WO2019088509A1 - Poudre d'argent traitée en surface et son procédé de préparation - Google Patents

Poudre d'argent traitée en surface et son procédé de préparation Download PDF

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Publication number
WO2019088509A1
WO2019088509A1 PCT/KR2018/012184 KR2018012184W WO2019088509A1 WO 2019088509 A1 WO2019088509 A1 WO 2019088509A1 KR 2018012184 W KR2018012184 W KR 2018012184W WO 2019088509 A1 WO2019088509 A1 WO 2019088509A1
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WIPO (PCT)
Prior art keywords
silver powder
treatment agent
conductive paste
silver
fatty acid
Prior art date
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PCT/KR2018/012184
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English (en)
Korean (ko)
Inventor
이미영
김영환
진우민
강태훈
최재원
이창근
Original Assignee
엘에스니꼬동제련 주식회사
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Application filed by 엘에스니꼬동제련 주식회사 filed Critical 엘에스니꼬동제련 주식회사
Priority to JP2020524301A priority Critical patent/JP6982688B2/ja
Priority to CN201880083265.9A priority patent/CN111511489B/zh
Publication of WO2019088509A1 publication Critical patent/WO2019088509A1/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
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B22F1/102—Metallic powder coated with organic material
    • 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
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • 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

Definitions

  • the present invention relates to a surface-treated silver powder and a method for producing the same, and more particularly to a silver powder suitable for use in a conductive paste for forming an electrode in an electronic component such as an electrode for a solar cell or an internal electrode of a multilayer capacitor, And a manufacturing method thereof.
  • the conductive metal paste is a paste in which electricity is applied to a dried or baked coating film having a coating ability capable of forming a coating film and is dispersed with a conductive filler (metal filler) alone or in a glass frit in a vehicle made of a resin- It is widely used for the formation of an electric circuit or the formation of an external electrode of a ceramic capacitor.
  • Silver Paste is the most chemically stable and excellent in conductivity among the conductive paste of composite system, and has a wide range of applications in various fields such as conductive bonding and coating and fine circuit formation.
  • the electronic parts such as PCBs (Printed Circuit Boards), which are particularly important for reliability, the use of silver paste is used for bonding or coating materials for STH (Silver Through Hole), for internal electrodes in multilayer capacitors, Is widely used as an electrode material.
  • the front electrode of the solar cell is formed by sintering after a conductive paste mainly composed of silver (Ag) powder is printed in a grid pattern on the antireflection film.
  • a conductive paste mainly composed of silver (Ag) powder is printed in a grid pattern on the antireflection film.
  • the front electrode penetrates the antireflection film in the sintering process through the heat treatment to form an ohmic contact with the N-type silicon layer, thereby lowering the series resistance of the solar cell to increase the conversion efficiency.
  • the rheology of the conductive paste is a major factor that determines the printing property (application suitability).
  • the conductive paste The rheological properties of the conductive paste are particularly important because screen printed electrodes for solar cells require an increase in the narrow line width and high thickness, that is, the aspect ratio, of the electrodes.
  • Properties including rheological properties are changed by a network structure formed by the interaction of a filler, a resin binder, a solvent, an additive, etc. constituting the conductive paste.
  • the silver powder which occupies the largest amount in the conductive paste is important in determining the shape of the network structure formed by varying the interaction force between the silver powder and the other constituents depending on the kind and content of the surface treatment agent coated on the surface thereof . Therefore, in order to control the printing properties and the rheological properties of the paste, it is necessary to control the surface chemical properties of the silver powder according to the kind and content of the surface treatment agent.
  • Japanese Patent Laid-Open Publication No. 2016-33259 provides a silver powder capable of obtaining a conductive paste having a high consumption ratio (low rpm viscosity / high rpm viscosity) for forming a fine pattern through screen printing and a method for producing the same have.
  • the present invention provides a surface treatment method for a silver powder used in a conductive paste for solving the above problems, and it is an object of the present invention to provide a method for surface treatment of a silver powder used for a conductive paste, And to provide a conductive paste favorable for high-speed printing and fine pattern printing.
  • the anionic surfactant may be any one selected from the group consisting of Aromatic alcohol phosphate, Fatty alcohol phosphate, Dialkyl sulfosuccinate, and Polypeptide. Or more.
  • the fatty acid may be selected from the group consisting of lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, linolic acid, And at least one selected from the group consisting of arachidonic acid.
  • the fatty acid salt may be prepared by dissolving the fatty acid in an aqueous medium such as calcium hydroxide, sodium hydroxide, ammonia, methylamine, dimethylamine, trimethylamine, ethylamine, And a fatty acid salt which forms a salt with diethylamine, triethylamine, ethanolamine, diethanolamine, or triethanolamine.
