above-mentioned objects, and other objects not mentioned will be clearly understood by those skilled in the art from the following description.
본 발명은 은 이온, 암모니아 및 질산을 포함하는 제1 반응액 및 환원제를 포함하는 제2 반응액을 제조하는 반응액제조단계(S21) 및 제1 반응액 및 제2 반응액을 반응시켜 은 분말을 얻는 석출단계(S22)를 포함하는 은 염 환원단계(S2);를 포함하는 은 분말 제조방법을 제공한다. The present invention is a silver powder by reacting the reaction solution preparation step (S21) and the first reaction solution and the second reaction solution to prepare a second reaction solution containing a first reaction solution and a reducing agent containing silver ions, ammonia and nitric acid It provides a silver powder manufacturing method comprising a; silver salt reduction step (S2) comprising a precipitation step (S22) to obtain.
또한 상기 암모니아는 상기 은 이온 100 중량부에 대하여 250 내지 600 중량부로 포함되는 것을 특징으로 한다.In addition, the ammonia is characterized in that it comprises 250 to 600 parts by weight based on 100 parts by weight of the silver ions.
또한 상기 질산은 상기 은 이온 100 중량부에 대하여 20 내지 230 중량부로 포함되는 것을 특징으로 한다.In addition, the nitric acid is characterized in that it comprises 20 to 230 parts by weight based on 100 parts by weight of the silver ions.
또한 상기 환원제는 상기 제1 반응액에 포함되는 은 이온 100 중량부에 대하여 50 내지 60 중량부로 포함되는 것을 특징으로 한다. 또한 상기 반응액제조단계(S21)는 용제에 은 이온, 암모니아 수용액 및 질산 수용액을 첨가하고 교반하여 용해시켜 제1 반응액을 제조하고, 상기 반응액제조단계(S21)는 용제에 환원제를 첨가하고 교반하여 용해시켜 제2 반응액을 제조하는 단계인 것을 특징으로 한다.In addition, the reducing agent is characterized in that it comprises 50 to 60 parts by weight based on 100 parts by weight of silver ions contained in the first reaction solution. In addition, the reaction solution production step (S21) is a silver ions, ammonia aqueous solution and nitric acid solution to the solvent and stirred to prepare a first reaction solution by dissolving, the reaction solution production step (S21) is to add a reducing agent to the solvent It is characterized in that the stirring to dissolve to prepare a second reaction solution.
또한 상기 석출단계(S22)는 상기 제1 반응액을 교반하는 상태에서 상기 제2 반응액을 적가하거나 일괄 첨가하여 반응시키는 단계인 것을 특징으로 한다.In addition, the precipitation step (S22) is characterized in that the step of reacting by dropwise addition or batch addition of the second reaction solution in the state of stirring the first reaction solution.
또한 상기 석출단계(S22)는 지방산, 지방산염, 계면활성제, 유기금속, 킬레이트 형성제 및 보호 콜로이드로 구성되는 군에서 선택되는 어느 1종 이상을 더 첨가하여 반응시키는 단계인 것을 특징으로 한다.In addition, the precipitation step (S22) is characterized in that the step of reacting by further adding any one or more selected from the group consisting of fatty acids, fatty acid salts, surfactants, organometallic, chelate forming agents and protective colloids.
또한 상기 환원제는 하이드로퀴논, 아스코르브산, 알칸올아민, 히드라진 및 포르말린으로 구성되는 군에서 선택되는 1종 이상인 것을 특징으로 한다.In addition, the reducing agent is characterized in that at least one member selected from the group consisting of hydroquinone, ascorbic acid, alkanolamine, hydrazine and formalin.
또한 본 발명은 결정자 평균 지름이 1.5um 내지 3um인 은 분말로서, 상기 은 분말을 이용하여 제조된 필름을 공기 중 승온 속도 3℃/min로 상온에서 260℃로 승온 후 2시간 유지, 승온 속도 3℃/min로 260℃에서 400℃까지 승온 후 2시간 유지하여, 260~400℃ 구간의 수축율이 10% 이하인 은 분말을 제공한다. In addition, the present invention is a silver powder having a crystallite average diameter of 1.5um to 3um, the film prepared using the silver powder is maintained at a temperature increase rate of 3 ℃ / min in air at room temperature to 260 ℃ 2 hours, temperature rising rate 3 After the temperature was raised from 260 ° C. to 400 ° C. at 2 ° C./min.
본 발명은 고온 소결형 도전성 페이스트용 은 분말의 제조방법으로서 암모니아와 질산사용량을 변화시켜 균일한 은분말을 제작할 수 있을 뿐만 아니라, 260~400℃에서의 수축율을 10% 미만으로 하여 기판과 은 분말의 열수축 거동의 차를 억제하여 고온 소결 후 신뢰성이 우수한 고온 소결형 도전성 페이스트를 제공할 수 있다. The present invention is a method for producing a silver powder for high-temperature sintered conductive paste, which can produce a uniform silver powder by varying the amount of ammonia and nitric acid, as well as a substrate and silver powder with a shrinkage of 260-400 ° C. of less than 10%. It is possible to provide a high-temperature sintered conductive paste having excellent reliability after high-temperature sintering by suppressing the difference in heat shrinkage behavior.
또한 260~400℃에서의 수축율을 억제할 수 있기 때문에, 특히 적층형 세라믹 콘덴서용의 소결형 도전성 페이스트에 사용하는 도전성 필러로서 호적하게 사용할 수 있다.Moreover, since shrinkage rate in 260-400 degreeC can be suppressed, it can use suitably as an electrically conductive filler used especially for the sintering type electrically conductive paste for laminated ceramic capacitors.
도 1에 은 분말의 열처리 온도 프로파일을 나타내었다. 1 shows the heat treatment temperature profile of the silver powder.
이하에 본 발명을 상세하게 설명하기에 앞서, 본 명세서에 사용된 용어는 특정의 실시예를 기술하기 위한 것일 뿐 첨부하는 특허청구의 범위에 의해서만 한정되는 본 발명의 범위를 한정하려는 것은 아님을 이해하여야 한다. 본 명세서에 사용되는 모든 기술용어 및 과학용어는 다른 언급이 없는 한은 기술적으로 통상의 기술을 가진 자에게 일반적으로 이해되는 것과 동일한 의미를 가진다.Prior to describing the present invention in detail below, it is understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the invention, which is limited only by the scope of the appended claims. shall. All technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art unless otherwise indicated.
