WO2013099818A1 - Particules fines d'argent, procédé de production associé, et pâte conductrice, membrane conductrice et dispositif électrique contenant lesdites particules fines d'argent - Google Patents

Particules fines d'argent, procédé de production associé, et pâte conductrice, membrane conductrice et dispositif électrique contenant lesdites particules fines d'argent Download PDF

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Publication number
WO2013099818A1
WO2013099818A1 PCT/JP2012/083336 JP2012083336W WO2013099818A1 WO 2013099818 A1 WO2013099818 A1 WO 2013099818A1 JP 2012083336 W JP2012083336 W JP 2012083336W WO 2013099818 A1 WO2013099818 A1 WO 2013099818A1
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Prior art keywords
fine particles
silver fine
silver
solution
mol
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PCT/JP2012/083336
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English (en)
Japanese (ja)
Inventor
岩崎　敬介
康男 柿原
哲二 飯田
峰子 大杉
山本　洋介
石谷　誠治
森井　弘子
林　一之
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戸田工業株式会社
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Application filed by 戸田工業株式会社 filed Critical 戸田工業株式会社
Priority to KR1020147016322A priority Critical patent/KR20140113910A/ko
Priority to CN201280062600.XA priority patent/CN104010752A/zh
Publication of WO2013099818A1 publication Critical patent/WO2013099818A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B22F1/056—Submicron particles having a size above 100 nm up to 300 nm
    • 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
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • 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
    • B22F2304/05—Submicron size particles
    • B22F2304/054—Particle size between 1 and 100 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures

Definitions

  • the present invention relates to silver fine particles having an average particle size of 30 to 120 nm excellent in low-temperature sinterability, a method for producing the same, and a conductive paste, a conductive film and an electronic device containing the silver fine particles.
  • the electrodes and circuit patterns of electronic devices are formed by printing electrodes and circuit patterns on a substrate using a conductive paste containing metal particles, and then baking by heating and sintering the metal particles contained in the conductive paste.
  • the heating and baking temperature tends to be lowered.
  • a polyimide flexible substrate is generally used because it can be heated up to about 300 ° C. and has excellent heat resistance.
  • Inexpensive PET (polyethylene terephthalate) substrates and PEN (polyethylene naphthalate) substrates are being investigated as alternative materials.
  • PET substrates and PEN substrates have lower heat resistance than polyimide flexible substrates, and in particular, PET film substrates used for membrane wiring boards need to be heated and fired at 150 ° C. or lower.
  • heating and firing can be performed at a temperature lower than 200 ° C., it becomes possible to form electrodes and circuit patterns on a substrate such as polycarbonate and paper, and it is expected that the use of various electrode materials will be expanded.
  • silver fine particles of nanometer order are expected.
  • the reason for this is that when the size of the metal particles is on the order of nanometers, the surface activity becomes high and the melting point is much lower than that of the bulk metal, so that it can be sintered at a low temperature.
  • silver fine particles are expensive compared to other conductive particles such as copper, and there is a defect that migration is likely to occur among metal particles, but it is difficult to oxidize compared to copper having the same specific resistance. It is easy to handle.
  • nanometer-order silver fine particles can be sintered at low temperatures, and heat resistance is maintained once sintered, which is also expected as a lead-free solder replacement material using a property not found in conventional solder. Has been.
  • Patent Document 1 a method of reducing silver ions in the presence of halide ions (Patent Document 1), at a curing heating temperature of a resin paste.
  • Patent Document 2 A silver powder containing halogen having a high shrinkage rate and a production method (Patent Document 2) for easily and inexpensively obtaining a silver powder containing the halogen have been proposed.
  • Patent Document 3 As a metal powder for producing a sintered product having excellent ductility by promoting sintering at a low temperature (around 600 ° C.), the surface of the metal powder contains 5 to 2,000 ppm of a halogen element or halide. (Patent Document 3) is known.
  • Patent Document 4 polycrystalline silver particles having an average particle size of 30 to 100 nm as a raw material for conductive paste that can be fired at low temperature.