  • an aqueous medium such as calcium hydroxide, sodium hydroxide, ammonia, methylamine, dimethylamine, trimethylamine, ethylamine, and a fatty acid salt which forms a salt with diethylamine, triethylamine, ethanolamine, diethanolamine, or triethanolamine.
  • the first surface treatment step (S41) may be performed by preparing a silver powder dispersion in which silver powder is dispersed in a solvent, adding the first treatment agent to a solvent and stirring to prepare a first coating solution, Adding the first coating liquid, and mixing and stirring.
  • the first surface treatment step (S41) is a step of mixing the silver powder dispersion and the first coating solution such that the first treating agent is mixed in an amount of 0.1 to 2 parts by weight based on 100 parts by weight of the silver powder.
  • the second surface treatment step (S42) is a step of dispersing the silver powder coated with the first treatment agent in a solvent, and then adding and stirring the alcohol solution containing the second treatment agent.
  • the second surface treatment step (S42) is a step of adding an alcohol solution containing a second treatment agent to 100 parts by weight of the silver powder coated with the first treatment agent so that the second treatment agent is mixed with 0.1 to 1.0 part by weight .
  • the present invention is an ion, ammonia (NH 3) and nitric acid (HNO 3)
  • the first reaction solution and for producing a second reaction solution containing a reducing agent in the reaction mixture prepared step (S21) and the first reaction solution containing the and A silver salt reducing step (S2) including a precipitation step (S22) of reacting the second reaction solution to obtain silver powder;
  • the present invention is a silver powder having an average particle size (D50) of 1.0 to 3.0 m, wherein the silver powder is subjected to a first surface treatment using a first treatment agent containing an anionic surfactant, And a silver powder for a conductive paste, which is a second surface-treated silver powder using the second treatment agent.
  • D50 average particle size
  • the present invention also relates to a metal powder including the silver powder for the conductive paste.
  • a glass vehicle comprising a solvent and an organic binder; And a conductive paste.
  • the conductive paste is characterized by having a viscosity ratio of 0.8 to 1.5 as measured at 1 rpm to a viscosity measured at 10 rpm when the viscosity (Pa ⁇ s) is measured at 25 ° C.
  • the conductive paste has a viscosity of 350 to 500 Pa ⁇ s measured at 10 rpm when the viscosity (Pa ⁇ s) is measured at 25 ° C.
  • a metal powder containing the silver powder for the conductive paste Glass frit; And an organic vehicle including a solvent and an organic binder.
  • the present invention relates to a silver paste which is surface-treated with a first treatment agent containing an anionic surfactant and a second treatment agent comprising a fatty acid or a fatty acid salt to provide silver paste and a conductive paste containing the silver paste, It is possible to provide a conductive paste favorable for pattern printing.
  • the present invention relates to a conductive paste containing a silver powder prepared by surface-treating a silver powder using a first surface treatment agent containing an anionic surfactant and a second surface treatment agent containing a fatty acid or a fatty acid salt in the production process, So as to provide a conductive paste particularly suitable for high speed printing and fine pattern printing.
  • a method of manufacturing a silver powder according to an embodiment of the present invention includes: a silver salt producing step (S1); Silver salt reduction step (S2); Purification step such as filtration and washing (S3); And a surface treatment step (S4).
  • the method for producing silver powder according to the present invention necessarily includes the surface treatment step (S4), and the other steps can be omitted. That is, the surface treatment step (S4) according to one embodiment of the present invention can be applied not only to the silver powder prepared through the above step but also to silver powder produced by a general method or a conventional method.
  • the silver salt preparation step S1 is a step of preparing a silver salt solution containing silver ions (Ag + ) by acid treatment of silver (Ag) in the form of ingots, comprising the steps of manufacturing, but can produce a powder to prepare a salt is passed through the step the solution directly, silver nitrate was purchased commercially (AgNO 3), the salt complex, or can proceed to the later steps, using the intermediate solution have.
  • the silver salt reducing step S2 is a step of reducing silver ions by adding a reducing agent and ammonia to a silver salt solution to precipitate silver particles, and silver ions, ammonia, and nitric acid (S21) for producing a second reaction solution containing a first reaction solution containing a reducing agent and a precipitation step (S22) for obtaining a silver powder by reacting the first reaction solution and the second reaction solution .
  • reaction solution preparation step (S21) ammonia and nitric acid are added to a silver salt solution containing silver ions, and the solution is stirred and dissolved to prepare a first reaction solution.
  • the silver ions are not limited as long as they are contained in the form of silver cations.