본 명세서 및 청구범위의 전반에 걸쳐, 다른 언급이 없는 한 포함(comprise, comprises, comprising)이라는 용어는 언급된 물건, 단계 또는 일군의 물건, 및 단계를 포함하는 것을 의미하고, 임의의 어떤 다른 물건, 단계 또는 일군의 물건 또는 일군의 단계를 배제하는 의미로 사용된 것은 아니다.Throughout this specification and claims, unless otherwise indicated, the termcomprise, constitutes, and configure means to include the referenced article, step, or group of articles, and step, and any other article It is not intended to exclude a stage or group of things or groups of stages.
한편, 본 발명의 여러 가지 실시예들은 명확한 반대의 지적이 없는 한 그 외의 어떤 다른 실시예들과 결합될 수 있다. 특히 바람직하거나 유리하다고 지시하는 어떤 특징도 바람직하거나 유리하다고 지시한 그 외의 어떤 특징 및 특징들과 결합될 수 있다. 이하, 첨부된 도면을 참조하여 본 발명의 실시예 및 이에 따른 효과를 설명하기로 한다. On the other hand, various embodiments of the present invention can be combined with any other embodiment unless clearly indicated to the contrary. Any feature indicated as particularly preferred or advantageous may be combined with any other feature and features indicated as preferred or advantageous. Hereinafter, with reference to the accompanying drawings will be described an embodiment of the present invention and the effects thereof.
본 발명의 일실시예에 따른 고온 소결형 도전성 페이스트용 은 분말의 제조방법은 은 염 제조단계(S1); 은 염 환원단계(S2); 여과 및 세척 등 정제단계(S3); 및 표면처리단계(S4);를 포함하여 이루어진다. 본 발명에 따른 은 분말의 제조방법은 은 염 환원단계(S2)를 반드시 포함하고, 이외의 단계는 생략 가능하다. Method for producing a silver powder for high temperature sintered conductive paste according to an embodiment of the present invention is a silver salt manufacturing step (S1); Silver salt reduction step (S2); Purification step such as filtration and washing (S3); And a surface treatment step (S4). The production method of silver powder according to the present invention necessarily includes a silver salt reduction step (S2), other steps can be omitted.
1.One. 은 염 제조단계(S1)Silver salt manufacturing step (S1)
본 발명의 일실시예에 따른 은 염 제조단계(S1)는 잉곳, 립, 그래뉼 형태의 은(silver, Ag)을 산처리하여 은 이온(Ag+)을 포함하는 은 염(silver salt) 용액을 제조하는 단계로서, 본 단계를 거쳐 은 염 용액을 직접 제조하여 은 분말을 제조할 수 있으나, 시중에서 구입한 질산은, 은염착체 또는 은 중간체 용액을 이용하여 이 후 단계를 진행할 수 있다.Silver salt preparation step (S1) according to an embodiment of the present invention is a silver salt solution containing silver ions (Ag + ) by acid treatment of silver (Ag + ) in the form of ingots, ribs, granules As a preparing step, the silver salt solution may be prepared by directly preparing a silver salt solution through this step, but commercially available silver nitrate may be performed afterwards using a silver salt complex or a silver intermediate solution.
2.2. 은 염 환원단계(S2)Silver salt reduction step (S2)
본 발명의 일실시예에 따른 은 염 환원단계(S2)는 은 염 용액에 환원제 및 암모니아를 첨가하여 은 이온을 환원시켜 은 입자(silver particle)를 석출하는 단계로서, 은 이온, 암모니아 및 질산을 포함하는 제1 반응액 및 환원제를 포함하는 제2 반응액을 제조하는 반응액제조단계(S21) 및 제1 반응액 및 제2 반응액을 반응시켜 은 분말을 얻는 석출단계(S22)를 포함한다. Silver salt reduction step (S2) according to an embodiment of the present invention is a step of depositing silver particles by reducing the silver ions by adding a reducing agent and ammonia to the silver salt solution, silver ions, ammonia and nitric acid It includes a reaction solution manufacturing step (S21) for producing a second reaction solution containing a first reaction solution and a reducing agent including and a precipitation step (S22) of reacting the first reaction solution and the second reaction solution to obtain a silver powder. .
본 발명의 일실시예에 따른 반응액제조단계(S21)는 은 이온을 포함하는 은 염 용액에 암모니아 및 질산을 첨가하고 교반하여 용해시켜 제1 반응액을 제조한다. In the reaction solution preparation step (S21) according to an embodiment of the present invention, ammonia and nitric acid are added to the silver salt solution containing silver ions, stirred, and dissolved to prepare a first reaction solution.
상기 은 이온은 은 양이온의 형태라면 제한되지 않는다. 일례로 질산은, 은염 착체 또는 은 중간체일 수 있다. 은 이온의 농도는 제한되지 않으나 6g/L 내지 40g/L 범위 내가 좋다. 6g/L 미만의 경우 수율이 낮아져 경제성이 문제되며, 40g/L 초과하는 경우 분말의 응집을 초래하는 문제점이 있다.The silver ions are not limited as long as they are in the form of silver cations. In one example silver nitrate may be a silver salt complex or silver intermediate. The concentration of silver ions is not limited but may be in the range of 6 g / L to 40 g / L. If it is less than 6g / L yield is low economic problem, and if more than 40g / L there is a problem that causes the aggregation of the powder.
