WO2018163619A1 - Procédé de production de nanoparticules d'argent - Google Patents

Procédé de production de nanoparticules d'argent Download PDF

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Publication number
WO2018163619A1
WO2018163619A1 PCT/JP2018/001793 JP2018001793W WO2018163619A1 WO 2018163619 A1 WO2018163619 A1 WO 2018163619A1 JP 2018001793 W JP2018001793 W JP 2018001793W WO 2018163619 A1 WO2018163619 A1 WO 2018163619A1
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silver
amine
oxalate
silver oxalate
heating
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PCT/JP2018/001793
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English (en)
Japanese (ja)
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祐樹 新谷
外村　卓也
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バンドー化学株式会社
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Priority to JP2018504302A priority Critical patent/JP6404523B1/ja
Publication of WO2018163619A1 publication Critical patent/WO2018163619A1/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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables

Definitions

  • the present invention relates to a method for producing silver nanoparticles.
  • the fine metal particles used in the conductive ink are nanometer-sized particles that are much smaller than the conductive fillers in the conventional conductive paste, so they can be sintered at low temperatures due to the melting point drop unique to nanoparticles.
  • high conductivity close to that of a metal foil can be realized. Examples of the type of metal used in such a conductive ink include silver, gold, and copper.
  • Patent Document 1 relates to a method for producing nanometer-sized silver ultrafine particles, and reacts silver oxalate with oleylamine to produce a complex compound containing at least silver, oleylamine, and oxalate ions, and the resulting complex compound Discloses a method for producing silver ultrafine particles by thermally decomposing the above.
  • Patent Document 2 relates to a method for producing metal nanoparticles, wherein a complexing reaction liquid is obtained by heating a mixture containing nickel carboxylate and primary amine to a temperature in the range of 100 to 165 ° C.
  • a method of obtaining a slurry of nickel nanoparticles coated with a primary amine by heating the crystallization reaction liquid to a temperature of 170 ° C. or higher by microwave irradiation to reduce nickel ions in the complexation reaction liquid is disclosed. .
  • Patent Documents 3 and 4 disclose a method for producing fine metal particles by irradiating and heating a microwave to an organic solvent in which a metal oxide or a metal hydroxide is dispersed.
  • Patent Document 5 in a method for producing metal nanoparticles in which metal nanoparticles are formed in a solution by a chemical reaction, a step of dispersing a powder of an inorganic compound that is a metal source in the solution, and a step of adding a dispersant
  • a method for producing metal nanoparticles which includes a step of irradiating at least one of heat and cavitation to reduce an inorganic compound, and microwaves are mentioned as a heat irradiation method.
  • a method of producing silver nanoparticles by producing a silver reduction reaction by heating using a mixture of amine and silver oxalate as a starting material is silver carbonate.
  • silver nanoparticles can be produced at a low temperature and silver nanoparticles with few impurities can be easily obtained.
  • the silver oxalate-amine complex has a high viscosity, and when heated and reduced by an ordinary method such as an oil bath, it takes time to synthesize silver nanoparticles, and thus the productivity is low.
  • Patent Document 1 describes that by using oleylamine, silver ultrafine particles having a narrow particle size distribution and excellent storage stability can be obtained.
  • a small amount of silver oxalate of 150 mmol or less is used.
  • There was room for improvement in terms of productivity because it was reduced by heating at 0 ° C. for 1 hour.
  • countermeasures against the difficulty in synthesizing particles with an increase in the charged amount have been demanded.
  • Patent Document 2 not only two-stage heating is performed for the formation of a complexing reaction solution and heat reduction, but also heat reduction is performed at a very high temperature, and a silver oxalate-amine complex is prepared. Unlike the method for producing silver nanoparticles at a low temperature, silver nanoparticles having excellent conductivity and low-temperature sintering properties for printed electronics are not produced.
  • heat reduction at a high temperature as in Patent Document 2 is performed, the volatilization of the amine proceeds excessively, and the amine coordinated to the particles is removed.
  • Patent Document 5 discloses a method of heating a solution by irradiating microwaves, but it does not heat a highly viscous silver oxalate-amine complex.
  • the present invention has been made in view of the above situation, and a silver nanoparticle production method capable of producing a large amount of silver nanoparticles having a narrow particle size distribution in a short time from a highly viscous silver oxalate-amine complex.