  • silver nitrate (AgNO 3 ), silver salt complex or silver intermediate may be used. It is preferable to use silver nitrate (AgNO 3 ).
  • AgNO 3 silver nitrate
  • the use of silver nitrate (AgNO 3 ) containing an ion will be described as an example.
  • Ammonia (NH 3 ) can be used in the form of an aqueous solution.
  • 25% ammonia aqueous solution 100 to 150 parts by weight of silver nitrate (AgNO 3 ) is added in 100 parts by weight.
  • the aqueous ammonia solution is added in an amount of less than 100 parts by weight, the reaction pH is low and silver ions are not completely reduced, or there is a problem in forming a uniform particle distribution.
  • the amount is more than 150 parts by weight, There is a problem that it becomes excessively high.
  • a 25% ammonia aqueous solution is added in an amount of 120 to 140 parts by weight based on 100 parts by weight of silver nitrate (AgNO 3 ).
  • the ammonia includes a derivative thereof.
  • the nitric acid (HNO 3 ) can be used in the form of an aqueous solution.
  • 60% nitric acid aqueous solution 40 to 120 parts by weight are added to 100 parts by weight of silver nitrate (AgNO 3 ).
  • the amount of the nitric acid (HNO 3 ) is less than 40 parts by weight, it is difficult to control the size of the powder.
  • the amount of the nitric acid (HNO 3 ) is more than 120 parts by weight, have.
  • a 60% nitric acid aqueous solution is added in an amount of 80 to 100 parts by weight based on 100 parts by weight of silver nitrate (AgNO 3 ).
  • the nitric acid includes a derivative thereof.
  • the first reaction solution containing silver ions, ammonia and nitric acid can be prepared in an aqueous solution state by adding a silver ion, an aqueous ammonia solution and an aqueous nitric acid solution to a solvent such as water and dissolving them by stirring to form a slurry form .
  • the reaction solution preparation step (S21) according to an embodiment of the present invention also produces a second reaction solution containing a reducing agent.
  • the reducing agent may be at least one member selected from the group consisting of ascorbic acid, alkanolamine, hydroquinone, hydrazine and formalin, and among them, hydroquinone can be preferably selected.
  • the content of the reducing agent is preferably 10 to 20 parts by weight based on 100 parts by weight of silver nitrate (AgNO 3 ) contained in the first reaction solution. If less than 10 parts by weight is used, silver ions may not be reduced at all, and when used in excess of 20 parts by weight, organic matter content increases.
  • the second reaction liquid is prepared by using 14 to 16 parts by weight of a reducing agent per 100 parts by weight of silver nitrate.
  • the second reaction solution containing a reducing agent can be prepared in an aqueous solution state by adding a reducing agent to a solvent such as water and dissolving it by stirring.
  • the precipitation step (S22) is a step of reacting the first reaction solution and the second reaction solution to obtain a silver powder, wherein the first reaction solution produced by the reaction solution production step (S21)
  • the second reaction solution may be slowly added dropwise or the reaction may be carried out in a batch.
  • the particles are added in a batch and further stirred for 5 minutes to 10 minutes to grow the particles in the mixed solution, so that the reduction reaction can be terminated in a short period of time to prevent agglomeration of the particles and increase dispersibility.
  • the silver powder dispersed in the aqueous solution or slurry is separated and washed by filtration after completing the silver particle precipitation reaction through the silver salt reducing step S2 Step S31. More specifically, after precipitating silver particles in the silver powder dispersion, the supernatant of the dispersion is discarded, filtered using a centrifugal separator, and the filter material is washed with pure water. The process of washing is done by completely removing the washing water from which the powder is washed. It is also possible to prevent agglomeration of the silver powder by optionally adding the above-mentioned dispersant to the reaction-completed solution before filtration.
  • the purification step S3 may further include a post-cleaning drying and decoloring step (S34).
  • the surface treatment step S4 is a method that can be generally applied to the silver powder produced by the general method or the conventional method as well as the silver powder prepared through the above step.
  • the surface treatment step S4 is a step of treating the rheological properties of the conductive paste including the silver powder prepared by surface treatment of the silver powder using the first treatment agent containing the anionic surfactant and the second treatment agent containing the fatty acid or the fatty acid salt Can be controlled.
  • the surface treatment step S4 includes a first surface treatment step S41 using the first treatment agent and a second surface treatment step S42 using the second treatment agent.
  • the first surface treatment step (S41) is a step of hydrophobizing the hydrophilic surface of the silver powder.
  • the silver powder is dispersed in a solvent, and a first treatment agent containing an anionic surfactant is added and mixed and stirred to coat the silver powder.
  • the first treatment agent includes at least one selected from the group consisting of aromatic alcohol phosphate, fatty alcohol phosphate, dialkyl sulfosuccinate, and a polypeptide. do.