본 발명은 제1 반응액에 암모니아와 질산을 첨가함으로써, 260~400℃ 소성구간에서의 수축율을 감소시킬 수 있다. 고온 소결용 도전성 페이스트가 사용되는 세라믹 시트는 보통 600℃ 이상에서 수축이 일어나는데, 도 1의 은 분말의 열처리 온도 프로파일에 나타나는 것과 같이, 은분말이 260℃~400℃ 유지구간에서 수축이 많이 일어나면, 세라믹 시트에 변형 또는 크랙이 발생하는 문제점이 있다. 따라서 260℃ 내지 400℃ 구간에서의 수축률을 감소시킴으로써 세라믹 시트에의 영향을 줄일 필요가 있으며, 일반적으로 260~400℃ 구간에서의 은 분말 수축율이 10% 미만이면 세라믹 시트에 거의 영향을 주지 않는 것으로 볼 수 있다.In the present invention, by adding ammonia and nitric acid to the first reaction solution, it is possible to reduce the shrinkage in the firing section of 260 ~ 400 ℃. Ceramic sheets using high-temperature sintering conductive paste usually shrink at 600 ° C or higher. As shown in the heat treatment temperature profile of the silver powder of FIG. 1, when the silver powder shrinks a lot in the holding period of 260 ° C to 400 ° C, the ceramic sheet There is a problem that deformation or crack occurs in the sheet. Therefore, it is necessary to reduce the influence on the ceramic sheet by reducing the shrinkage in the 260 ℃ to 400 ℃ section, in general, if the silver powder shrinkage in the 260 ~ 400 ℃ section is less than 10% to have little effect on the ceramic sheet. can see.
본 발명은 은 염 용액에 암모니아 및 질산을 첨가함으로써, 질산염과 암모늄 이온이 결합한 질산암모늄이 제조(석출)되는 은 분말에 포함되어 소성 온도를 증가시키는 것으로 추정되며, 질산과 암모니아를 대신하여 질산암모늄을 사용하여도 동일한 효과를 나타낼 수 있다.The present invention is believed to increase the firing temperature by adding ammonia and nitric acid to the silver salt solution to include silver powder in which ammonium nitrate combined with nitrate and ammonium ions is produced (precipitated), thereby increasing the firing temperature. The same effect can be obtained using.
암모니아는 수용액 형태로 사용될 수 있으며, 암모니아 수용액의 사용량은 은 이온 100 중량부에 대하여 250 내지 600 중량부로 첨가하는 것이 좋다. 암모니아가 250 중량부 미만으로 첨가되는 경우 열수축율 감소 효과가 미비하며, 암모니아가 600 중량부를 초과하여 첨가되는 경우 제조된 은 분말의 크기(size)가 크게 감소하는 문제점이 있다. 25% 암모니아 수용액을 사용하는 경우 은 이온 100 중량부에 대하여 60 내지 150 중량부로 첨가하는 것이 좋다. 상기 암모니아는 그 유도체를 포함한다. Ammonia may be used in the form of an aqueous solution, and the amount of the aqueous ammonia solution may be added in an amount of 250 to 600 parts by weight based on 100 parts by weight of silver ions. When ammonia is added below 250 parts by weight, the effect of reducing heat shrinkage is insignificant, and when ammonia is added in excess of 600 parts by weight, there is a problem in that the size of the silver powder produced is greatly reduced. When using a 25% aqueous solution of ammonia, it is preferable to add 60 to 150 parts by weight based on 100 parts by weight of silver ions. The ammonia includes its derivatives.
질산의 사용량은 은 이온 100 중량부에 대하여 20 내지 230 중량부로 첨가하는 것이 좋다. 질산이 20 중량부 미만으로 첨가되는 경우 수축율 감소 효과가 미비하며, 질산이 230 중량부를 초과하여 첨가되는 경우 제조된 은 분말의 크기(size)와 유기물 함량이 크게 증가하는 문제점이 있다. 상기 질산은 그 유도체를 포함한다. The amount of nitric acid used is preferably added in an amount of 20 to 230 parts by weight based on 100 parts by weight of silver ions. When the nitric acid is added less than 20 parts by weight, the shrinkage reduction effect is insignificant, and when the nitric acid is added in excess of 230 parts by weight there is a problem that the size (size) and organic matter content of the silver powder is significantly increased. The nitric acid includes its derivatives.
은 이온, 암모니아 및 질산을 포함하는 제1 반응액은 물 등의 용제에 은 이온, 암모니아 수용액, 질산 수용액을 첨가하고 교반하여 용해시켜 수용액 상태로 제조될 수 있으며, 또한 슬러리 형태로 제조될 수 있다. The first reaction solution containing silver ions, ammonia and nitric acid may be prepared in the form of a slurry by adding silver ions, aqueous ammonia and nitric acid to a solvent such as water, stirring and dissolving the solution. .
본 발명의 일실시예에 따른 반응액제조단계(S21)는 또한 환원제를 포함하는 제2 반응액을 제조한다. Reaction liquid preparation step (S21) according to an embodiment of the present invention also prepares a second reaction liquid containing a reducing agent.
상기 환원제는 아스코르브산, 알칸올아민, 하이드로퀴논, 히드라진 및 포르말린으로 이루어지는 군으로부터 선택되는 1종 이상일 수 있으며, 이 중에서 하이드로퀴논을 바람직하게 선택할 수 있다. 환원제의 함량은 제1 반응액에 포함되는 은 이온 100 중량부에 대하여 50 내지 60 중량부로 포함되는 것이 바람직하다. 50 중량부 미만을 사용하는 경우, 은 이온이 모두 환원되지 않을 수 있고, 60 중량부를 초과하여 사용하는 경우 유기물 함량이 증가하여 문제가 될 수 있다. The reducing agent may be at least one selected from the group consisting of ascorbic acid, alkanolamine, hydroquinone, hydrazine and formalin, and among these, hydroquinone may be preferably selected. The amount of the reducing agent is preferably included in an amount of 50 to 60 parts by weight based on 100 parts by weight of silver ions contained in the first reaction solution. When using less than 50 parts by weight, all of the silver ions may not be reduced, and when used in excess of 60 parts by weight may increase the organic content may be a problem.
환원제를 포함하는 제2 반응액은 물 등의 용매에 환원제를 첨가하고 교반하여 용해시켜 수용액 상태로 제조될 수 있다. The second reaction solution containing a reducing agent may be prepared in an aqueous solution state by adding a reducing agent to a solvent such as water and stirring the solution.