  • Patent Document 1 discloses a method of reducing silver ions in the presence of halide ions.
  • the amount of halide added as shown in the following Comparative Example Since the generated silver fine particles become a dispersion system and the subsequent cleaning becomes insufficient, the amount of carbon of the obtained silver fine particles cannot be reduced to 0.25% by weight or less, and is excellent in low-temperature sinterability. It becomes difficult to obtain silver fine particles.
  • Patent Document 2 discloses silver powder containing halogen, but since the timing of adding the halide is after the silver reduction reaction, silver chloride is formed during the reduction reaction and insolubilized. In comparison, the halogen contained is easily desorbed or ionized.
  • the silver fine particles used for the conductive paste and conductive film used in the formation of the electrode and circuit pattern of the present invention include the particle surface. It is not preferable because halogen is attached in a state of being easily ionized.
  • Patent Document 3 discloses that the surface of a metal powder contains 5 to 2,000 ppm of a halogen element or halide. However, the metal powder described in Patent Document 3 is formed by pressing a metal powder. Thus, a green compact is prepared and sintered at 500 to 900 ° C., and the addition of halogen is intended to reduce ductility and dimensional shrinkage of the sintered part. Silver fine particles used for the conductive paste and conductive film used for forming the electrode and circuit pattern of the present invention are not preferable because halogen is attached to the particle surface in a state of being easily ionized.
  • Patent Document 4 discloses polycrystallized silver particles having an average particle diameter of 30 to 100 nm as a raw material for conductive pastes and the like that can be fired at a low temperature by controlling the entire process from reaction to drying at 30 ° C. or lower.
  • the halide fine particles are not added, the generated fine silver particles become a dispersion system, and the subsequent cleaning becomes insufficient. .25% by weight or less cannot be obtained, and it becomes difficult to obtain silver fine particles having better low-temperature sinterability.
  • it is necessary to control a drying temperature to 30 degrees C or less it is industrially disadvantageous.
  • the present invention prepares an alcohol solution of an amine complex of silver nitrate prepared using silver nitrate and one or more water-soluble or water-soluble aliphatic amines having 2 to 4 carbon atoms (solution A).
  • solution A an aqueous solution in which ascorbic acid or erythorbic acid and a halide are dissolved separately from the liquid A (liquid B), and mix the liquid A and the liquid B using a static mixer.
  • a halogen of 1.6 ⁇ 10 ⁇ 3 mol or more per mol of silver nitrate in the solution B This is a method for producing silver fine particles characterized by adding a chemical compound (Invention 1).
  • the present invention also relates to silver fine particles obtained by the method of the present invention 1 wherein the carbon content of the silver fine particles is 0.25% by weight or less (Invention 2).
  • the present invention is the silver fine particle of the present invention 2 in which the particle surface of the silver fine particle is coated with a polymer compound having a molecular weight of 10,000 or more (Invention 3).
  • this invention is the silver fine particle of this invention 2 or this invention 3 whose average particle diameter (D SEM ) is 30 nm or more and 120 nm or less (this invention 4).
  • the present invention is a conductive paste containing the silver fine particles according to any one of the present invention 2 to the present invention 4 (the present invention 5).
  • the present invention is a conductive film formed using the conductive paste of the present invention 5 (Invention 6).
  • the present invention is an electronic device having the conductive film of the present invention 6 (present invention 7).
  • the silver fine particles according to the present invention are suitable as a raw material for conductive pastes and the like that can be fired at a low temperature because the carbon content after the reduction reaction is low.
  • the method for producing silver fine particles according to the present invention can reduce the carbon content of the silver fine particles after the reduction reaction, and can obtain silver fine particles in a high yield, so that it has excellent low-temperature sinterability. It is suitable as a method for producing silver fine particles.
  • Silver fine particles according to the present invention are prepared by preparing an alcohol solution of an amine complex of silver nitrate prepared using silver nitrate and one or more water-soluble or water-soluble aliphatic amines having 2 to 4 carbon atoms (solution A). ), An aqueous solution in which ascorbic acid or erythorbic acid and a halide are dissolved separately from the liquid A (liquid B), and the liquid A and the liquid B mixed using a static mixer, After adding to a container containing water and stirring, the obtained silver fine particles can be obtained by washing and drying.
