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WO2016052362A1 - Poudre d'argent, son procédé de production et pâte conductrice hydrophile - Google Patents

Poudre d'argent, son procédé de production et pâte conductrice hydrophile Download PDF

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Publication number
WO2016052362A1
WO2016052362A1 PCT/JP2015/077212 JP2015077212W WO2016052362A1 WO 2016052362 A1 WO2016052362 A1 WO 2016052362A1 JP 2015077212 W JP2015077212 W JP 2015077212W WO 2016052362 A1 WO2016052362 A1 WO 2016052362A1
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WIPO (PCT)
Prior art keywords
silver powder
silver
mass
phosphorus
conductive paste
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
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PCT/JP2015/077212
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English (en)
Japanese (ja)
Inventor
直樹 田原
徳昭 野上
洋 神賀
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Dowa Electronics Materials Co Ltd
Original Assignee
Dowa Electronics Materials Co Ltd
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 Dowa Electronics Materials Co Ltd filed Critical Dowa Electronics Materials Co Ltd
Priority to CN201580052235.8A priority Critical patent/CN107000050B/zh
Priority to US15/514,879 priority patent/US10272490B2/en
Priority to KR1020177011674A priority patent/KR102308923B1/ko
Priority claimed from JP2015188835A external-priority patent/JP6096261B2/ja
Publication of WO2016052362A1 publication Critical patent/WO2016052362A1/fr
Anticipated expiration legal-status Critical
Priority to US16/298,595 priority patent/US10807161B2/en
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/16—Metallic particles coated with a non-metal
    • 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
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C5/00—Alloys based on noble metals
    • C22C5/06—Alloys based on silver

Definitions

  • the present invention relates to silver powder, a method for producing the same, and a hydrophilic conductive paste.
  • silver powder is added to an organic vehicle and kneaded as a conductive paste for use in electronic components such as internal electrodes of multilayer capacitors, conductor patterns of circuit boards, and electrodes and circuits of substrates for solar cells and display panels.
  • a conductive paste to be manufactured is used.
  • Such silver powder for conductive paste is required to have a reasonably small particle size and uniform particle size in order to cope with downsizing of electronic parts, high density of conductor patterns, fine lines, and the like. ing.
  • the silver powder When using a highly water-soluble organic solvent or water as the solvent used in the conductive paste, the silver powder does not disperse in the conductive paste unless the silver powder used in the conductive paste is compatible with the organic solvent or water.
  • the conductive paste When the conductive paste is applied to a substrate or the like, the thickness of the film made of the conductive paste becomes non-uniform so that the conductivity of the conductor formed by firing the conductive paste There is a problem that the adhesive strength deteriorates.
  • an alkali or complexing agent is added to the silver salt-containing aqueous solution to produce a silver oxide-containing slurry or a silver complex salt-containing aqueous solution, and the silver particles are reduced and precipitated by adding a reducing agent.
  • Add at least one chelate forming agent selected from fatty acids, fatty acid salts, surfactants, organic metals, protective colloids, compounds having an azole structure, dicarboxylic acids, oxycarboxylic acids, and salts thereof as dispersants to the slurry solution Have been proposed (see, for example, Patent Documents 1 and 2).
  • a slurry-like reaction system 2 before or after the reduction precipitation of silver particles or during the reduction precipitation.
  • a hydrophobic dispersant such as benzotriazole, stearic acid, or oleic acid
  • a hydrophilic dispersant such as gelatin or collagen peptide
  • the silver powder cannot be dispersed in the conductive paste as a result. Also, depending on the type of surfactant to be added, depending on the pH of the reaction solution and coexisting ions, the dispersion effect may be insufficient or the effect may not appear, and the type of surfactant that can be used is limited, Moreover, it is difficult to control the exact coating amount on the surface of the silver powder.
  • a phosphate ester-based surfactant is used when the wet cake having a water content of 20% to 80% is crushed by a mixer without drying after washing the reduced silver powder by filtration and washing.
  • a method has been proposed in which a surfactant is attached by removing the presence of the reaction solution by adding, washing again with filtered water, and drying (see Patent Document 1).
  • a dispersion formed by dispersing silver particles and an alkylamine-based or alkylamine salt-based or phosphoric ester-based surfactant having a phosphorus content of 0.5% by mass to 10% by mass in a solvent is used.
  • an object of the present invention is to provide silver powder suitable for a conductive paste having excellent hydrophilicity and using a highly water-soluble solvent and water, a method for producing the same, and a hydrophilic conductive paste.
  • silver powder is dispersed without adding a surfactant in the volume-based particle size distribution measurement by the laser diffraction particle size distribution measurement method.
  • IPA isopropyl alcohol
  • D 50 -IPA 50% cumulative particle diameter D 50 in the case of using water as the measurement solvent for dispersing the silver powder - Assuming W ( ⁇ m)
  • silver powder satisfying D 50 -IPA> D 50 -W has excellent hydrophilicity and is suitable for a conductive paste using a highly water-soluble solvent or water. .