본 발명의 일실시예에 따른 석출단계(S22)는 제1 반응액 및 제2 반응액을 반응시켜 은 분말을 얻는 단계로서, 반응액제조단계(S21)에 의해 제조된 제1 반응액을 교반하는 상태에서 제2 반응액을 천천히 적가하거나, 일괄 첨가하여 반응시킬 수 있다. 바람직하기로는 일괄 첨가하는 것이 빠른 시간 내에 환원 반응이 일괄 종료되어 입자끼리의 응집을 방지하고 분산성을 높일 수 있어 좋다.Precipitation step (S22) according to an embodiment of the present invention is a step of obtaining a silver powder by reacting the first reaction solution and the second reaction solution, stirring the first reaction solution prepared by the reaction solution preparation step (S21) The second reaction liquid can be slowly added dropwise or added in a batch to react. Preferably, the batch reaction may be completed in a short time to collectively add the bulk to prevent aggregation of the particles and to improve dispersibility.
한편, 본 발명의 실시예에서는 은 입자의 분산성 향상 및 응집 방지를 위해 상기 분산제가 더 첨가되어 반응시키는 것을 권리범위에서 제외하지 않는다. 분산제의 예로는 지방산, 지방산염, 계면활성제, 유기 금속, 킬레이트 형성제 및 보호 콜로이드 등을 들 수 있다. On the other hand, in the embodiment of the present invention does not exclude the addition of the dispersant to react in order to improve the dispersibility of the silver particles and prevent aggregation. Examples of dispersants include fatty acids, fatty acid salts, surfactants, organometallics, chelate formers and protective colloids.
그러나, 상기 분산제가 첨가되는 경우, 잔존 유기물 함량이 증가하여 문제될 수 있으므로, 분산제의 첨가 없이 은 분말의 입경, 잔존 유기물 함량 및 결정자 지름을 제어하는 것이 바람직하다. However, when the dispersant is added, the remaining organic matter content may be increased, so it is desirable to control the particle size, the remaining organic matter content, and the crystallite diameter of the silver powder without adding the dispersant.
3.3. 정제단계(S3)Purification step (S3)
본 발명의 일실시예에 따른 정제단계(S3)는 은 염 환원단계(S2)를 통해 은 입자 석출 반응을 완료한 후 수용액 또는 슬러리 내에 분산되어 있는 은 분말을 여과 등을 이용하여 분리하고 세척하는 단계(S31)를 포함한다. 더욱 구체적으로는 은 분말 분산액 중의 은 입자를 침강시킨 후, 분산액의 상등액을 버리고 원심분리기를 이용하여 여과하고, 여재를 순수로 세정한다. 세척을 하는 과정은 분말을 세척한 세척수를 완전히 제거를 해야 이루어 진다. 따라서 함수율 10% 미만으로 감소시킨다. 선택적으로 여과 전에 반응 완료 용액에 상기 언급된 분산제를 첨가하여 은 분말의 응집을 방지하는 것도 가능하다. Purification step (S3) according to an embodiment of the present invention is a silver salt reduction step (S2) after completing the silver particle precipitation reaction to remove and wash the silver powder dispersed in an aqueous solution or slurry using filtration and the like Step S31 is included. More specifically, after the silver particles in the silver powder dispersion are precipitated, the supernatant of the dispersion is discarded and filtered using a centrifuge, and the filter medium is washed with pure water. The washing process must be done by completely removing the wash water from which the powder has been washed. Therefore, the water content is reduced to less than 10%. It is also possible to optionally add the aforementioned dispersants to the reaction complete solution prior to filtration to prevent aggregation of the silver powder.
또한 본 발명의 일실시예에 따른 정제단계(S3)는 세척 후 건조 및 해쇄단계(S34)를 더 포함할 수 있다. In addition, the purification step (S3) according to an embodiment of the present invention may further comprise a drying and disintegration step (S34) after washing.
4.4. 표면처리단계(S4)Surface treatment step (S4)
본 발명의 일실시예에 따른 표면처리단계(S4)는 은 분말의 친수 표면을 소수화하는 단계로서, 선택적으로 이루어질 수 있다. 더욱 구체적으로는 여과 후 얻어지는 습윤 케이크(wet cake)의 함수율을 10% 미만으로 조절한 후 은 분말의 표면처리를 위해 표면처리제를 첨가하고 함수율을 70% ~ 85%로 조절할 수 있다. 이 후 건조, 해쇄 과정을 거쳐 은 분말을 얻을 수 있다. 은 분말을 표면처리할 때 분말의 분산이 잘 되어야 표면처리가 충분히 이루어지고, 함수율이 낮으면 분산 효율이 떨어지기 때문에 일정량을 함수율을 가지고 표면처리를 하는 것이 좋다. Surface treatment step (S4) according to an embodiment of the present invention is a step of hydrophobizing the hydrophilic surface of the silver powder, it may be made selectively. More specifically, after controlling the moisture content of the wet cake (wet cake) obtained after filtration to less than 10% can be added to the surface treatment agent for the surface treatment of the silver powder and the moisture content can be adjusted to 70% to 85%. Thereafter, silver powder can be obtained through drying and pulverization. When surface treatment of silver powder, the powder should be well dispersed, and the surface treatment is sufficient. If the water content is low, the dispersion efficiency is poor, so it is better to surface-treat a certain amount with water content.
본 발명의 일실시예에 따라 제조된 은 분말은 주사전자현미경(SEM)을 이용하여 파우더 100개 각각의 지름 크기를 측정한 후 평균을 내어 측정한 size가 1.5um 내지 3um 범위 내이며, 공기 중 승온 속도 10℃/min로 상온에서 500℃까지의 범위에서 TGA 분석을 행하여 측정된 유기물 함량이 1.0 중량% 이하이다. Silver powder prepared according to an embodiment of the present invention by measuring the diameter size of each of the 100 powders using a scanning electron microscope (SEM) and the average size is measured in the range of 1.5um to 3um, in the air The organic matter content measured by TGA analysis in the range from normal temperature to 500 degreeC at the temperature increase rate of 10 degreeC / min is 1.0 weight% or less.
또한 본 발명의 일실시예에 따라 제조된 은 분말을 이용하여 제조된 필름 시편을 공기 중 승온 속도 3℃/min로 상온에서 260℃, 260℃ 2시간 유지, 승온 속도 3℃/min로 400℃까지 승온, 400℃에서 2시간 유지하여 260~400℃ 구간의 수축율이 10% 이하이다. In addition, the film specimen prepared using the silver powder prepared according to an embodiment of the present invention is maintained at 260 ℃, 260 ℃ 2 hours at room temperature at a heating rate of 3 ℃ / min in air, 400 ℃ at a heating rate of 3 ℃ / min To maintain the temperature at 400 ℃ for 2 hours until the shrinkage of 260 ~ 400 ℃ section is 10% or less.