  • the alcohol solution (A solution) of the silver nitrate amine complex in the present invention is obtained by mixing silver nitrate and one or more of water-soluble or water-soluble aliphatic amines having 2 to 4 carbon atoms in the alcohol solution. be able to.
  • the addition amount of the aliphatic amine is preferably 2.0 to 2.5 mol, more preferably 2.0 to 2.3 mol, relative to 1 mol of silver nitrate. When the amount of the aliphatic amine is less than 2.0 mol with respect to 1 mol of silver nitrate, large grains tend to be generated.
  • aliphatic amine having 2 to 4 carbon atoms in the present invention it is important to use a water-soluble or water-soluble one, specifically, ethylamine, n-propylamine, iso-propylamine, n-butylamine. Iso-butylamine and the like can be used, but n-propylamine and n-butylamine are preferable in consideration of the low-temperature sintering property and handling property of the silver fine particles.
  • alcohol in the present invention those having compatibility with water can be used. Specifically, methanol, ethanol, propanol, isopropanol, and the like can be used, and methanol and ethanol are preferable. These alcohols may be used alone or in combination.
  • an aqueous solution in which ascorbic acid or erythorbic acid and a halide are dissolved is prepared (liquid B).
  • the amount of ascorbic acid or erythorbic acid added is preferably 1.0 to 2.0 mol, more preferably 1.0 to 1.8 mol, per mol of silver nitrate in the liquid A to be mixed.
  • ascorbic acid or erythorbic acid exceeds 2.0 mol with respect to 1 mol of silver nitrate, the generated silver fine particles tend to aggregate, which is not preferable.
  • Examples of the halide in the present invention include potassium chloride (KCl), sodium chloride (NaCl), ammonium chloride (NH 4 Cl), potassium bromide (KBr), sodium bromide (NaBr), ammonium bromide (NH 4 Br).
  • potassium chloride (KCl) sodium chloride (NaCl), ammonium chloride (NH 4 Cl), potassium bromide (KBr), sodium bromide (NaBr), ammonium bromide (NH 4 Br).
  • potassium iodide (KI), sodium iodide (NaI) and ammonium iodide (NH 4 I) can be used, preferably potassium chloride (KCl), sodium chloride Chloride such as (NaCl).
  • the added amount of the halide is preferably 1.6 ⁇ 10 ⁇ 3 to 8.0 ⁇ 10 ⁇ 3 mol, more preferably 1.7 ⁇ 10 ⁇ to 1 mol of silver nitrate in the liquid A to be mixed. 3 to 6.0 ⁇ 10 ⁇ 3 mol, and even more preferably 1.8 ⁇ 10 ⁇ 3 to 4.0 ⁇ 10 ⁇ 3 mol.
  • the added amount of halide exceeds 8.0 ⁇ 10 ⁇ 3 mol with respect to 1 mol of silver nitrate, the effect of making the slurry of silver fine particles obtained by adding the halide agglomerated is saturated, Existence of halides more than necessary is not preferable for silver fine particles used for conductive pastes and conductive film applications used for forming electrodes and circuit patterns.
  • the amount of halide added is less than 1.6 ⁇ 10 ⁇ 3 mol relative to 1 mol of silver nitrate, the amount of halide present is too small, and the resulting silver fine particle slurry becomes dispersed, and thereafter Insufficient cleaning of the silver fine particles makes it difficult to reduce the carbon content of the silver fine particles to 0.25% by weight or less.
  • the alcohol solution of silver nitrate amine complex (liquid A) and the aqueous solution (liquid B) in which ascorbic acid or erythorbic acid and halide are dissolved are mixed using a static mixer and added to a container containing water. And stir.
  • a method in which an aqueous solution (liquid B) in which ascorbic acid or erythorbic acid and a halide are dissolved is dropped into an alcohol solution (liquid A) of an amine complex of silver nitrate, or an aqueous solution (liquid B) in which erythorbic acid and a halide are dissolved.
