WO2018070817A1 - Poudre d'argent pour frittage à haute température et son procédé de préparation - Google Patents

Poudre d'argent pour frittage à haute température et son procédé de préparation Download PDF

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Publication number
WO2018070817A1
WO2018070817A1 PCT/KR2017/011282 KR2017011282W WO2018070817A1 WO 2018070817 A1 WO2018070817 A1 WO 2018070817A1 KR 2017011282 W KR2017011282 W KR 2017011282W WO 2018070817 A1 WO2018070817 A1 WO 2018070817A1
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WO
WIPO (PCT)
Prior art keywords
silver powder
reaction solution
silver
high temperature
sintered
Prior art date
Application number
PCT/KR2017/011282
Other languages
English (en)
Korean (ko)
Inventor
이창근
강태훈
권태현
진우민
이미영
최재원
Original Assignee
엘에스니꼬동제련 주식회사
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 엘에스니꼬동제련 주식회사 filed Critical 엘에스니꼬동제련 주식회사
Priority to CN201780076559.4A priority Critical patent/CN110114175B/zh
Publication of WO2018070817A1 publication Critical patent/WO2018070817A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2201/00—Treatment under specific atmosphere
    • B22F2201/01—Reducing atmosphere
    • B22F2201/016—NH3
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2301/00—Metallic composition of the powder or its coating
    • B22F2301/25—Noble metals, i.e. Ag Au, Ir, Os, Pd, Pt, Rh, Ru
    • B22F2301/255—Silver or gold
    • 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
    • B22F2304/00—Physical aspects of the powder
    • B22F2304/10—Micron size particles, i.e. above 1 micrometer up to 500 micrometer

Definitions

  • the present invention relates to a high-temperature sintered silver powder and a method for manufacturing the same, and particularly, a high-temperature sintered type suitable for use in a conductive paste for forming an electrode in an electronic component such as a solar cell electrode, an internal electrode of a multilayer capacitor, and a conductor pattern of a circuit board.
  • Silver powder and a method for producing the same are particularly known as a high-temperature sintered silver powder and a method for manufacturing the same, and particularly, a high-temperature sintered type suitable for use in a conductive paste for forming an electrode in an electronic component such as a solar cell electrode, an internal electrode of a multilayer capacitor, and a conductor pattern of a circuit board.
  • 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
  • the silver paste (Silver Paste) is the most chemically stable and excellent conductivity among the composite-based conductive paste has a wide range of applications in a variety of fields, such as for conductive adhesion and coating, and the formation of fine circuits.
  • silver paste is used in various ways, such as silver through hole (STH), adhesive or coating material.
  • 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.
  • a fine metal powder is used as the conductive filler.
  • the sintered density of the metal powder is the theoretical density of the metal. The lower the density, the lower the sintered density of the metal powder has a problem that the electrical conductivity of the coating film prepared using the conductive paste is also lowered.
  • the present invention is to provide a high-temperature sintered silver powder having a high sintered density at a high temperature of 600 °C or more as a silver powder used in the conductive paste (Paste) to solve the above problems and a method for producing the same.
  • the present invention obtains a silver powder by reacting a reaction solution preparing step (S21) for preparing a first reaction solution containing silver ions and ammonia and a second reaction solution including a reducing agent and the first reaction solution and the second reaction solution.
  • a reaction solution preparing step (S21) for preparing a first reaction solution containing silver ions and ammonia and a second reaction solution including a reducing agent and the first reaction solution and the second reaction solution.
  • a silver powder manufacturing method comprising; silver salt reduction step (S2) comprising a precipitation step (S22),
  • High temperature sintered silver powder manufacturing method characterized in that when preparing the first reaction solution in the reaction solution manufacturing step (S21) by controlling the stirring speed and stirring time to produce a silver powder having a high sintered density at high temperature sintering To provide.
  • the first reaction solution in the reaction solution production step (S21) is characterized in that the silver ions and the ammonia is mixed with a stirrer, and stirred for 30 to 180 minutes.
  • the first reaction solution is prepared by mixing 30 to 160 parts by weight of the ammonia based on 100 parts by weight of the silver ions.
  • the reducing agent is characterized in that at least one member selected from the group consisting of ascorbic acid, alkanolamine, hydroquinone, hydrazine and formalin.
  • the second reaction solution may be prepared by mixing the reducing agent with 80 to 120 parts by weight based on 100 parts by weight of the silver ions.
  • 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 present invention provides a high-temperature sintered silver powder having a mean particle size of 0.7 to 1.2 ⁇ m, the sintered density is 9.0 g / cc or more when the silver powder is sintered at a high temperature of 600 °C or more.
  • the present invention can provide a high-temperature sintered silver powder having a sintered density of 9.0 g / cc or more at a high temperature of 600 ° C. or higher and a method of manufacturing the same.
  • the silver paste manufactured using the silver powder having a high sintering density according to the present invention has a low specific resistance after high temperature sintering, thereby increasing the electrical conductivity of the electrode manufactured using the same.
  • the present patent can provide a method of increasing the final sintered density by controlling the stirring time after mixing AgNO 3 and NH 4 OH.
  • Method for producing a high-temperature sintered silver powder is a silver salt manufacturing step (S1), silver salt reduction step (S2), filtration and washing step such as purification step (S3) and surface treatment step (S4) It is made to include.
  • the high temperature sintered silver powder manufacturing method 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 containing silver ions (Ag + ) by acid treatment of silver (Ag) in the form of ingot, lip, granule ),
  • a silver salt solution may be prepared by directly preparing a silver salt solution through this step, but commercially available silver nitrate may be used in a subsequent step 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) is a step of preparing a first reaction solution by adding ammonia to the silver salt solution containing silver ions and stirred to dissolve.
  • 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.
  • 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.
  • 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 30 to 160 parts by weight based on 100 parts by weight of silver ions. If ammonia is added in an amount less than 30 parts by weight, there is a problem in forming silver oxide or forming a uniform particle distribution due to insufficient formation of ammonia salts. When ammonia is added in excess of 160 parts by weight, the organic content of the silver powder produced is excessive. There is a problem that the size is large or the particle size (size) is greatly reduced. When using a 25% aqueous solution of ammonia, it is preferable to add 120 to 600 parts by weight based on 100 parts by weight of silver ions.
  • the ammonia includes its derivatives.
  • the first reaction solution containing silver ions and ammonia may be prepared in the form of an aqueous solution by adding silver ions and an aqueous ammonia solution to a solvent such as water, stirring and dissolving the same, and also preparing a slurry.
  • the stirring is performed at a speed of 2 to 10 m / sec based on the impeller linear speed of the stirrer. If the stirring is less than 2m / sec there is a problem of particle size imbalance due to the lack of agitation force is not uniform mixing, and when the stirring is more than 10m / sec, the phenomenon of the solution is remarkably generated and bubbles in the solution There is a problem that is collected inside the powder.
  • stirring at a speed of 3m / sec to 4m / sec.
  • Reaction liquid preparation step (S21) is a step for preparing 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 content of the reducing agent in the second reaction liquid is different depending on the type of reducing agent, but it is included in the 80 to 120 parts by weight based on 100 parts by weight of silver ions included in the first reaction liquid based on the amount of reducing agent calculated by the theoretical reaction formula It is preferable. When using less than 80 parts by weight, all of the silver ions may not be reduced, when using more than 120 parts by weight may increase the organic content and increase the manufacturing cost 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.
  • 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 to prevent aggregation.
  • dispersants 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 adjusting the water content of the wet cake obtained after filtration to less than 10%, a surface treatment agent may be added for the surface treatment of the silver powder, and the water content may 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.
  • the silver powder prepared according to the embodiment of the present invention has a sintered density of 9.0 g / cc or more when sintered at a high temperature of 600 ° C. or higher, and measures the diameter size of each of 100 powders using a scanning electron microscope (SEM). The average was then measured to a size of 0.7 to 1.2 ⁇ m.
  • SEM scanning electron microscope
  • a conductive silver paste for forming an electrode of an electronic component such as a solar cell or a multilayer capacitor, a conductor pattern of a circuit board, or the like can be provided.
  • silver powder is mainly disperse
  • the coating film is formed using the silver paste containing the silver powder prepared according to the present invention, since the sintered density is high as 9.0 g / cc, it has excellent electrical conductivity.
  • the 1st aqueous solution was made to stir, the 2nd aqueous solution was added collectively to this 1st aqueous solution, and further stirred for 5 minutes after completion
  • silver powder was obtained in the same manner as in Example 1 except that the stirring linear velocity and the stirring time were changed as shown in Table 1 below.
  • 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. The results are shown in Table 2.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Powder Metallurgy (AREA)