  • the purpose is to provide.
  • the inventors of the present invention have studied various methods for producing silver nanoparticles, and have focused on a method for obtaining silver nanoparticles from a silver oxalate-amine complex.
  • a method for obtaining silver nanoparticles from a silver oxalate-amine complex due to the high viscosity of the silver oxalate-amine complex, it has been difficult to produce silver nanoparticles with a narrow particle size distribution in a short time with an increase in the charged amount by a normal method such as an oil bath.
  • the present inventors have found that microwave absorption of alkylamine and alkoxyamine is good, and combined at least one of alkylamine and alkoxyamine with heating by microwave irradiation. As a result of the reduction, it was found that silver nanoparticles could be synthesized in just a few minutes, and the present invention was completed.
  • the method for producing silver nanoparticles of the present invention comprises a mixing step of mixing an amine and silver oxalate to obtain a silver oxalate-amine complex in which the amine is coordinated to silver oxalate, and the above silver oxalate-amine complex. Heating with microwave irradiation and reducing the silver oxalate-amine complex, wherein the amine contains at least one compound selected from at least one of alkylamines and alkoxyamines. It is characterized by.
  • the method for producing silver nanoparticles of the present invention may include a step of adding a solvent to the silver oxalate-amine complex between the mixing step and the heating step.
  • the amine preferably includes at least one compound selected from at least one of an alkylamine having 5 or less carbon atoms and an alkoxyamine having 5 or less carbon atoms.
  • a large amount of silver nanoparticles having a narrow particle size distribution can be produced from a highly viscous silver oxalate-amine complex in a short time.
  • the method for producing silver nanoparticles of the present invention comprises a mixing step of mixing an amine and silver oxalate to obtain a silver oxalate-amine complex in which the amine is coordinated to silver oxalate, and the above silver oxalate-amine complex. Heating with microwave irradiation and reducing the silver oxalate-amine complex, wherein the amine contains at least one compound selected from at least one of alkylamines and alkoxyamines. It is characterized by.
  • the method for producing silver nanoparticles of the present invention includes a mixing step of mixing an amine and silver oxalate to obtain a silver oxalate-amine complex in which the amine is coordinated with silver oxalate.
  • the amine includes at least one compound selected from at least one of alkylamine and alkoxyamine. Specifically, only one type of compound classified as an alkylamine may be used, two or more types of compounds classified as an alkylamine may be used, or 1 classified as an alkoxyamine. Only one type of compound may be used, two or more types of compounds classified as alkoxyamines may be used, or one or more types of compounds classified as alkylamines and 1 classified as alkoxyamines Two or more kinds of compounds may be used in combination.
  • the amine mixed with silver oxalate is preferably at least one of alkylamine and alkoxyamine, but other than alkylamine and alkoxyamine as long as it does not cause a reduction reaction before the heating step.
  • An amine may be added.
  • an amine having a hydroxyl group such as an alkanolamine is highly polar for use as a ligand, and if the amount is large, it may cause a reduction reaction before the heating step.
  • an amine other than alkylamine and alkoxyamine it is preferably 5 equivalents or less based on the number of moles of silver oxalate used.
  • the alkylamine may be any one having an alkyl group and an amine functional group in the molecule, and may be a diamine having two amine functional groups in the molecule. Further, the alkylamine may be any of primary amine, secondary amine, and tertiary amine, but is preferably a primary amine from the viewpoint of promoting the formation of a complex.
  • the alkyl group may be linear or branched, and may partially contain a saturated carbocycle, but a linear alkylamine is preferably used.
  • alkylamine examples include ethylamine, propylamine, butylamine, pentylamine, hexylamine, 1,2-ethanediamine, 1,4-butanediamine, 1,5-pentanediamine and the like.
  • alkylamines having 5 or less carbon atoms are preferably used from the viewpoint of promoting the formation of a complex and enhancing the dispersibility in a highly polar solvent.
  • any alkoxyamine may be used as long as it has an alkoxy group and an amine functional group in the molecule.
  • the alkoxyamine may be any of primary amine, secondary amine, and tertiary amine, but is preferably a primary amine from the viewpoint of promoting the formation of a complex.
  • the alkoxy group may be linear or branched, and may partially contain a saturated carbocyclic ring or an unsaturated carbocyclic ring, but a linear alkoxyamine is preferably used.