  • aromatic alcohol phosphate fatty alcohol phosphate
  • dialkyl sulfosuccinate a polypeptide.
  • a polypeptide e.g. an aliphatic alcohol phosphate.
  • solvent water, ethanol, isopropyl alcohol, ethylene glycol hexyl ether, diethylene glycol, butyl ether, propylene glycol, propyl ether and the like can be used, and water is preferably used.
  • the first surface treatment step (S41) is a step of first treating the surface of the silver powder with the first treatment agent so as to coat the second treatment agent more effectively.
  • the silver powder dispersion is prepared by dispersing silver powder in a solvent, A first treatment agent is added to a solvent and stirred to prepare a first coating solution, and then the first coating solution is added to the silver powder dispersion, followed by mixing and stirring.
  • Silver powder is obtained by adding silver powder to a solvent having a mass of 2 to 5 times the mass of the silver powder and agitating the powder at 2000 to 5000 rpm for 10 to 30 minutes using a stirrer. Preferably 3000 to 4000 rpm, for 15 to 25 minutes to obtain a silver powder dispersion.
  • the first coating liquid is prepared by placing the first treating agent in a solvent having a mass of 5 to 20 times the mass of the first treating agent, and then stirring the mixture with ultrasonic waves for 5 to 20 minutes.
  • the first coating liquid is added to the silver powder dispersion prepared above, and the mixture is stirred at 2000 to 5000 rpm for 10 to 30 minutes using a stirrer to perform a first surface treatment. At this time, the silver powder dispersion and the first coating solution are added so that the first treating agent is treated with 0.1 to 2 parts by weight per 100 parts by weight of the powder.
  • the amount of the first surface treatment agent is less than 0.1 part by weight, the amount of the first surface treatment agent adsorbed on the surface of the powder is so small that there is a problem in that it is difficult to produce a conductive paste having a low consumption, Excessive bubbles are generated in the surface treatment process and the workability is poor and there is a problem that the electrical conductivity of the electrode manufactured by adsorbing an excessive amount of the surface treatment agent on the surface of the silver powder may be deteriorated.
  • 0.5 to 1.5 parts by weight of the first treatment agent is applied to 100 parts by weight of the silver powder.
  • the second surface treatment step (S42) is a step of secondary treatment with the second treatment agent so that the surface of the silver powder coated with the first treatment agent is coated with the second treatment agent, 5-fold mass of a solvent, adding an alcohol solution containing a second treatment agent, stirring the solution, filtering, washing and drying to obtain a second surface-treated silver powder.
  • silver powder is added to an alcohol solution containing a fatty acid or a fatty acid salt as a second treatment agent and stirred.
  • an alcohol solution in which a fatty acid or a fatty acid salt is dissolved in an amount of 5 to 20 wt% based on the total weight of the solution is used.
  • the alcohol may be methanol, ethanol, n-propanol, benzyl alcohol, terpineol or the like, preferably ethanol.
  • the alcohol solution containing the second treatment agent is added to the solution in which the primary surface-treated silver powder is dispersed, and the mixture is stirred at 2000 to 5000 rpm for 10 to 30 minutes using a stirrer to perform the second surface treatment.
  • 0.1 to 1.0 part by weight of the second treating agent is mixed with 100 parts by weight of the silver powder coated with the first treating agent.
  • the second treating agent is mixed at less than 0.1 part by weight, the amount of the second treating agent adsorbed on the surface of the powder is small and aggregation occurs between the powders, and the dispersibility of the paste is lowered due to low compatibility with the vehicle during the production of the conductive paste There is a problem that it is difficult to obtain the desired rheological characteristics of the paste.
  • the silver powder When the silver powder is mixed in an amount exceeding 1.0 part by weight, excessive electrical conductivity of the electrode, which is produced by adsorbing excess surface treatment agent on the silver powder surface, There is a problem.
  • 0.1 to 0.5 parts by weight of the second treating agent is mixed with 100 parts by weight of the silver powder.
  • the fatty acid may be selected from the group consisting of lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, linolic acid, And arachidonic acid.
  • the fatty acid may be at least one selected from the group consisting of calcium hydroxide, sodium hydroxide, ammonia, methylamine, dimethylamine, trimethylamine, ethylamine, And a fatty acid salt which forms a salt with diethylamine, triethylamine, ethanolamine, diethanolamine or triethanolamine.
  • stearic acid or ammonium stearate or ammonium oleate in which oleic acid forms a salt with ammonia water is preferably used.
  • the silver powder finally surface-treated through the purification step (S3) once more can be obtained.