  • the mixed concentration of liquid A and liquid B in which the initial reduction reaction occurs is constant, so that the particle size distribution of the obtained silver fine particles is more uniform. Things are easy to get.
  • a silver nitrate amine complex alcohol solution (liquid A) and an aqueous solution (liquid B) in which ascorbic acid or erythorbic acid and a halide are dissolved are mixed using a static mixer, and water is added to the resulting reaction solution.
  • the resulting silver fine particles are filtered using alcohol and water by a conventional method. ⁇ Wash with water. At this time, washing is performed until the electric conductivity of the filtrate is 60 ⁇ S / cm or less.
  • the washed silver fine particle cake is redispersed in a hydrophilic organic solvent, the water on the surface of the silver fine particles is replaced with the hydrophilic organic solvent, and then the silver fine particles filtered by a conventional method are heated at a temperature of 40 ° C. or lower, preferably 30.
  • the silver fine particles of the present invention can be obtained by pulverizing by a conventional method after drying at a temperature not higher than ° C. or vacuum drying. By replacing the water on the surface of the silver fine particles with a hydrophilic organic solvent, it is possible to prevent the silver fine particles after drying from being firmly agglomerated with each other, and subsequent grinding treatment or surface treatment / grinding treatment, etc. It becomes easy.
  • hydrophilic organic solvent examples include methanol, ethanol and propanol, acetone and the like. Considering removal of the solvent by drying, methanol and ethanol are preferred.
  • the silver fine particles according to the present invention are preferably surface-treated with a polymer compound having a molecular weight of 10,000 or more before pulverization.
  • the coating amount with a polymer compound having a molecular weight of 10,000 or more is preferably 0.2 to 4% by weight, more preferably 0.3 to 3% by weight, based on the silver fine particles.
  • the treatment amount with the polymer compound is within the above range, a sufficient treatment effect by the pulverization treatment can be obtained.
  • a high pulverization effect can be obtained in the subsequent pulverization treatment, and a more uniform pulverization treatment is possible.
  • the surface treatment of the silver fine particles with the polymer compound is carried out by redispersing the silver fine particles after substitution and drying with a hydrophilic organic solvent in a polymer compound solution obtained by dissolving the polymer compound in the organic solvent, for 30 to 300 minutes. After gently stirring, the organic solvent is removed and drying is performed.
  • Silver fine particles according to the present invention are silver fine particles obtained by the above production method, and the carbon content of the silver fine particles obtained by washing and drying the silver fine particle slurry after the reduction reaction is 0.25% by weight or less. To do.
  • the amount of carbon in the silver fine particles obtained by washing and drying the silver fine particle slurry after the reduction reaction exceeds 0.25% by weight, the low-temperature sinterability is impaired, which is not preferable.
  • a lower limit is 0.15 weight% normally, and when it falls below this, there exists a tendency for the wettability to a solvent and resin to fall. More preferred is 0.15 to 0.24% by weight, and even more preferred is 0.16 to 0.23% by weight.
  • the average particle diameter (D SEM ) of the silver fine particles according to the present invention is preferably 30 nm to 120 nm, more preferably 35 nm to 110 nm, and still more preferably 40 nm to 100 nm.
  • the average particle diameter (D SEM ) is in the above range, the electronic device obtained using this can be easily miniaturized.
  • the average particle size (D SEM ) is less than 30 nm, the surface activity of the silver fine particles increases, and it is not preferable because a large amount of organic matter or the like needs to be adhered in order to stably maintain the fine particle size. .
  • the crystallite diameter (D X ) of the silver fine particles according to the present invention is preferably 30 nm or less, more preferably 10 to 29 nm, and still more preferably 10 to 28 nm.
  • the crystallite diameter (D X ) exceeds 30 nm, the reactivity in the silver fine particles is lowered, and the low-temperature sinterability is impaired.