실시예 및 비교예 Examples and Comparative Examples
<실시예 1><Example 1>
상온의 순수 880g에 질산은 용액 64g, 암모니아 용액(농도 25%) 58g 및 질산 용액(농도 60%) 11g을 넣고 교반하여 용해시켜 제1 반응액을 조제하였다. 한편 상온의 순수 1000g에 하이드로퀴논 10g을 넣고 교반하여 용해시켜 제2 반응액을 조제하였다. 64 g of silver nitrate solution, 58 g of ammonia solution (concentration 25%), and 11 g of nitric acid solution (concentration 60%) were added to 880 g of pure water at room temperature, followed by stirring to dissolve the first reaction solution. On the other hand, 10 g of hydroquinone was added to 1000 g of pure water at room temperature, and stirred to dissolve to prepare a second reaction solution.
이어서, 제1 반응액을 교반한 상태로 하고, 이 제1 반응액에 제2 반응액을 일괄 첨가하여, 첨가 종료 후부터 5분간 더 교반하여 혼합액 중에서 입자를 성장시켰다. 그 후 교반을 멈추고, 혼합액 중의 입자를 침강시킨 후, 혼합액의 상등액을 버리고 혼합액을 원심분리기를 이용하여 여과하고, 여재를 순수로 세정하고, 건조하여, 은분을 얻었다.Subsequently, the 1st reaction liquid was made to stir, the 2nd reaction liquid was added to this 1st reaction liquid collectively, and further stirred for 5 minutes after completion | finish of addition, and the particle was grown in the mixed liquid. After that, stirring was stopped, the particles in the mixed solution were allowed to settle, the supernatant of the mixed solution was discarded, the mixed solution was filtered using a centrifugal separator, the media was washed with pure water, dried, and silver powder was obtained.
<실시예2>Example 2
상온의 순수 850g에 질산은 용액 64g, 암모니아 용액(농도 25%) 87g 및 질산 용액(농도 60%) 17g을 넣고 교반하여 용해시켜 제1 반응액을 조제하였다. 한편 상온의 순수 1000g에 하이드로퀴논 10g을 넣고 교반하여 용해시켜 제2 반응액을 조제하였다. 64 g of silver nitrate solution, 87 g of ammonia solution (concentration 25%), and 17 g of nitric acid solution (concentration 60%) were added to 850 g of pure water at room temperature, followed by stirring to dissolve the first reaction solution. On the other hand, 10 g of hydroquinone was added to 1000 g of pure water at room temperature, and stirred to dissolve to prepare a second reaction solution.
이어서, 제1 반응액을 교반한 상태로 하고, 이 제1 반응액에 제2 반응액을 일괄 첨가하여, 첨가 종료 후부터 5분간 더 교반하여 혼합액 중에서 입자를 성장시켰다. 그 후 교반을 멈추고, 혼합액 중의 입자를 침강시킨 후, 혼합액의 상등액을 버리고 혼합액을 원심분리기를 이용하여 여과하고, 여재를 순수로 세정하고, 건조하여, 은분을 얻었다.Subsequently, the 1st reaction liquid was made to stir, the 2nd reaction liquid was added to this 1st reaction liquid collectively, and further stirred for 5 minutes after completion | finish of addition, and the particle was grown in the mixed liquid. After that, stirring was stopped, the particles in the mixed solution were allowed to settle, the supernatant of the mixed solution was discarded, the mixed solution was filtered using a centrifugal separator, the media was washed with pure water, dried, and silver powder was obtained.
<실시예3>Example 3
상온의 순수 830g에 질산은 용액 64g, 암모니아 용액(농도 25%) 87g 및 질산 용액 41g을 넣고 교반하여 용해시켜 제1 반응액을 조제하였다. 한편 상온의 순수 1000g에 하이드로퀴논 10g을 넣고 교반하여 용해시켜 제2 반응액을 조제하였다. 64 g of silver nitrate solution, 87 g of ammonia solution (concentration 25%), and 41 g of nitric acid solution were added to 830 g of pure water at room temperature, followed by stirring to dissolve the first reaction solution. On the other hand, 10 g of hydroquinone was added to 1000 g of pure water at room temperature, and stirred to dissolve to prepare a second reaction solution.
이어서, 제1 반응액을 교반한 상태로 하고, 이 제1 반응액에 제2 반응액을 일괄 첨가하여, 첨가 종료 후부터 5분간 더 교반하여 혼합액 중에서 입자를 성장시켰다. 그 후 교반을 멈추고, 혼합액 중의 입자를 침강시킨 후, 혼합액의 상등액을 버리고 혼합액을 원심분리기를 이용하여 여과하고, 여재를 순수로 세정하고, 건조하여, 은분을 얻었다.Subsequently, the 1st reaction liquid was made to stir, the 2nd reaction liquid was added to this 1st reaction liquid collectively, and further stirred for 5 minutes after completion | finish of addition, and the particle was grown in the mixed liquid. After that, stirring was stopped, the particles in the mixed solution were allowed to settle, the supernatant of the mixed solution was discarded, the mixed solution was filtered using a centrifugal separator, the media was washed with pure water, dried, and silver powder was obtained.
<실시예4>Example 4
상온의 순수 920g에 질산은 용액 64g, 암모니아 용액(농도 25%) 29g 및 질산 용액 7g, 질산암모늄 용액 10g을 넣고 교반하여 용해시켜 제1 반응액을 조제하였다. 한편 상온의 순수 1000g에 하이드로퀴논 10g을 넣고 교반하여 용해시켜 제2 반응액을 조제하였다. 64 g of silver nitrate solution, 29 g of ammonia solution (concentration 25%), 7 g of nitric acid solution, and 10 g of ammonium nitrate solution were added to 920 g of pure water at room temperature to prepare a first reaction solution. On the other hand, 10 g of hydroquinone was added to 1000 g of pure water at room temperature, and stirred to dissolve to prepare a second reaction solution.