  • the silver powder produced by the silver powder production method according to an embodiment of the present invention has an average particle size (D50) of 0.5 to 5.0 mu m, more specifically 1.0 to 3.0 mu m.
  • D50 average particle size
  • the adsorption amount of the first treatment agent which is measured as the difference between the organic matter content (%) of the silver powder after the first surface treatment and the organic matter content (%) of the powder before the first surface treatment, is 0.05 to 0.2% (%) Of the silver powder after the secondary surface treatment and the adsorption amount of the second treating agent measured by the difference of the organic matter content (%) of the powder before the secondary surface treatment (after the primary surface treatment) Is at least 0.05%.
  • Amount of adsorbed amount of first treating agent (%) amount of powdered organic matter (%) after first surface treatment Powder organic matter content (%) before first surface treatment
  • the present invention also provides a conductive paste comprising silver powder prepared according to an embodiment of the present invention.
  • the conductive paste includes a metal powder and an organic vehicle.
  • a surface-treated silver powder is used according to an embodiment of the present invention.
  • the content of the metal powder is preferably 85 to 95 wt% based on the total weight of the conductive paste composition, considering the thickness of the electrode formed during printing and the line resistance of the electrode.
  • the organic vehicle preferably contains 5 to 15% by weight, based on the total weight of the conductive paste composition, of an organic binder mixed with 5 to 15% by weight of a solvent.
  • Examples of the organic binder include a cellulose ester compound such as cellulose acetate and cellulose acetate butyrate.
  • Examples of the cellulose ether compound include ethyl cellulose, methyl cellulose, hydroxypropyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose , And hydroxyethyl methyl cellulose.
  • Examples of the acrylic compound include polyacrylamide, polymethacrylate, polymethylmethacrylate, and polyethylmethacrylate.
  • Examples of the vinyl compound include polyvinyl butyrate Polyvinyl acetate, polyvinyl alcohol, and the like. At least one or more organic binders may be selected and used.
  • Examples of the solvent used for diluting the composition include alcohols such as methanol, ethanol, n-propanol, benzyl alcohol and terpineol; Ketones such as acetone, methyl ethyl ketone, cyclohexanone, isophorone, and acetylacetone; Amides such as N, N-dimethylformamide and N, N-dimethylacetamide; Ethers such as tetrahydrofuran, dioxane, methyl cellosolve, diglyme and butyl carbitol; Esters such as methyl acetate, ethyl acetate, diethyl carbonate, TXIB (1-isopropyl-2,2-dimethyltrimethylene diisobutyrate), acetic acid carbitol and acetic acid butyl carbitol; Sulfoxides and sulfones such as dimethyl sulfoxide and sulfolane; Aliphatic
  • the conductive paste according to the present invention comprises a metal powder, a glass frit, and an organic vehicle.
  • a surface-treated silver powder is used according to an embodiment of the present invention.
  • the content of the metal powder is preferably 85 to 95% by weight based on the total weight of the conductive paste composition, taking into account the electrode thickness formed during printing and the line resistance of the electrode.
  • the composition, particle diameter and shape of the glass frit are not particularly limited. It is possible to use not only flexible glass frit but also lead-free glass frit.
  • the content and content of the glass frit are 5 to 29 mol% of PbO, 20 to 34 mol% of TeO 2 , 3 to 20 mol% of Bi 2 O 3 , 20 mol% or less of SiO 2 , 10 mol% or less of B 2 O 3 , 10 to 20 mol% of an alkali metal (Li, Na, K, etc.) and an alkaline earth metal (Ca, Mg, etc.)
  • the average particle diameter of the glass frit is not limited, but it may have a particle diameter in the range of 0.5 to 10 mu m, and a mixture of various particles having different average particle diameters may be used.
  • at least one kind of glass frit has an average particle diameter (D50) of not less than 2 mu m and not more than 10 mu m.
  • the content of the glass frit is preferably 1 to 5% by weight based on the total weight of the conductive paste composition. If the amount is less than 1% by weight, incomplete firing may occur to increase electrical resistivity. If the amount exceeds 5% by weight, There is a possibility that the electrical resistivity becomes too high due to too much component.
  • the organic vehicle is not limited, but organic binders, solvents, and the like may be included. Solvents may sometimes be omitted.
  • the organic vehicle is not limited, but is preferably 1 to 10% by weight based on the total weight of the conductive paste composition.
  • the organic vehicle is required to have a property of keeping the metal powder and the glass frit uniformly mixed.
  • the conductive paste becomes homogeneous, And a property to suppress the flow and to improve the discharging property and the plate separability of the conductive paste from the screen plate.
  • the organic binder contained in the organic vehicle is not limited, but examples of the cellulose ester compound include cellulose acetate and cellulose acetate butyrate.