  • a silver powder suitable for a conductive paste using a highly water-soluble solvent or water can be efficiently produced by adding a compound containing phosphorus having a phosphorus content of more than 10% by mass to 30% by mass to any of them. I found out.
  • This invention is based on the said knowledge by this inventor, and as a means for solving the said subject, it is as follows. That is, ⁇ 1> In the measurement of the volume-based particle size distribution by the laser diffraction particle size distribution measurement method, the cumulative 50% particle size when isopropyl alcohol (IPA) is used as a measurement solvent for dispersing silver powder is D 50 -IPA ( ⁇ m ), And when water is used as a measurement solvent for dispersing silver powder, the cumulative 50% particle diameter is D 50 -W ( ⁇ m), and D 50 -IPA> D 50 -W is satisfied, and phosphorus contained in the silver powder The silver powder is characterized in that the rate is 0.01% by mass or more and 0.3% by mass or less.
  • IPA isopropyl alcohol
  • ⁇ 2> The silver powder according to ⁇ 1>, wherein the surface of the silver powder has a compound containing phosphorus.
  • ⁇ 3> The silver powder according to ⁇ 2>, wherein the compound containing phosphorus is phytic acid.
  • ⁇ 4> is a 50% cumulative particle diameter D 50 0.1 ⁇ m or 5 ⁇ m or less, the BET specific surface area is less than 0.1 m 2 / g or more 5 m 2 / g to any one of ⁇ 1> to ⁇ 3> It is the described silver powder.
  • ⁇ 5> a step of reducing and precipitating silver particles by adding a reducing agent to an aqueous reaction system containing silver ions;
  • ⁇ 6> The method for producing a silver powder according to ⁇ 5>, wherein the phosphorus-containing compound is a phosphoric ester of inositol.
  • ⁇ 7> The silver powder production method according to ⁇ 6>, wherein the inositol phosphate is phytic acid.
  • ⁇ 8> The silver powder according to any one of ⁇ 5> to ⁇ 7>, wherein the reducing agent is at least one selected from ascorbic acid, alkanolamine, sodium borohydride, hydroquinone, hydrazine, and formalin. Is the method.
  • ⁇ 9> A silver powder characterized by having phytic acid on the surface.
  • ⁇ 10> A hydrophilic conductive paste comprising the silver powder according to any one of ⁇ 1> to ⁇ 4> and ⁇ 9>.
  • ⁇ 11> A hydrophilic conductive paste comprising the silver powder according to any one of ⁇ 1> to ⁇ 4> and ⁇ 9>, a resin, and a solvent, wherein the solvent is water.
  • silver powder suitable for a conductive paste having excellent hydrophilicity and a highly water-soluble solvent or water can be obtained.
  • silver powder can be efficiently produced without adding a new step in the method for producing silver powder by adding a reducing agent to the aqueous reaction system containing silver ions to reduce and precipitate silver particles and drying. Can do.
  • FIG. 1 is a graph showing the measurement results of the particle size distribution of the silver powder of Example 1.
  • FIG. 2 is a graph showing the measurement results of the particle size distribution of the silver powder of Example 2.
  • the silver powder of the present invention has a cumulative 50% particle diameter of D 50 ⁇ when isopropyl alcohol (IPA) is used as a measurement solvent for dispersing the silver powder in the volume-based particle size distribution measurement by the laser diffraction particle size distribution measurement method. It is characterized by satisfying D 50 -IPA> D 50 -W, where D 50 -W ( ⁇ m) is the cumulative 50% particle diameter when water is used as a measurement solvent for dispersing silver powder with IPA ( ⁇ m). To do.
  • IPA isopropyl alcohol
  • it is a silver powder characterized by having phytic acid on the surface.
  • the silver powder of the present invention has excellent hydrophilicity and is suitable for a conductive paste using a highly water-soluble solvent or water.
  • a surfactant or the like is not added, and only isopropyl alcohol (IPA) or only water is used as a measurement solvent.
  • IPA isopropyl alcohol
  • the silver powder does not satisfy the relationship of D 50 -IPA> D 50 -W, it may not be suitable for a conductive paste using a highly water-soluble solvent or water.
  • the cumulative 50% particle size D 50 is preferably 0.1 ⁇ m or more 5 ⁇ m or less, more preferably 0.5 ⁇ m or more 3 ⁇ m or less.
  • the 50% cumulative particle diameter D 50 is a value measured using isopropyl alcohol as a measurement solvent.
  • the 50% cumulative particle diameter D 50 is less than 0.1 [mu] m, but corresponds to the fine line of is possible, high activity of the silver particles, when using the silver powder sintering conductive paste It may not be suitable for baking at 500 ° C. or higher.