  • the crystallite diameter (D X ) is less than 10 nm, the silver fine particles become unstable and partial sintering and fusion start even at room temperature, which is not preferable.
  • the polycrystallinity [the ratio of the average particle size (D SEM ) to the crystallite size (D X ) (D SEM / D X )] of the silver fine particles according to the present invention is 2.8 or more, more preferably 3. It is 0 or more, still more preferably 3.2 or more.
  • the degree of polycrystallinity is less than 2.8, the crystallite diameter in the silver fine particles becomes large and approaches a single crystal, so that the reactivity in the silver fine particles is lowered and the low-temperature sinterability is impaired. Absent.
  • the upper limit of the polycrystallinity is about 10, more preferably about 8.
  • the low-temperature sinterability of the silver fine particles according to the present invention is the change rate of crystallite diameter (D X ) due to heating described later [(crystallite diameter (D X ) of silver fine particles after heating at 150 ° C. for 30 minutes / before heating).
  • the crystallite diameter (D X )) ⁇ 100] of the silver fine particles is evaluated, and the change rate of the crystallite diameter (D X ) by heating at 150 ° C. is preferably 130% or more, more preferably 135%. That's it.
  • the change rate of the crystallite diameter (D X ) is less than 130%, it cannot be said that the low temperature sinterability is excellent.
  • the change rate of the crystallite diameter (D X ) is preferably 140% or more, and more preferably 150% or more.
  • the BET specific surface area value of the silver fine particles according to the present invention is preferably 10 m 2 / g or less, more preferably 8 m 2 / g or less.
  • the BET specific surface area value exceeds 10 m 2 / g, the viscosity of the conductive paste obtained by using this is not preferable.
  • the halogen content of the silver fine particles according to the present invention is preferably 1.6 ⁇ 10 ⁇ 3 to 8.0 ⁇ 10 ⁇ 3 mol of halogen, more preferably 1.7 ⁇ 10 ⁇ 3 to 1 mol of silver. It is 6.0 ⁇ 10 ⁇ 3 mol, and even more preferably 1.8 ⁇ 10 ⁇ 3 to 4.0 ⁇ 10 ⁇ 3 mol.
  • the halogen content exceeds 8.0 ⁇ 10 ⁇ 3 mol with respect to 1 mol of silver, the halogen content is too high, so the conductive paste and conductive film used for forming electrodes and circuit patterns are used.
  • the silver fine particles used in are not preferred.
  • the particle shape of the silver fine particles according to the present invention is preferably spherical or granular.
  • the surface of the silver fine particles obtained by washing and drying the silver fine particle slurry after the reduction reaction is preferably coated with a polymer compound having a molecular weight of 10,000 or more.
  • a polymer compound having a molecular weight of 10,000 or more When the molecular weight is less than 10,000, agglomerates are produced in the subsequent pulverization treatment, and the resulting silver fine particles are not preferable because dispersibility in the conductive paste becomes difficult.
  • the upper limit of the molecular weight of the polymer compound is about 100,000, and if the molecular weight is increased beyond this, the viscosity increases and it becomes difficult to uniformly treat the surface of the silver fine particles.
  • a dispersant having both an acidic functional group and a basic functional group or a dispersant having an acid value and an amine value It is preferable to use together with the dispersing agent which has.
  • polymer dispersant those commercially available as pigment dispersants can be used, and specifically, ANTI-TERRA-U, ANTI-TERRA-205, DISPERBYK-101, DISPERBYK-102. , DISPERBYK-106, DISPERBYK-108, DISPERBYK-109, DISPERBYK-110, DISPERBYK-111, DISPERBYK-112, DISPERBYK-116, DISPERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-142, DISPERBYK-142, DISPERBYK-142, DISPERBYK-142 -162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-166, D SPERBYK-167, DISPERBYK-168, DISPERBYK-170, DISPERBYK-171, DISPERBYK-
  • the conductive paste according to the present invention may be in any form of a fired paste and a polymer paste.
  • the conductive paste is composed of the silver fine particles and the glass frit according to the present invention.
  • Other components may be blended.