이어서, 제1 반응액을 교반한 상태로 하고, 이 제1 반응액에 제2 반응액을 일괄 첨가하여, 첨가 종료 후부터 5분간 더 교반하여 혼합액 중에서 입자를 성장시켰다. 그 후 교반을 멈추고, 혼합액 중의 입자를 침강시킨 후, 혼합액의 상등액을 버리고 혼합액을 원심분리기를 이용하여 여과하고, 여재를 순수로 세정하고, 건조하여, 은분을 얻었다.Subsequently, the 1st reaction liquid was made to stir, the 2nd reaction liquid was added to this 1st reaction liquid collectively, and further stirred for 5 minutes after completion | finish of addition, and the particle was grown in the mixed liquid. After that, stirring was stopped, the particles in the mixed solution were allowed to settle, the supernatant of the mixed solution was discarded, the mixed solution was filtered using a centrifugal separator, the media was washed with pure water, dried, and silver powder was obtained.
<실시예5>Example 5
상온의 순수 920g에 질산은 용액 64g, 암모니아 용액(농도 25%) 29g 및 질산 용액 7g, 질산암모늄 용액 33g을 넣고 교반하여 용해시켜 제1 반응액을 조제하였다. 한편 상온의 순수 1000g에 하이드로퀴논 10g을 넣고 교반하여 용해시켜 제2 반응액을 조제하였다. 64 g of silver nitrate solution, 29 g of ammonia solution (concentration 25%), 7 g of nitric acid solution, and 33 g of ammonium nitrate solution were added to 920 g of pure water at room temperature to prepare a first reaction solution. On the other hand, 10 g of hydroquinone was added to 1000 g of pure water at room temperature, and stirred to dissolve to prepare a second reaction solution.
이어서, 제1 반응액을 교반한 상태로 하고, 이 제1 반응액에 제2 반응액을 일괄 첨가하여, 첨가 종료 후부터 5분간 더 교반하여 혼합액 중에서 입자를 성장시켰다. 그 후 교반을 멈추고, 혼합액 중의 입자를 침강시킨 후, 혼합액의 상등액을 버리고 혼합액을 원심분리기를 이용하여 여과하고, 여재를 순수로 세정하고, 건조하여, 은분을 얻었다.Subsequently, the 1st reaction liquid was made to stir, the 2nd reaction liquid was added to this 1st reaction liquid collectively, and further stirred for 5 minutes after completion | finish of addition, and the particle was grown in the mixed liquid. After that, stirring was stopped, the particles in the mixed solution were allowed to settle, the supernatant of the mixed solution was discarded, the mixed solution was filtered using a centrifugal separator, the media was washed with pure water, dried, and silver powder was obtained.
<실시예6>Example 6
상온의 순수 920g에 질산은 용액 64g, 암모니아 용액(농도 25%) 29g 및 질산 용액 7g, 질산암모늄 용액 50g을 넣고 교반하여 용해시켜 제1 반응액을 조제하였다. 한편 상온의 순수 1000g에 하이드로퀴논 10g을 넣고 교반하여 용해시켜 제2 반응액을 조제하였다. 64 g of silver nitrate solution, 29 g of ammonia solution (concentration 25%), 7 g of nitric acid solution, and 50 g of ammonium nitrate solution were added to 920 g of pure water at room temperature, and the mixture was stirred to prepare a first reaction solution. On the other hand, 10 g of hydroquinone was added to 1000 g of pure water at room temperature, and stirred to dissolve to prepare a second reaction solution.
이어서, 제1 반응액을 교반한 상태로 하고, 이 제1 반응액에 제2 반응액을 일괄 첨가하여, 첨가 종료 후부터 5분간 더 교반하여 혼합액 중에서 입자를 성장시켰다. 그 후 교반을 멈추고, 혼합액 중의 입자를 침강시킨 후, 혼합액의 상등액을 버리고 혼합액을 원심분리기를 이용하여 여과하고, 여재를 순수로 세정하고, 건조하여, 은분을 얻었다.Subsequently, the 1st reaction liquid was made to stir, the 2nd reaction liquid was added to this 1st reaction liquid collectively, and further stirred for 5 minutes after completion | finish of addition, and the particle was grown in the mixed liquid. After that, stirring was stopped, the particles in the mixed solution were allowed to settle, the supernatant of the mixed solution was discarded, the mixed solution was filtered using a centrifugal separator, the media was washed with pure water, dried, and silver powder was obtained.
<비교예 1>Comparative Example 1
상온의 순수 930g에 질산은 용액 64g, 암모니아 용액(농도 25%) 30g을 넣고 교반하여 용해시켜 제1 반응액을 조제하였다. 한편 상온의 순수 1000g에 하이드로퀴논 10g을 넣고 교반하여 용해시켜 제2 반응액을 조제하였다. 64 g of silver nitrate solution and 30 g of ammonia solution (concentration 25%) were added to 930 g of pure water at room temperature, and the mixture was stirred and dissolved to prepare a first reaction solution. On the other hand, 10 g of hydroquinone was added to 1000 g of pure water at room temperature, and stirred to dissolve to prepare a second reaction solution.
이어서, 제1 반응액을 교반한 상태로 하고, 이 제1 반응액에 제2 반응액을 일괄 첨가하여, 첨가 종료 후부터 5분간 더 교반하여 혼합액 중에서 입자를 성장시켰다. 그 후 교반을 멈추고, 혼합액 중의 입자를 침강시킨 후, 혼합액의 상등액을 버리고 혼합액을 원심분리기를 이용하여 여과하고, 여재를 순수로 세정하고, 건조하여, 은분을 얻었다.Subsequently, the 1st reaction liquid was made to stir, the 2nd reaction liquid was added to this 1st reaction liquid collectively, and further stirred for 5 minutes after completion | finish of addition, and the particle was grown in the mixed liquid. After that, stirring was stopped, the particles in the mixed solution were allowed to settle, the supernatant of the mixed solution was discarded, the mixed solution was filtered using a centrifugal separator, the media was washed with pure water, dried, and silver powder was obtained.