  • the cumulative 50% particle diameter D 50 exceeds 5 ⁇ m, the dispersibility of the silver powder is inferior, and it may be difficult to cope with fine lines.
  • the cumulative 50% particle size D 50 is obtained by adding 0.1 g of a silver powder sample to 40 mL of a measurement solvent (isopropyl alcohol or water) and dispersing it for 2 minutes with an ultrasonic homogenizer with a tip diameter of 20 mm. Measurement is carried out using Microtrac MT3300EXII). The obtained measurement results were graphed to determine the cumulative particle size distribution of the silver particles.
  • the cumulative 50% particle size when the measurement solvent is water is expressed as D 50 -W
  • the cumulative 50% particle size when the measurement solvent is isopropyl alcohol is expressed as D 50 -IPA.
  • the surface of the silver powder has a compound containing phosphorus.
  • “having a compound containing phosphorus on the surface of the silver powder” means that the compound containing phosphorus is attached to the surface of the silver powder by some method such as adsorption or coating, As long as it has a compound containing phosphorus on at least a part of the surface, it may have a compound containing phosphorus on the entire surface of the silver powder, or a part of the surface of the silver powder may contain a compound containing phosphorus. You may do it. In addition, you may have the compound containing phosphorus inside silver powder.
  • the phosphorus content in the phosphorus-containing compound is preferably more than 10% by mass and 30% by mass or less, more preferably 20% by mass to 30% by mass
  • examples include polyphosphoric acid, phosphate compounds, and phosphate esters.
  • the phosphate compound include hypophosphite, orthophosphite, metaphosphite, hypophosphate, orthophosphate, metaphosphate, monoperoxyphosphate, peroxydiphosphorus And acid salts, tripolyphosphates, tetrapolyphosphates, pyrophosphates, and the like.
  • the phosphate esters include trialkyl phosphate esters, dialkyl phosphate esters, monoalkyl phosphate esters, polyphosphate esters, and inositol phosphate esters.
  • the phosphate group that can be an adsorbing functional group with the silver powder surface has one or two hydroxyl groups.
  • inositol phosphate is preferable.
  • the inositol phosphates include phytic acid.
  • the phytic acid is inositol hexaphosphate (myo-inositol hexaphosphate), the compositional formula is C 6 H 18 O 24 P 6 , and is represented by the following structural formula.
  • the phytic acid has a phosphorus content in the compound of 28.2% by mass, and there are two hydroxyl groups in the phosphate group, a strong chelating action, and a strong adsorption power on the metal surface. Dispersibility can be improved.
  • the silver powder has a phosphorus content in the silver powder of 0.01% by mass to 0.3% by mass, and preferably 0.01% by mass to 0.25% by mass.
  • the phosphorus content is less than 0.01% by mass, the effect may be insufficient.
  • the content exceeds 0.3% by mass, the compound contains phosphorus that is liberated without being adsorbed on the silver powder. The amount of the excessive amount may adversely affect the paste characteristics.
  • Phosphorus content in the silver powder was determined by adding phosphorus to the silver powder using a ICP mass spectrometer (manufactured by Hitachi High-Tech Science Co., Ltd., SPS-5100) for the filtrate from which solid components were removed by filtration. The phosphorus content in silver powder can be calculated.
  • the phosphorus content rate in the said silver powder in this invention is the value which measured the phosphorus in the component which exists in the silver powder surface.
  • the presence of phytic acid on the surface of the silver powder means that, for example, a solution obtained by extracting silver powder with 1% by mass of trichloroacetic acid or HCl / MeOH is ion chromatograph (DC-500, manufactured by Dionex Co., Ltd., Ionpac AS17- By measuring using C), the phytic acid on the surface of the silver powder can be qualitatively analyzed by detecting a peak indicating phytic acid.
  • DC-500 ion chromatograph
  • BET specific surface area of the silver powder is preferably from 0.1 m 2 / g or more 5 m 2 / g or less, more preferably 0.1 m 2 / g or more 2m 2 / g. If the BET specific surface area exceeds 5 m 2 / g, the viscosity of the conductive paste may be too high, and printability may deteriorate. On the other hand, when the BET specific surface area is less than 0.1 m 2 / g, silver particles may be too large, and it may be difficult to cope with fine lines.
  • the BET specific surface area is, for example, MONOSORB HM-model 1210 (manufactured by MOUNTECH), using He: 70%, N 2 : 30% carrier gas, 3 g of silver powder in a cell, and degassing at 60 ° C. After a minute, it can be measured by the BET one point method.
  • the silver powder of the present invention having excellent hydrophilicity as described above can be efficiently produced by the method for producing silver powder of the present invention described below.
  • the method for producing silver powder of the present invention includes a step of reducing and depositing silver particles by adding a reducing agent to an aqueous reaction system containing silver ions (hereinafter referred to as “silver particle production step”), and Contains phosphorus whose phosphorus content in the compound is more than 10% by mass and less than 30% by mass at least one of before reduction deposition of the silver particles, during reduction deposition of the silver particles, and after reduction deposition of the silver particles.