  • a polymer type paste it consists of silver fine particles and a solvent according to the present invention, and if necessary, other components such as a binder resin, a curing agent, a dispersant, and a rheology modifier may be blended.
  • binder resin those known in the art can be used.
  • cellulose resins such as ethyl cellulose and nitrocellulose
  • various modified materials such as polyester resins, urethane modified polyester resins, epoxy modified polyester resins, and acrylic modified polyesters.
  • These binder resins can be used alone or in combination of two or more.
  • solvent those known in the art can be used, and examples thereof include tetradecane, toluene, xylene, ethylbenzene, diethylbenzene, isopropylbenzene, amylbenzene, p-cymene, tetralin, and petroleum aromatic hydrocarbon mixtures.
  • Hydrocarbon solvents ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol mono-t-butyl ether, diethylene glycol monoethyl ether, diethylene glycol Monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monobutyl ether, tri Ether or glycol ether solvents such as propylene glycol monomethyl ether; glycol ester solvents such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate Ketone solvents such as methyl isobutyl ketone and cyclohexanone; terpen
  • the content of silver fine particles in the conductive paste varies depending on the application, but it is preferably as close to 100% by weight as possible, for example, in the case of wiring formation.
  • the conductive paste according to the present invention is obtained by mixing and dispersing each component using various kneaders and dispersers such as a laika machine, a pot mill, a three roll mill, a rotary mixer, a twin screw mixer, and the like. Can do.
  • the conductive paste according to the present invention can be applied to various coating methods such as screen printing, ink jet method, gravure printing, transfer printing, roll coating, flow coating, spray coating, spin coating, dipping, blade coating, and plating.
  • the conductive paste according to the present invention is used for forming electrodes such as FPD (flat panel display), solar cell, organic EL, wiring for LSI substrates, and wiring for filling fine trenches, via holes, contact holes, etc. It can be used as a material.
  • FPD flat panel display
  • organic EL organic EL
  • wiring for LSI substrates and wiring for filling fine trenches, via holes, contact holes, etc.
  • It can be used as a material.
  • FPD flat panel display
  • organic EL organic EL
  • An important point in the present invention is that an alcohol solution of an amine complex of silver nitrate prepared using silver nitrate and one or more water-soluble or water-soluble aliphatic amines having 2 to 4 carbon atoms is prepared (solution A). ), An aqueous solution in which ascorbic acid or erythorbic acid and a halide are dissolved separately from the liquid A (liquid B), and the liquid A and the liquid B mixed using a static mixer, It is a fact that the silver fine particles according to the present invention obtained by washing and drying the obtained silver fine particles after adding to a container containing water and stirring are excellent in low-temperature sinterability.
  • the present inventors reduced 1.6 ⁇ 10 ⁇ 3 mol of halide to 1 mol of silver nitrate.
  • the resulting silver fine particle slurry becomes an agglomerated system, which facilitates subsequent cleaning, so that the carbon content of the silver fine particles could be reduced to 0.25% by weight or less. I believe that.
  • the silver fine particle obtained has the polycrystallinity whose polycrystallinity degree is 2.8 or more.
  • the average particle size of the silver fine particles was obtained by taking a photograph of the particles using a scanning electron micrograph “S-4800” (manufactured by HITACHI) and measuring the particle size equivalent to a sphere for 100 or more particles using the photograph. The average value was calculated and used as the average particle size (D SEM ).
  • the specific surface area of the silver fine particles was represented by a value measured by BET method using “Monosorb MS-11” (manufactured by Kantachrome Co., Ltd.).
  • the amount of carbon in the silver fine particles obtained by washing and drying the silver fine particle slurry after the reduction reaction was determined using “Horiba Metal Carbon / Sulfur Analyzer EMIA-2200 type” (manufactured by Horiba, Ltd.).
  • the crystallite size (D X ) of the silver fine particles is the peak of the plane index (1,1,1) plane using the K ⁇ ray of Cu as the radiation source using an X-ray diffractometer “RINT 2500” (manufactured by Rigaku Corporation). And the crystallite diameter was calculated from the Scherrer equation.