  • examples of the cellulose ether compound include ethylcellulose, methylcellulose, hydroxypropylcellulose, hydroxyethylcellulose
  • examples of the acrylic compound include polyacrylamide, polymethacrylate, polymethylmethacrylate, and polyethylmethacrylate, and the like.
  • examples of the acrylic compound include polyacrylamide, polymethacrylate, polymethylmethacrylate, and polyethylmethacrylate
  • examples of vinyl based ones include polyvinyl butyral, polyvinyl acetate, polyvinyl alcohol, and the like. At least one or more organic binders may be selected and used.
  • Examples of the solvent used for diluting the composition include alpha-terpineol, texanol, dioctyl phthalate, dibutyl phthalate, cyclohexane, hexane, toluene, benzyl alcohol, dioxane, diethylene glycol, ethylene glycol monobutyl ether, ethylene Glycol monobutyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, and the like.
  • the conductive paste composition according to the present invention may further contain additives commonly known in the art, for example, dispersants, plasticizers, viscosity regulators, surfactants, oxidizing agents, metal oxides, metal organic compounds and the like.
  • the present invention also provides a method of forming an electrode of a solar cell and a solar cell electrode produced by the method, wherein the conductive paste is applied on a substrate, followed by drying and firing.
  • the methods used for producing substrates, printing, drying, and firing can be generally those used for manufacturing solar cells, except that conductive pastes containing silver powder having the above- to be.
  • the substrate may be a silicon wafer.
  • Production Example 1 is a step for preparing powder
  • DW De-Mineralized Water
  • 500 g of the silver powder prepared in the above Preparation Example were placed in a 5 L beaker, and silver powder was dispersed in a homo-mixer at 4000 rpm for 20 minutes to prepare silver slurry.
  • 30 ml of pure water was added to a 50 ml beaker, 5 g of PS-810E (ADEKA) (Fatty alcohol phosphate) was added thereto, and the mixture was stirred with ultrasonic waves for 10 minutes to prepare a first coating solution.
  • the first coating solution was added to the silver slurry and agitated at 4000 rpm for 20 minutes to perform primary surface treatment of the silver powder, followed by further washing with pure water through centrifugation to prepare a primary coated silver powder.
  • the silver powder was dispersed again in 2 L of pure water, and then a second coating solution of ammonium stearate solution dissolved in 15 ml of ethanol was added and stirred at 4000 rpm for 20 minutes to subject the silver powder to a second surface treatment,
  • the surface-treated silver powder was prepared by washing with the same process.
  • the surface-treated silver powder was prepared in the same manner as in Example 1 except that the composition of the surface-treated coating liquid was changed as shown in Table 1 below.
  • Comparative Examples 2 to 13 which were surface-treated silver powders, were prepared in the same manner as in Example 1 except that the surface treatment was not carried out in Comparative Example 1 and the composition of the surface-treated coating liquid was changed as shown in Table 1 below.
  • the first treatment agent The second treatment agent ingredient Content (g) ingredient Content (g)
  • Example 1 500 Fatty alcohol phosphate 5 Ammonium stearate 1.5
  • Example 2 500 Aromatic alcohol phosphate 5 Ammonium stearate 1.5
  • Example 3 500 Dialkyl sulfosuccinate 5 Ammonium stearate 1.5
  • Example 4 500 Polypeptide 5 Ammonium stearate 1.5
  • Example 5 500 Fatty alcohol phosphate 5 Stearic acid 1.5
  • Example 6 500 Fatty alcohol phosphate 5 Oleic acid 1.5
  • Example 7 500 Fatty alcohol phosphate 5 Ammonium oleate 1.5
  • Example 8 500 Fatty alcohol phosphate 5 Triethanolamine myristate 1.5
  • Example 9 500 Fatty alcohol phosphate 0.5 Ammonium stearate 1.5
  • Example 10 500 Fatty alcohol phosphate 2.5 Ammonium stearate 1.5
  • Example 11 500 Fatty alcohol phosphate 7.5 Ammonium stearate 1.5
  • Example 12 500 Fatty alcohol phosphate 10 Ammonium ste
  • the surface-treated silver powder was measured for weight loss at room temperature and 500 ° C at a temperature rising rate of 10 ° C / min in the air using a Seiko Instrument TG / DTA EXART 6600 to determine the ignition loss Respectively.
  • the conductive paste prepared in Preparation Example 2 was measured for viscosity at 25 ° C by a Brookfield viscometer (HBDVII + Pro) at a shear rate of 1 rpm at 10 rpm, as shown in Table 2 below. Rick consumption means the ratio of 1 rpm viscosity (low rpm) to 10 rpm viscosity (high rpm).