  • a step of adding a compound to be added hereinafter referred to as “compound addition step containing phosphorus”
  • a silver powder suitable for a conductive paste having a compound containing phosphorus on the surface and using a highly water-soluble solvent or water is used as an aqueous reaction system containing silver ions.
  • a reducing agent is added to reduce and precipitate silver particles and then dried, it can be efficiently produced without adding a new step.
  • the highly water-soluble solvent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include ketones such as acetone and dimethyl ketone, esters such as ethyl acetate and diethylene glycol ethyl ether acetate, and ethanol. And alcohols such as isopropyl alcohol, glycols such as ethylene glycol and propylene glycol, and glycol ethers such as ethyl cellosolve and methyl cellosolve.
  • the silver particle preparation step is a step of reducing and depositing silver particles by adding a reducing agent to an aqueous reaction system containing silver ions.
  • an aqueous reaction system containing silver ions for example, an aqueous solution containing silver nitrate, a silver complex or a silver intermediate, or a slurry can be used. Among these, an aqueous solution containing a silver complex is preferable.
  • the aqueous solution containing the silver complex can be prepared by adding aqueous ammonia, ammonium salt, chelate compound or the like to the aqueous silver nitrate solution.
  • the slurry containing the silver intermediate can be prepared by adding sodium hydroxide, sodium chloride, sodium carbonate or the like to the silver nitrate aqueous solution.
  • an ammine complex aqueous solution obtained by adding ammonia water to a silver nitrate aqueous solution is preferable because the silver powder has an appropriate particle size and a spherical shape. Since the coordination number of ammonia in the ammine complex aqueous solution is 2, it is preferable to add 2 moles or more of ammonia per mole of silver. Further, if the amount of ammonia added is too large, the complex becomes too stable and the reduction is difficult to proceed. Therefore, the amount of ammonia added is preferably 8 mol or less per mol of silver.
  • a pH adjuster to the aqueous reaction system containing a silver ion.
  • general acids and bases can be used, and for example, nitric acid, sodium hydroxide and the like can be used.
  • reducing agent examples include ascorbic acid, sulfite, alkanolamine, hydrogen peroxide, formic acid, ammonium formate, sodium formate, glyoxal, tartaric acid, sodium hypophosphite, sodium borohydride, hydroquinone, hydrazine, and hydrazine compounds. , Pyrogallol, glucose, gallic acid, formalin, anhydrous sodium sulfite, Rongalite and the like. These may be used individually by 1 type and may use 2 or more types together.
  • ascorbic acid, alkanolamine, sodium borohydride, hydroquinone, hydrazine, and formalin are preferable, and hydrazine and formalin are particularly preferable because silver particles having an appropriate particle diameter can be obtained.
  • the amount of the reducing agent added is preferably 1 equivalent or more with respect to silver in order to increase the reaction yield of silver, and when a reducing agent having a weak reducing power is used, it is 2 with respect to silver. It is preferable to add an equivalent or more reducing agent, and it is more preferable to add a 10 to 20 equivalent reducing agent with respect to silver.
  • the phosphorus content is more than 10% by mass and more than 30% at least before the reduction precipitation of the silver particles, during the reduction precipitation of the silver particles, and after the reduction precipitation of the silver particles. It is a step of adding a phosphorus-containing compound that is not more than%.
  • a compound other than the compound containing phosphorus may be interposed between the silver powder and the compound containing phosphorus by adding another compound or the like. .
  • the phosphorus-containing compound can be appropriately selected from the same phosphorus-containing compounds as those described for the silver powder, but inositol phosphates are preferred, and phytic acid is more preferred.
  • the addition of the phosphorus-containing compound is performed by wet-adding the phosphorus-containing compound at least one of before the silver particle reduction precipitation, during the silver particle reduction precipitation, and after the silver particle reduction precipitation. , By stirring.
  • the addition amount of the phosphorus-containing compound is preferably 0.05% by mass or more and 5% by mass or less with respect to the silver powder charged into the aqueous reaction system. In the range of 0.05 mass% or more and 5 mass%, a silver powder suitable for a conductive paste using a highly water-soluble solvent or water can be obtained.
  • the slurry containing the obtained silver powder is filtered and washed with water to obtain a lump cake containing 1% by mass to 200% by mass of water and almost no fluidity with respect to the silver powder.
  • the filtration method is not particularly limited as long as it is a method used for solid-liquid separation, and can be appropriately selected according to the purpose. Examples thereof include a centrifugal filter, a filter press, and a Buchner funnel.
  • the water in the cake may be replaced with a lower alcohol or a polyol.
  • the silver powder drying step is a step of drying the cake obtained in the silver powder washing step.