  • the degree of polycrystallinity of the silver fine particles was indicated by the ratio (D SEM / D X ) between the average particle diameter (D SEM ) and the crystallite diameter (D X ).
  • the halogen content in the silver fine particles was determined by a combustion tube type oxygen combustion / ion chromatography method in which 20 mg of a measurement sample was burned in a combustion tube at 1100 ° C., and the generated gas was collected and measured by ion chromatography. .
  • the change rate (%) of the crystallite diameter due to heating of the silver fine particles is the crystallite diameter (D X ) after heating the silver fine particles at 150 ° C. for 30 minutes and the crystallite diameter (D X ) of the silver fine particles before heating. It is the value calculated according to the following formula 1. Note that the rate of change in crystallite diameter was determined in the same manner when the heating condition was changed to 210 ° C. for 30 minutes.
  • the specific resistance of the conductive coating is obtained by applying a conductive paste, which will be described later, onto a polyimide film, pre-drying at 120 ° C., and then heating and curing at 150 ° C., 210 ° C., and 300 ° C. for 30 minutes.
  • a conductive paste which will be described later
  • Each of the obtained conductive films was measured using a four-terminal electric resistance measuring device “Loresta GP / MCP-T600” (manufactured by Mitsubishi Chemical Analytech Co., Ltd.), and the specific resistance was calculated from the sheet resistance and the film thickness.
  • Example 1-1 Production of silver fine particles> After adding 5.16 kg of silver nitrate, 25.8 L of methanol, and 4.89 kg of n-butylamine to a 50 L container, the mixture A was prepared by mixing and stirring while cooling to 15 ° C. or lower. Separately, 27.8 L of water and 8.03 kg of erythorbic acid were weighed and dissolved in a 50 L container, and then 3.78 g of sodium chloride was added and mixed and stirred while cooling to 15 ° C. or lower. B liquid was prepared.
  • liquid A and liquid B were added to a container containing 7 L of water while mixing using a static mixer, stirred for 5 hours while cooling the reaction system to 25 ° C. or lower, and then allowed to stand for 30 minutes. The solid was allowed to settle. After removing the supernatant liquid by decantation, suction filtration was performed using a filter paper, followed by washing and filtration using methanol and pure water.
  • a part of the solid matter of the obtained silver fine particles was dried in a dryer at 40 ° C. for 6 hours and then pulverized to obtain silver fine particles of Example 1-1.
  • the obtained silver fine particles have a granular shape, a carbon amount of 0.20% by weight, an average particle size (D SEM ) of 81.7 nm, a crystallite size D X of 23.8 nm, and a polycrystallinity (D SEM / D X ) is 3.4, BET specific surface area value is 5.3 m 2 / g, halogen content is 690 ppm, change rate of crystallite size (150 ° C. ⁇ 30 minutes) is 138%, change of crystallite size The rate (210 ° C. ⁇ 30 minutes) was 161%.
  • Example 2-1 Production of conductive paste> 11.0 parts by weight of polyester resin and 1.4 parts by weight of curing agent with respect to 100 parts by weight of silver fine particles of Example 1-1, and diethylene glycol monoethyl so that the content of silver fine particles in the conductive paste is 70 wt%.
  • Ether is added and premixed using a rotating / revolving mixer “Awatori Nertaro ARE-310” (registered trademark, manufactured by Sinky Corporation), and then uniformly mixed and dispersed using three rolls. Conductive paste was obtained.
  • the conductive paste obtained above was applied onto a polyimide film having a thickness of 50 ⁇ m and heated at 120 ° C., 210 ° C. and 300 ° C. for 30 minutes, respectively, to obtain a conductive coating film.
  • the specific resistance when the obtained conductive film is heat-treated at 120 ° C. for 30 minutes is 9.5 ⁇ 10 ⁇ 6 ⁇ ⁇ cm
  • the specific resistance when heat-treated at 210 ° C. for 30 minutes is 4.1. ⁇ a 10 -6 ⁇ ⁇ cm
  • the specific resistance in the case of heat treatment at 300 ° C. 30 minutes was 2.6 ⁇ 10 -6 ⁇ ⁇ cm.