  • Example 1 0.16 0.06 380 369 1.03
  • Example 2 0.19 0.08 370 320 1.16
  • Example 3 0.08 0.19 540 377 1.43
  • Example 4 0.1 0.19 470 457 1.03
  • Example 5 0.19 0.17 380 443 0.86
  • Example 6 0.08 0.12 310 322 0.96
  • Example 7 0.08 0.05 380 410 0.93
  • Example 8 0.12 0.11 390 400 0.98
  • Example 9 0.06 0.14 530 358 1.48
  • Example 10 0.09 0.11 400 354 1.13
  • Example 11 0.17 0.16 430 464 0.93
  • Example 12 0.06 0.2 480 410 1.17
  • Example 13 0.2 0.17 370 319 1.16
  • Example 14 0.13 0.17 410 498 0.82
  • Example 15 0.08 0.2 490 412 1.19 Comparative Example 1 - - 720 326 2.21 Comparative Example 2 0.01 0.17
  • the viscosity at 1 rpm is 600 to 850 Pa ⁇ s and the viscosity at 10 rpm is 250 to 450 Pa ⁇ s.
  • the slip property of the paste is decreased and the tacky is increased, so that the print quality may be deteriorated.
  • the electroconductive paste prepared in Preparation Example 2 was applied on an alumina substrate using a 360 mesh screen manufactured by Murakami Co., Ltd. with a screen distance of 1.5 mm, a squeegee pressure of 75 N, and a printing speed of 300 mm /
  • the line width pattern was screen printed and dried at 100 DEG C for 30 minutes.
  • the line width of the dried electrode pattern was measured using an optical microscope.
  • Example 10 Line width ( ⁇ m) Line width spreading rate (%) Example 1 48.5 21.3 Example 2 52.9 32.3 Example 3 54.7 36.8 Example 4 52.7 31.8 Example 5 50.6 26.5 Example 6 52.4 31.0 Example 7 51.6 29.0 Example 8 49.2 23.0 Example 9 54.4 36.0 Example 10 51.3 28.3 Example 11 51.1 27.8 Example 12 53.8 34.5 Example 13 53.1 32.8 Example 14 49.5 23.8 Example 15 54.2 35.5 Comparative Example 1 65.4 63.5 Comparative Example 2 59.2 48.0 Comparative Example 3 58.6 46.5 Comparative Example 4 63.8 59.5 Comparative Example 5 66.8 67.0 Comparative Example 6 66.8 67.0 Comparative Example 7 65.7 64.3 Comparative Example 8 63.5 58.8 Comparative Example 9 60.7 51.8 Comparative Example 10 57.8 44.5 Comparative Example 11 55.6 39.0 Comparative Example 12 71.1 77.8 Comparative Example 13 61.8 54.5
  • the line width spreading ratio was at least 21.3% and the maximum was 36.8%, and the line width spreading ratio of the comparative example was at least 44.5% It can be seen that the fine pattern formation is excellent. In particular, it can be seen that, in Examples 1, 7, 8, 10, and 11, the line width spreading rate is 30% or less and the fine pattern formation is further superior.

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Abstract

La présente invention concerne un procédé de traitement de surface d'une poudre d'argent et un procédé de préparation d'une poudre d'argent traitée en surface, et fournit une pâte conductrice ayant un faible rapport thixotrope et comprenant une poudre d'argent traitée en surface par traitement de surface d'une poudre d'argent avec un premier agent de traitement comprenant un tensioactif anionique et un second agent de traitement comprenant un acide gras ou un sel d'acide gras, et, par conséquent, une pâte conductrice est avantageuse pour une impression à grande vitesse et une impression de micromotif.