  • Silver powder is obtained by drying the said cake with dryers, such as a forced circulation type
  • dryers such as a forced circulation type
  • crushing instead of crushing, silver particles are put into a device that can mechanically fluidize the particles, and the particles are mechanically collided with each other, thereby smoothing irregularities and angular portions on the surface of the silver powder.
  • Surface smoothing treatment may be performed.
  • the integrated apparatus For example, the dry meister made from Hosokawa Micron Corporation, a micron dryer, etc.
  • a silver powder having excellent hydrophilicity suitable for a conductive paste using a highly water-soluble solvent or water can be obtained.
  • the silver powder of the present invention has excellent hydrophilicity, it can be applied to a conductive paste suitable for ink jet printing utilizing low-temperature baking and quick drying in an inert gas, for example, for solar cells.
  • Conductive coating is performed by coating or printing directly on various substrates such as silicon wafers, touch panel films, glass for EL devices, etc., or if necessary on these films on which a transparent conductive film is further provided.
  • a film can be suitably formed.
  • it is suitably used for a current collecting electrode of a solar battery cell, an external electrode of a chip-type electronic component, an RFID, an electromagnetic wave shield, a vibrator adhesion, a membrane switch, an electroluminescence electrode, or an electrical wiring application.
  • the hydrophilic conductive paste means a paste using a highly water-soluble solvent or water and can contain 1% by mass or more of water.
  • the hydrophobic conductive paste can be distinguished from the hydrophilic conductive paste since water is separated when 1% by mass or more of water is added.
  • the hydrophilic conductive paste of the present invention contains silver powder, a resin, and a solvent, and further contains other components as necessary.
  • the silver powder of the present invention is used as the silver powder.
  • silver powder having phytic acid on the surface is preferably used.
  • the solvent examples include a highly water-soluble solvent and water.
  • the highly water-soluble solvent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include ketones such as acetone and dimethyl ketone; esters such as ethyl acetate and diethylene glycol ethyl ether acetate; ethanol And alcohols such as isopropyl alcohol; glycols such as ethylene glycol and propylene glycol; and glycol ethers such as ethyl cellosolve and methyl cellosolve. These may be used individually by 1 type and may use 2 or more types together.
  • As the solvent water is preferable.
  • the resin is not particularly limited and may be appropriately selected depending on the intended purpose.
  • phenol resin methylol urea resin, methylol melamine resin, polyvinyl alcohol, polyethylene oxide, methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, Examples thereof include hydroxyethyl methyl cellulose, hydroxypropyl cellulose, acrylic resin, polyacrylamide resin, polyester resin, styrene resin, and maleic acid resin. These may be used individually by 1 type and may use 2 or more types together.
  • the other component is not particularly limited and may be appropriately selected depending on the intended purpose.
  • examples thereof include a surfactant that can be mixed with water at an arbitrary ratio, a water-soluble dispersant, and a dispersion stabilizer.
  • the method for producing the hydrophilic conductive paste is not particularly limited and may be appropriately selected depending on the purpose.
  • the silver powder, the resin, the solvent, and, if necessary, the other components For example, it can be produced by mixing using ultrasonic dispersion, a disper, a three-roll mill, a ball mill, a bead mill, a twin-screw kneader, a self-revolving stirrer and the like.
  • the hydrophilic conductive paste has a wider application target than the hydrophobic conductive paste that repels water depending on the application target. Moreover, since the hydrophilic conductive paste can reduce the amount of the organic solvent used, it can reduce the environmental load. In particular, a hydrophilic conductive paste that does not use an organic solvent as a solvent and uses water as a solvent can greatly reduce the environmental burden and necessary equipment during drying and baking.
  • Example 1 Silver ion containing 3,600 g of silver nitrate solution containing 52 g of silver, 160 g of 28% by weight ammonia aqueous solution (made by Junsei Chemical Co., Ltd., special grade) added thereto, and 95 g of 20% by weight sodium hydroxide aqueous solution added thereto An aqueous reaction system containing was prepared, and the liquid temperature was adjusted to 25 ° C. To the aqueous reaction system containing silver ions, 13 g of an 80% by mass hydrazine aqueous solution (manufactured by Otsuka Chemical Co., Ltd.) as a reducing agent was added and stirred sufficiently to obtain a slurry containing silver powder.
  • an 80% by mass hydrazine aqueous solution manufactured by Otsuka Chemical Co., Ltd.
  • the cumulative 50% particle size D 50 -W, D 50 -IPA, and BET specific surface area in the volume-based particle size distribution measurement by the laser diffraction particle size distribution measurement method are obtained as follows. It was. As a result, D 50 -W was 1.0 ⁇ m, D 50 -IPA was 1.3 ⁇ m, and D 50 -W ⁇ D 50 -IPA was satisfied. The BET specific surface area was 1.8 m 2 / g. With respect to the obtained silver powder, the concentration of phosphorus was measured using an ICP analyzer (manufactured by Hitachi High-Tech Science Co., Ltd., SPS-5100), and the phosphorus content in the silver powder was calculated to be 0.03% by mass. . These results are shown in Table 2.