Abstract

La présente invention concerne un procédé de préparation d'une poudre d'argent pour frittage à haute température, ainsi qu'un procédé de préparation d'une poudre d'argent par préparation d'une première solution de réactif comprenant des ions argent et de l'ammoniac et d'une seconde solution de réactif comprenant un agent réducteur, puis par précipitation d'une poudre d'argent en faisant réagir la première solution de réactif et la seconde solution de réactif préparées. Comme le temps d'agitation est régulé lorsque la première solution de réactif est préparée, une poudre d'argent ayant une densité de frittage élevée peut être préparée pendant un frittage à haute température.
PCT/KR2017/011282 2016-10-13 2017-10-13 Poudre d'argent pour frittage à haute température et son procédé de préparation WO2018070817A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201780076559.4A CN110114175B (zh) 2016-10-13 2017-10-13 高温烧结型银粉末及其制造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020160132885A KR101853420B1 (ko) 2016-10-13 2016-10-13 고온 소결형 은 분말 및 이의 제조방법
KR10-2016-0132885 2016-10-13

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WO2018070817A1 true WO2018070817A1 (fr) 2018-04-19

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KR (1) KR101853420B1 (fr)
CN (1) CN110114175B (fr)
WO (1) WO2018070817A1 (fr)

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JP6845444B1 (ja) * 2019-10-15 2021-03-17 千住金属工業株式会社 接合材、接合材の製造方法及び接合体
CN111558728B (zh) * 2020-05-13 2022-12-27 哈尔滨工业大学(深圳)(哈尔滨工业大学深圳科技创新研究院) 一种多尺寸复合的纳米银膏及其制备方法

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KR20090045508A (ko) * 2007-11-02 2009-05-08 주식회사 지오션 더블-제트형 연속식 용액환원에 의해 은 분말을 제조하기위한 장치 및 방법
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Also Published As

Publication number Publication date
KR20180040935A (ko) 2018-04-23
CN110114175A (zh) 2019-08-09
KR101853420B1 (ko) 2018-04-30
CN110114175B (zh) 2022-06-14

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