PCT/KR2018/012184 2017-10-31 2018-10-16 Poudre d'argent traitée en surface et son procédé de préparation WO2019088509A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113275584A (zh) * 2021-05-20 2021-08-20 苏州星翰新材料科技有限公司 一种微纳米银粉及其制备方法和应用

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102454264B1 (ko) * 2020-03-25 2022-10-14 엘에스니꼬동제련 주식회사 점도 안정성이 향상된 전도성 페이스트용 은 분말 및 이의 제조방법
KR102401091B1 (ko) * 2020-11-03 2022-05-23 엘에스니꼬동제련 주식회사 탄성도가 우수한 전도성 페이스트용 은 분말 및 이의 제조방법
CN115070058B (zh) * 2022-08-16 2022-11-01 西安锐创微米科技有限公司 一种抗氧化能力强的高结晶度高球形度钯粉的制备方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000231829A (ja) * 1999-02-10 2000-08-22 Toko Inc 誘電体磁器組成物
KR20070085446A (ko) * 2004-11-29 2007-08-27 다이니뽄 잉끼 가가꾸 고오교오 가부시끼가이샤 표면 처리된 은함유 분말의 제조 방법, 및 표면 처리된은함유 분말을 사용한 은 페이스트
KR20120099587A (ko) * 2011-03-01 2012-09-11 도와 일렉트로닉스 가부시키가이샤 도전용 은코팅 유리분말 및 그 제조 방법, 및 도전성 페이스트
KR20140093670A (ko) * 2011-11-18 2014-07-28 스미토모 긴조쿠 고잔 가부시키가이샤 은 분말, 은 분말의 제조 방법 및 도전성 페이스트
KR20170019727A (ko) * 2015-08-12 2017-02-22 엘에스니꼬동제련 주식회사 고온 소결형 도전성 페이스트용 은 분말의 제조방법
KR20170038860A (ko) * 2014-07-30 2017-04-07 도와 일렉트로닉스 가부시키가이샤 은 분말 및 그의 제조 방법

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62295960A (ja) * 1986-06-16 1987-12-23 Toho Chem Ind Co Ltd 導電性塗布剤組成物
JP4025839B2 (ja) * 1996-09-12 2007-12-26 Ｄｏｗａエレクトロニクス株式会社 銀粉および銀粉の製造方法
JP2000231828A (ja) 1999-02-12 2000-08-22 Murata Mfg Co Ltd 導電性ペースト
JP2005190907A (ja) * 2003-12-26 2005-07-14 Mitsui Mining & Smelting Co Ltd 表面処理金属粉、その表面処理金属粉を用いた導電性ペースト、及びその導電性ペーストを用いて得られるプリント配線板及びチップ部品
CN100577328C (zh) * 2004-11-29 2010-01-06 大日本油墨化学工业株式会社 表面处理的含银粉末的制造方法、以及使用表面处理的含银粉末的银糊剂
JP5139659B2 (ja) * 2006-09-27 2013-02-06 Ｄｏｗａエレクトロニクス株式会社 銀粒子複合粉末およびその製造法
JP2010199034A (ja) * 2009-02-27 2010-09-09 Dic Corp 太陽電池用導電性ペースト及びその製造方法
US8574338B2 (en) * 2010-11-17 2013-11-05 E I Du Pont De Nemours And Company Reactor and continuous process for producing silver powders
KR20130035014A (ko) * 2011-09-29 2013-04-08 삼성전기주식회사 금속 입자의 제조방법, 이를 이용하여 제조된 잉크 조성물 및 페이스트 조성물
JP6389091B2 (ja) * 2013-10-01 2018-09-12 Ｄｏｗａエレクトロニクス株式会社 銀被覆銅粉及びその製造方法、並びに導電性ペースト
JP6029720B2 (ja) * 2014-07-31 2016-11-24 Ｄｏｗａエレクトロニクス株式会社 銀粉及びその製造方法、並びに導電性ペースト
US10272490B2 (en) * 2014-09-29 2019-04-30 Dowa Electronics Materials Co., Ltd. Silver powder, method for producing same, and hydrophilic conductive paste

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000231829A (ja) * 1999-02-10 2000-08-22 Toko Inc 誘電体磁器組成物
KR20070085446A (ko) * 2004-11-29 2007-08-27 다이니뽄 잉끼 가가꾸 고오교오 가부시끼가이샤 표면 처리된 은함유 분말의 제조 방법, 및 표면 처리된은함유 분말을 사용한 은 페이스트
KR20120099587A (ko) * 2011-03-01 2012-09-11 도와 일렉트로닉스 가부시키가이샤 도전용 은코팅 유리분말 및 그 제조 방법, 및 도전성 페이스트
KR20140093670A (ko) * 2011-11-18 2014-07-28 스미토모 긴조쿠 고잔 가부시키가이샤 은 분말, 은 분말의 제조 방법 및 도전성 페이스트
KR20170038860A (ko) * 2014-07-30 2017-04-07 도와 일렉트로닉스 가부시키가이샤 은 분말 및 그의 제조 방법
KR20170019727A (ko) * 2015-08-12 2017-02-22 엘에스니꼬동제련 주식회사 고온 소결형 도전성 페이스트용 은 분말의 제조방법

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113275584A (zh) * 2021-05-20 2021-08-20 苏州星翰新材料科技有限公司 一种微纳米银粉及其制备方法和应用
CN113275584B (zh) * 2021-05-20 2023-11-14 苏州星翰新材料科技有限公司 一种微纳米银粉及其制备方法和应用

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KR102061720B1 (ko) 2020-01-02
JP6982688B2 (ja) 2021-12-17

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