  • ⁇ Cumulative 50% by mass particle size (D 50 ) by laser diffraction particle size distribution measurement method Add 0.1 g of silver powder sample to 40 mL of water or isopropyl alcohol as a measurement solvent, disperse for 2 minutes with an ultrasonic homogenizer with a tip diameter of 20 mm, and measure using a Macrotrac particle size distribution analyzer (Microtrac MT3300EXII, manufactured by Nikkiso Co., Ltd.) did. The obtained measurement results were graphed to determine the cumulative particle size distribution of the silver particles.
  • FIG. 1 shows the particle size distribution of both water and isopropyl alcohol in Example 1. The cumulative 50% particle size when the measurement solvent is water is expressed as D 50 -W, and the cumulative 50% particle size when the measurement solvent is isopropyl alcohol is expressed as D 50 -IPA.
  • Example 2 Silver ion containing 3,600 g of silver nitrate solution containing 52 g of silver, 160 g of 28% by weight ammonia aqueous solution (made by Junsei Chemical Co., Ltd., special grade) added thereto, and 5 g of 20% by weight sodium hydroxide aqueous solution added thereto An aqueous reaction system containing was prepared, and the liquid temperature was 28 ° C. To the aqueous reaction system containing the silver ions, 240 g of a 37 mass% formalin aqueous solution (manufactured by Nippon Kasei Co., Ltd.) was added as a reducing agent and sufficiently stirred to obtain a slurry containing silver powder.
  • a 37 mass% formalin aqueous solution manufactured by Nippon Kasei Co., Ltd.
  • Example 3 Silver ion containing 3,600 g of silver nitrate solution containing 52 g of silver, 160 g of 28% by weight ammonia aqueous solution (made by Junsei Chemical Co., Ltd., special grade) added thereto, and 95 g of 20% by weight sodium hydroxide aqueous solution added thereto An aqueous reaction system containing was prepared, and the liquid temperature was adjusted to 25 ° C.
  • the obtained silver powder was evaluated in the same manner as in Example 1. As a result, D 50 -W was 0.9 ⁇ m, D 50 -IPA was 1.2 ⁇ m, and D 50 -W ⁇ D 50 -IPA was satisfied. .
  • the BET specific surface area was 4.4 m 2 / g. Moreover, it was 0.24 mass% when the density
  • Example 4 Silver ion containing 3,600 g of silver nitrate solution containing 52 g of silver, 160 g of 28% by weight ammonia aqueous solution (made by Junsei Chemical Co., Ltd., special grade) added thereto, and 5 g of 20% by weight sodium hydroxide aqueous solution added thereto An aqueous reaction system containing was prepared, and the liquid temperature was 28 ° C. After adding 0.41 g of a 50% by mass aqueous solution of phytic acid (manufactured by Tsukino Food Industry Co., Ltd., the phosphorus content in the phytic acid is 28.2% by mass) to the aqueous reaction system containing silver ions, a reducing agent.
  • phytic acid manufactured by Tsukino Food Industry Co., Ltd.
  • the obtained silver powder was evaluated in the same manner as in Example 1. As a result, D 50 -W was 2.0 ⁇ m, D 50 -IPA was 2.2 ⁇ m, and D 50 -W ⁇ D 50 -IPA was satisfied. .
  • the BET specific surface area was 1.2 m 2 / g.
  • concentration of phosphorus was measured like Example 1 and the phosphorus content rate in silver powder was computed, it was 0.10 mass%.
  • Example 5 Silver ion containing 3,600 g of silver nitrate solution containing 52 g of silver, adding 160 g of 28% by weight ammonia aqueous solution (manufactured by Junsei Chemical Co., Ltd., special grade), and adding 20 g of 20% by weight sodium hydroxide aqueous solution An aqueous reaction system containing was prepared, and the liquid temperature was 28 ° C.
  • the obtained silver powder was evaluated in the same manner as in Example 1. As a result, D 50 -W was 0.8 ⁇ m, D 50 -IPA was 1.0 ⁇ m, and D 50 -W ⁇ D 50 -IPA was satisfied. .
  • the BET specific surface area was 2.5 m 2 / g.
  • concentration of phosphorus was measured like Example 1 about the obtained silver powder and the phosphorus content rate in silver powder was computed, it was 0.14 mass%.
  • Example 1 the dispersant is polyoxyethylene tridecyl ether phosphate (Pricesurf A212C, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., phosphorus content is less than 5.6% by mass), and the addition amount is 0.21 g.
  • the silver particles were aged in the same manner as in Example 1 except for changing to.
  • the slurry aged as described above was filtered, washed with water, and crushed to obtain a silver powder of Comparative Example 1.
  • the obtained silver powder was evaluated in the same manner as in Example 1.