  • Silver fine particles and a conductive paste were prepared according to Example 1-1 and Example 2-1. Various characteristics of each production condition and the obtained silver fine particle powder and electric paste are shown.
  • Examples 1-2 to 1-3 and Comparative Examples 1-1 to 1-2 Silver fine particles were obtained by variously changing the production conditions of the silver fine particles.
  • Examples 1-5 to 1-6 Silver fine particles were obtained by variously changing the kind of polymer compound and the processing conditions.
  • Examples 2-2 to 2-6 and comparative examples 2-1 to 2-2 A conductive paint and a conductive film were produced according to the method for producing a conductive paint of Example 2-1 except that the kind of silver fine particles was variously changed.
  • Table 4 shows the manufacturing conditions and various characteristics of the obtained conductive coating film.
  • the silver fine particles according to the present invention are suitable as a raw material for conductive pastes and the like that can be fired at a low temperature because the carbon content after the reduction reaction is low.
  • the method for producing silver fine particles according to the present invention can reduce the carbon content of the silver fine particles after the reduction reaction, and can obtain silver fine particles in a high yield, so that it has excellent low-temperature sinterability. It is suitable as a method for producing silver fine particles.

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Abstract

La présente invention concerne : des particules fines d'argent avec une excellente aptitude au frittage à basse température ; un procédé de production associé ; et une pâte conductrice, une membrane conductrice et un dispositif électronique, contenant les particules fines d'argent. Dans un procédé permettant de produire des particules fines d'argent qui comprend les étapes consistant à préparer une solution alcoolique (A) d'un complexe nitrate d'argent-amine préparé en utilisant du nitrate d'argent et au moins une amine aliphatique C2-4 hydrosoluble, préparer, séparément de la solution (A), une solution aqueuse (B) dans laquelle soit un acide ascorbique soit un acide érythorbique et un halogénure sont dissous, ajouter un mélange de la solution (A) à la solution (B) dans un récipient dans lequel de l'eau a été versé, mélanger le mélange obtenu, et soumettre ensuite les particules fines d'argent ainsi obtenues au lavage et au séchage, au moins 1,6×10-3 mol d'un halogénure par mol de nitrate d'argent est ajouté à la solution (B), ce qui permet d'obtenir une bouillie de particules fines d'argent agrégées pour faciliter le lavage ultérieur. Ainsi, des particules fines d'argent qui présentent une teneur en argent de 0,25 % en poids ou moins et ainsi présentent une excellente aptitude au frittage à basse température peuvent être obtenues.
PCT/JP2012/083336 2011-12-28 2012-12-21 Particules fines d'argent, procédé de production associé, et pâte conductrice, membrane conductrice et dispositif électrique contenant lesdites particules fines d'argent WO2013099818A1 (fr)

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CN201280062600.XA CN104010752A (zh) 2011-12-28 2012-12-21 银微粒及其制造方法、以及含有该银微粒的导电性糊、导电性膜和电子器件

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WO2015190076A1 (fr) * 2014-06-11 2015-12-17 バンドー化学株式会社 Dispersion de fines particules d'argent, fines particules d'argent, et son procédé de production
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JP7183504B2 (ja) * 2017-09-06 2022-12-06 住友金属鉱山株式会社 湿式ニッケル粉末の粗大粒子低減方法
CN109465467B (zh) * 2018-12-24 2022-04-12 北京光禾生物科技有限公司 液态纳米银制备方法
CN114054769B (zh) * 2021-11-17 2024-05-03 广东羚光新材料股份有限公司 一种银微粉及其制备方法和应用
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WO2015190076A1 (fr) * 2014-06-11 2015-12-17 バンドー化学株式会社 Dispersion de fines particules d'argent, fines particules d'argent, et son procédé de production
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US11407030B2 (en) * 2015-10-30 2022-08-09 Dowa Electronics Materials Co., Ltd. Silver powder and method for producing same

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