<비교예 2>Comparative Example 2
상온의 순수 930g에 질산은 용액 64g, 암모니아 용액(농도 25%) 29g 및 질산 용액 8g, 질산칼륨 용액 42g, 황산암모늄 28g을 넣고 교반하여 용해시켜 제1 반응액을 조제하였다.한편 상온의 순수 1000g에 하이드로퀴논 10g을 넣고 교반하여 용해시켜 제2 반응액을 조제하였다. Into 930 g of pure water at room temperature, 64 g of silver nitrate solution, 29 g of ammonia solution (concentration 25%), 8 g of nitric acid solution, 42 g of potassium nitrate solution, and 28 g of ammonium sulfate were added and stirred to prepare a first reaction solution. 10 g of hydroquinone was added and stirred to dissolve to prepare a second reaction solution.
이어서, 제1 반응액을 교반한 상태로 하고, 이 제1 반응액에 제2 반응액을 일괄 첨가하여, 첨가 종료 후부터 5분간 더 교반하여 혼합액 중에서 입자를 성장시켰다. 그 후 교반을 멈추고, 혼합액 중의 입자를 침강시킨 후, 혼합액의 상등액을 버리고 혼합액을 원심분리기를 이용하여 여과하고, 여재를 순수로 세정하고, 건조하여, 은분을 얻었다.Subsequently, the 1st reaction liquid was made to stir, the 2nd reaction liquid was added to this 1st reaction liquid collectively, and further stirred for 5 minutes after completion | finish of addition, and the particle was grown in the mixed liquid. After that, stirring was stopped, the particles in the mixed solution were allowed to settle, the supernatant of the mixed solution was discarded, the mixed solution was filtered using a centrifugal separator, the media was washed with pure water, dried, and silver powder was obtained.
제1 반응액First reaction solution
용제solvent 질산은 용액Silver nitrate solution 암모니아수 (25%) 용액Ammonia water (25%) solution 질산 용액 (60%)Nitric acid solution (60%) 추가 물질Additional substances
실시예 1Example 1 H2O880gH 2 O880g AgNO3 64gAgNO 3 64 g 58g58 g 11g11 g
실시예 2Example 2 H2O850gH 2 O850g AgNO364gAgNO 3 64 g 87g87 g 17g17 g
실시예 3Example 3 H2O830gH 2 O830 g AgNO364gAgNO 3 64 g 87g87 g 41g41 g
실시예 4Example 4 H2O920gH 2 O920g AgNO364gAgNO 3 64 g 29g29 g 7g7 g NH4NO310gNH 4 NO 3 10g
실시예 5Example 5 H2O920gH 2 O920g AgNO364gAgNO 3 64 g 29g29 g 7g7 g NH4NO333gNH 4 NO 3 33 g
실시예 6Example 6 H2O920gH 2 O920g AgNO3 64gAgNO 3 64 g 29g29 g 7g7 g NH4NO350gNH 4 NO 3 50 g
비교예 1Comparative Example 1 H2O930gH 2 O930g AgNO364gAgNO 3 64 g 30g30 g --
비교예 2Comparative Example 2 H2O920gH 2 O920g AgNO364gAgNO 3 64 g 29g29 g 8g8 g KNO3 42g(NH4)2SO4 28gKNO 3 42g (NH 4 ) 2 SO 4 28g
실험예Experimental Example
(1) SEM size 측정(1) SEM size measurement
본 발명의 실시예 및 비교예에 따라 제조된 은 분말을 지올(JEOL) 회사제 주사전자현미경을 이용하여, 파우더 100개 각각의 지름 크기를 측정한 후 평균을 내어 측정하였다.The silver powders prepared according to the Examples and Comparative Examples of the present invention were measured by averaging the diameters of 100 powders using a scanning electron microscope manufactured by JEOL.
(2) 유기물 함량 측정(2) organic matter content measurement
본 발명의 실시예 및 비교예에 따라 제조된 은 분말을 세이코 인스트루먼트(Seiko Instruments) 회사제 TG/DTA EXART6600을 이용하여, 공기 중, 승온 속도 10℃/min로 상온에서 500℃까지의 범위에서 TGA 분석을 행하여 유기물 함량을 측정하였다.Silver powders prepared according to Examples and Comparative Examples of the present invention using TG / DTA EXART6600 manufactured by Seiko Instruments, Inc., in the air, at a temperature rising rate of 10 ° C./min at room temperature to 500 ° C. in a range of TGA. Analysis was performed to determine the organic content.
(3) 열수축율 측정 (3) heat shrinkage rate measurement
본 발명의 실시예 및 비교예에 따라 제조된 은 분말을 티에이 인스트루먼트 (TA Instruments) 회사제 TMA Q400을 이용하여, 공기 중, 승온 속도 3℃/min로 상온에서 260℃, 260℃ 2시간 유지, 승온 속도 3℃/min로 400℃까지 승온, 400℃에서 2시간 유지하여 260~400℃ 구간의 수축율을 측정하였다.Silver powders prepared according to Examples and Comparative Examples of the present invention using TMA Q400 manufactured by TA Instruments, Inc., in air, at a temperature increase rate of 3 ° C./min, maintained at 260 ° C. and 260 ° C. for 2 hours, The temperature increase rate was raised to 400 ° C. at 3 ° C./min and maintained at 400 ° C. for 2 hours to measure the shrinkage in the 260-400 ° C. section.
SEM size (㎛)SEM size (㎛) 유기물 함량 (wt.%)Organic matter content (wt.%) 열수축율(%)Heat Shrinkage (%)
실시예 1Example 1 1.541.54 0.220.22 7.87.8
실시예 2Example 2 1.671.67 0.400.40 6.36.3
실시예 3Example 3 1.611.61 0.680.68 7.57.5
실시예 4Example 4 1.821.82 0.210.21 7.57.5
실시예 5Example 5 1.951.95 0.100.10 6.06.0
실시예 6Example 6 1.611.61 0.100.10 3.73.7
비교예 1Comparative Example 1 1.431.43 0.490.49 16.216.2
비교예 2Comparative Example 2 1.291.29 0.100.10 14.614.6
표 2에 나타난 바와 같이, 암모니아와 질산을 사용했을 때, 260~400도 구간 수축율이 10% 미만임을 확인할 수 있다. 또한 암모니아 용액 및 질산 용액만을 사용한 경우(실시예 1 내지 실시예 3)뿐만 아니라 질산암모늄을 함께 사용하여 암모늄 이온, 질산 이온을 공급하더라도 수축률 감소의 효과가 동등 이상으로 나타나는 것을 알 수 있으며, 비교예 2를 통해 암모늄 이온 및 질산 이온을 제공하는 질산칼륨 및 황산암모늄을 사용하더라도 수축율 감소에 효과가 없음을 알 수 있다. As shown in Table 2, when using ammonia and nitric acid, it can be confirmed that the shrinkage ratio of 260 ~ 400 degrees is less than 10%. In addition, when only the ammonia solution and the nitric acid solution were used (Examples 1 to 3), as well as the supply of ammonium ions and nitrate ions using ammonium nitrate together, the effect of shrinkage reduction was found to be equal or more. 2 shows that the use of potassium nitrate and ammonium sulfate, which provides ammonium ions and nitrate ions, has no effect on reducing shrinkage.