  • D 50 -W was 4.0 ⁇ m
  • D 50 -IPA was 2.8 ⁇ m
  • D 50 -W> D 50 -IPA. Sex was low.
  • the BET specific surface area was 1.0 m 2 / g. Moreover, it was 0.004 mass% when the density
  • Example 2 the dispersant is polyoxyethylene tridecyl ether phosphate (Pricesurf A212C, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., phosphorus content is less than 5.6% by mass), and the addition amount is 0.21 g.
  • the silver particles were aged in the same manner as in Example 2 except for changing to.
  • the slurry aged as described above was filtered, washed with water, and crushed to obtain a silver powder of Comparative Example 2.
  • the obtained silver powder was evaluated in the same manner as in Example 1. As a result, D 50 -W was 8.6 ⁇ m, D 50 -IPA was 4.5 ⁇ m, and D 50 -W> D 50 -IPA. Sex was low.
  • Example 3 In Example 1, the dispersing agent was changed to polyphosphoric acid 116% (manufactured by Junsei Co., Ltd., phosphorus content 36.2% by mass), and the addition amount was changed to 0.21 g. The silver particles were aged. The slurry aged as described above was filtered, washed with water, and crushed to obtain a silver powder of Comparative Example 3. The obtained silver powder was evaluated in the same manner as in Example 1. As a result, D 50 -W was 4.2 ⁇ m, D 50 -IPA was 3.5 ⁇ m, and D 50 -W> D 50 -IPA. Sex was low. Further, the BET specific surface area was 1.4 m 2 / g. Moreover, about the obtained silver powder, when the density
  • Example 4 silver particles were aged in the same manner as in Example 1 except that the dispersant was gelatin (E-200, manufactured by Zerais Co., Ltd.) and the addition amount was changed to 0.21 g.
  • the slurry aged as described above was filtered, washed with water, and crushed to obtain a silver powder of Comparative Example 4.
  • the obtained silver powder was evaluated in the same manner as in Example 1.
  • D 50 -W was 1.7 ⁇ m
  • D 50 -IPA was 1.6 ⁇ m
  • the BET specific surface area was 1.5 m 2 / g.
  • about the obtained silver powder when the density
  • Example 5 (Comparative Example 5) In Example 1, silver particles were aged in the same manner as in Example 1 except that no dispersant was added. The slurry aged as described above was filtered, washed with water, and crushed to obtain a silver powder of Comparative Example 5. The obtained silver powder was evaluated in the same manner as in Example 1. As a result, D 50 -W was 7.8 ⁇ m, D 50 -IPA was 7.7 ⁇ m, and D 50 -W> D 50 -IPA. Sex was low. The BET specific surface area was 1.0 m 2 / g. Moreover, about the obtained silver powder, when the density
  • Example 6 silver particles were aged in the same manner as in Example 2 except that no dispersant was added. The slurry aged as described above was filtered, washed with water, and crushed to obtain a silver powder of Comparative Example 6. The obtained silver powder was evaluated in the same manner as in Example 1. As a result, D 50 -W was 8.9 ⁇ m, D 50 -IPA was 6.1 ⁇ m, and D 50 -W> D 50 -IPA. Sex was low. Since this silver powder floated on the surface of the water and formed a porridge on the bottom, it was added to the measuring apparatus while stirring. The BET specific surface area was 0.3 m 2 / g. Moreover, about the obtained silver powder, when the density
  • Example 6 The silver powder obtained in Example 2 was confirmed to have phytic acid at least on its surface by a method using an ion chromatograph (Dionex DC-500, column is Ionpac AS17-C manufactured by Dionex). 0.01 g of the silver powder obtained in Example 2, 1.6 g of resin (manufactured by Nisshinsei Co., Ltd., CELLOSIZEQP-09L), and 18.4 g of ion-exchanged water are weighed with an electronic balance, and a metal spatula is used for 1 minute. Stir. Then, the dispersion liquid was obtained by performing dispersion
  • ion chromatograph Dionex
  • Example 2 90% by mass of the silver powder obtained in Example 2, 0.8% by mass of resin (manufactured by Nihon Kasei Co., Ltd., CELLOSIZEQP-09L), and 9.2% by mass of ion-exchanged water were obtained in the same manner as described above.
  • a hydrophilic conductive paste 1 was obtained by pasting.
  • a 1-inch substrate of 96% alumina is prepared, and the hydrophobic conductive paste 1 and the hydrophilic conductive paste 1 are applied to the surface of the alumina substrate by a screen printing machine (MT-320T, manufactured by Microtech Co., Ltd.).
  • Printed formed an electrode shape with a width of 500 ⁇ m and a length of 37,500 ⁇ m, dried for 10 minutes at 150 ° C. with a hot air drier, and fired an IR furnace (4 chamber furnace made by NGK Corporation) at peak temperature Baked at 850 ° C.
  • volume resistance resistance value ( ⁇ ) ⁇ film thickness ( ⁇ m) ⁇ 500 ( ⁇ m) ⁇ 0.0001 ⁇ 37500 ( ⁇ m) Table 3 shows the obtained resistance value, film thickness, and volume resistance.
  • Example 7 (Comparative Example 7)
  • stearic acid manufactured by Wako Pure Chemical Industries, Ltd., reagent special grade
  • the addition amount was changed to 0.21 g, and the silver particles were treated in the same manner as in Example 2.
  • the aged slurry was filtered, washed with water, and crushed to obtain a silver powder of Comparative Example 7.
  • the obtained silver powder was evaluated in the same manner as in Example 1.
  • D 50 -W was 8.6 ⁇ m
  • D 50 -IPA was 4.5 ⁇ m
  • Sex was low. Since this silver powder floated on the surface of the water and formed a porridge on the bottom, it was added to the measuring apparatus while stirring.
  • the BET specific surface area was 0.3 m 2 / g.
  • the obtained silver powder was dispersed in 0.01 g of the above silver powder into 1.6 g of resin (manufactured by Nihon Kasei Co., Ltd., CELLOSIZEQP-09L) and 18.4 g of ion-exchanged water. As a result, silver powder repelled ion-exchanged water, and no dispersion was obtained.
  • the obtained silver powder was 90% by mass of silver powder, 0.8% by mass of resin (manufactured by Wako Pure Chemical Industries, Ltd., ethyl cellulose), and solvent (Wako Pure Chemical Industries, Ltd.).
  • the hydrophilic conductive paste which can use water as a solvent is obtained by using phytic acid as a surface treating agent,
  • the volume resistance is the hydrophobic conductive paste using the same silver powder of Example 6.
  • the silver powder of the present invention has excellent hydrophilicity and can use a highly water-soluble solvent or water as a solvent for the conductive paste, for example, it makes use of low-temperature firing and quick drying in an inert gas.
  • the present invention can be applied to a conductive paste suitable for inkjet printing or the like.
  • the hydrophilic conductive paste of the present invention is used for, for example, a collector electrode of a solar battery cell, an external electrode of a chip-type electronic component, an RFID, an electromagnetic wave shield, a vibrator adhesive, a membrane switch, an electroluminescence electrode, or an electrical wiring application. Preferably used.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Conductive Materials (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Powder Metallurgy (AREA)

Abstract

L'invention concerne une poudre d'argent caractérisée en ce que, en mesurant la distribution de diamètre particulaire en fonction du volume par un procédé de mesure de distribution granulométrique de type à diffraction laser, l'exigence D50-IPA>D50-W est satisfaite [dans laquelle : D50-IPA représente le diamètre particulaire cumulé à 50 % (μm) mesuré en utilisant comme solvant de mesure de l'alcool isopropylique (IPA) dans lequel la poudre d'argent est dispersée ; et D50-W représente le diamètre particulaire cumulé à 50 % (μm) mesuré en utilisant comme solvant de mesure de l'eau dans laquelle la poudre d'argent est dispersée], et la teneur en phosphore dans la poudre d'argent va de 0,01 à 0,3 % en masse, inclus.
PCT/JP2015/077212 2014-09-29 2015-09-25 Poudre d'argent, son procédé de production et pâte conductrice hydrophile Ceased WO2016052362A1 (fr)

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CN201580052235.8A CN107000050B (zh) 2014-09-29 2015-09-25 银粉及其制备方法、以及亲水性导电浆料
US15/514,879 US10272490B2 (en) 2014-09-29 2015-09-25 Silver powder, method for producing same, and hydrophilic conductive paste
KR1020177011674A KR102308923B1 (ko) 2014-09-29 2015-09-25 은 분말, 그 제조방법 및 친수성 도전성 페이스트
US16/298,595 US10807161B2 (en) 2014-09-29 2019-03-11 Silver powder, method for producing same, and hydrophilic conductive paste

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JP2014198979 2014-09-29
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JP2015188835A JP6096261B2 (ja) 2014-09-29 2015-09-25 銀粉及びその製造方法、並びに親水性導電ペースト

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JP6313896B1 (ja) * 2016-11-08 2018-04-18 Ｄｏｗａエレクトロニクス株式会社 銀粒子分散液およびその製造方法並びにその銀粒子分散液を用いた導電膜の製造方法
CN112404450A (zh) * 2020-11-05 2021-02-26 成都市天甫金属粉体有限责任公司 一种高分散高球形度多孔银粉的化学合成方法
CN116864182A (zh) * 2023-08-25 2023-10-10 南通大学 一种水性环保型太阳能电池细栅银浆

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CN112404450B (zh) * 2020-11-05 2023-04-07 成都市天甫金属粉体有限责任公司 一种高分散高球形度多孔银粉的化学合成方法
CN116864182A (zh) * 2023-08-25 2023-10-10 南通大学 一种水性环保型太阳能电池细栅银浆

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