전술한 각 실시예에서 예시된 특징, 구조, 효과 등은 실시예들이 속하는 분야의 통상의 지식을 가지는 자에 의하여 다른 실시예들에 대해서도 조합 또는 변형되어 실시 가능하다. 따라서 이러한 조합과 변형에 관계된 내용들은 본 발명의 범위에 포함되는 것으로 해석되어야 할 것이다.Features, structures, effects, and the like illustrated in the above-described embodiments may be combined or modified with respect to other embodiments by those skilled in the art to which the embodiments belong. Therefore, contents related to such combinations and modifications should be construed as being included in the scope of the present invention.

Claims (9)

  1. 은 이온, 암모니아 및 질산을 포함하는 제1 반응액 및 환원제를 포함하는 제2 반응액을 제조하는 반응액제조단계(S21) 및 Reaction liquid preparation step (S21) for preparing a first reaction liquid containing silver ions, ammonia and nitric acid and a second reaction liquid containing a reducing agent and
    제1 반응액 및 제2 반응액을 반응시켜 은 분말을 얻는 석출단계(S22)를 포함하는 은 염 환원단계(S2);를 포함하는 은 분말 제조방법. Silver salt reduction step (S2) comprising a precipitation step (S22) to obtain a silver powder by reacting the first reaction solution and the second reaction solution.
  2. 제1항에 있어서,The method of claim 1,
    상기 암모니아는 상기 은 이온 100 중량부에 대하여 250 내지 600 중량부로 포함되는 것을 특징으로 하는 은 분말 제조방법.The ammonia is a silver powder manufacturing method, characterized in that contained in 250 to 600 parts by weight based on 100 parts by weight of the silver ions.
  3. 제2항에 있어서,The method of claim 2,
    상기 질산은 상기 은 이온 100 중량부에 대하여 20 내지 230 중량부로 포함되는 것을 특징으로 하는 은 분말 제조방법. The nitric acid is a silver powder manufacturing method, characterized in that it comprises 20 to 230 parts by weight based on 100 parts by weight of the silver ions.
  4. 제3항에 있어서,The method of claim 3,
    상기 환원제는 상기 제1 반응액에 포함되는 은 이온 100 중량부에 대하여 50 내지 60 중량부로 포함되는 것을 특징으로 하는 은 분말 제조방법.The reducing agent is a silver powder manufacturing method, characterized in that contained in 50 to 60 parts by weight based on 100 parts by weight of silver ions contained in the first reaction solution.
  5. 제1항에 있어서,The method of claim 1,
    상기 반응액제조단계(S21)는 용제에 은 이온, 암모니아 수용액 및 질산 수용액을 첨가하고 교반하여 용해시켜 제1 반응액을 제조하고, In the preparing of the reaction solution (S21), silver ions, an aqueous ammonia solution, and an aqueous nitric acid solution are added to the solvent, stirred, and dissolved to prepare a first reaction solution.
    또한 상기 반응액제조단계(S21)는 용제에 환원제를 첨가하고 교반하여 용해시켜 제2 반응액을 제조하는 단계인 것을 특징으로 하는 은 분말 제조방법.In addition, the reaction solution production step (S21) is a silver powder production method, characterized in that the step of preparing a second reaction solution by adding a reducing agent to the solvent and stirring to dissolve.
  6. 제5항에 있어서,The method of claim 5,
    상기 석출단계(S22)는 상기 제1 반응액을 교반하는 상태에서 상기 제2 반응액을 적가하거나 일괄 첨가하여 반응시키는 단계인 것을 특징으로 하는 은 분말 제조방법.The precipitation step (S22) is a silver powder manufacturing method, characterized in that for reacting by dropwise addition or batch addition of the second reaction solution in the state of stirring the first reaction solution.
  7. 제6항에 있어서,The method of claim 6,
    상기 석출단계(S22)는 지방산, 지방산염, 계면활성제, 유기금속, 킬레이트 형성제 및 보호 콜로이드로 구성되는 군에서 선택되는 어느 1종 이상을 더 첨가하여 반응시키는 단계인 것을 특징으로 하는 은 분말 제조방법. The precipitation step (S22) is the production of silver powder, characterized in that the step of adding any one or more selected from the group consisting of fatty acids, fatty acid salts, surfactants, organometallic, chelate forming agent and protective colloid further react. Way.
  8. 제4항에 있어서,The method of claim 4, wherein
    상기 환원제는 하이드로퀴논, 아스코르브산, 알칸올아민, 히드라진 및 포르말린으로 구성되는 군에서 선택되는 1종 이상인 것을 특징으로 하는 은 분말 제조방법. The reducing agent is a silver powder production method, characterized in that at least one selected from the group consisting of hydroquinone, ascorbic acid, alkanolamine, hydrazine and formalin.
  9. 결정자 평균 지름이 1.5um 내지 3um인 은 분말로서, Silver powder having a crystallite mean diameter of 1.5 μm to 3 μm,
    상기 은 분말을 이용하여 제조된 필름을 공기 중 승온 속도 3℃/min로 상온에서 260℃로 승온 후 2시간 유지, 승온 속도 3℃/min로 260℃에서 400℃까지 승온 후 2시간 유지하여, 260~400℃ 구간의 수축율이 10% 이하인 은 분말.The film prepared using the silver powder is maintained at room temperature in a heating rate of 3 ℃ / min at 260 ℃ at room temperature for 2 hours, the temperature rising rate at 3 ℃ / min and maintained at 260 ℃ to 400 ℃ for 2 hours, Silver powder with a shrinkage of 10% or less in the 260-400 ° C section.
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