  • Specific examples of the alkoxyamine include N- (3-methoxypropyl) propane-1,3-diamine, 2-methoxyethylamine, 3-methoxypropylamine, 3-ethoxypropylamine and the like.
  • an alkoxyamine having 5 or less carbon atoms is preferably used.
  • the silver oxalate is the simplest silver dicarboxylate, and the silver oxalate-amine complex synthesized using silver oxalate is reduced at a low temperature in a short time. This is suitable for the synthesis of silver fine particles. Further, when silver oxalate is used, no by-product is generated at the time of synthesis, and only carbon dioxide derived from oxalate ions is produced outside the system.
  • a mixing ratio of the amine and the silver oxalate it is preferable to increase the number of moles of the amine rather than the number of moles of silver atoms, and it is more preferable to add 2 moles or more of the amine to 1 mole of silver atoms. .
  • an appropriate amount of amine can be attached to the surface of the silver nanoparticles produced by the reduction, and the silver nanoparticles can be provided with excellent dispersibility and low-temperature sinterability with respect to various dispersion media.
  • the mixing method of the amine and the silver oxalate is not particularly limited. However, since the viscosity increases due to the complex formation of the amine and silver oxalate, for example, a mixed solution of an amine and silver oxalate is used as a magnetic stirrer. A method of stirring using a rotating body such as is used. Stirring is preferably performed at room temperature (10 to 30 ° C.). The appearance of a silver oxalate-amine complex can be visually confirmed by the formation of a viscous white substance.
  • substances other than amine and silver oxalate may be added as long as they do not interfere with the formation of the silver oxalate-amine complex.
  • a polymer dispersant may be used.
  • a commercially available polymer dispersant can be used as the polymer dispersant.
  • polymer dispersants examples include, for example, Solsperse 11200, Solsperse 13940, Solsperse 16000, Solsperse 17000, Solsperse 18000, Solsperse 20000, Solsperse 24000, Solsperse 26000, Solsperse 27000, Solsperse 28000 (above, Nippon Lubrizol Corporation) DISPERBYK-102, 110, 111, 170, 190.194N, 2015, 2090, 2096 (above, manufactured by Big Chemie Japan); EFKA-46, EFKA-47, EFKA-48, EFKA-49 (above, EFKA Chemical Co.); polymer 100, polymer 120, polymer 150, polymer 400, polymer 401, polymer 402, polymer 4 3, polymer 450, polymer 451, polymer 452, polymer 453 (manufactured by EFKA Chemical Co., Ltd.); Ajisper PB711, Ajisper PA111, Ajisper PB
  • the method for producing silver nanoparticles of the present invention may include a step of adding a solvent to the silver oxalate-amine complex between the mixing step and the heating step. Since the silver oxalate-amine complex is a paste-like thickener, the particle size of the silver nanoparticles obtained after the heating step can be reduced by adding a solvent before heating to lower the viscosity. It is possible to improve the dispersibility of the silver nanoparticles.
  • the solvent is not particularly limited as long as it can disperse the silver oxalate-amine complex obtained in the mixing step and reduce the viscosity.
  • the solvent is compatible with the dispersion medium in producing the conductive ink.
  • a solvent that can be a good solvent for the silver nanoparticles to be produced for example, an organic solvent is used.
  • the solvent acts as a reducing agent for the silver oxalate-amine complex. It is desirable not to.
  • organic solvent examples include good solvents such as N-methylpyrrolidone, terpene, terpineol (terpineol), dihydroterpinyl acetate, isophorone, tripropylene glycol dimethyl ether, toluene, and tridecane.
  • good solvents such as N-methylpyrrolidone, terpene, terpineol (terpineol), dihydroterpinyl acetate, isophorone, tripropylene glycol dimethyl ether, toluene, and tridecane.
  • the said solvent only 1 type may be used and a mixed solvent may be used.
  • a solvent may be added to the silver oxalate-amine complex in the heating step.
  • the silver oxalate-amine complex itself can be directly heated, the silver oxalate can be used even in a thickened state containing almost no solvent.
  • -It is easy to reduce the amine complex on a scale of 100 mmol or more based on silver oxalate, and is excellent in that it can be carried out on a large scale of 1 mol or more.
  • the method for producing silver nanoparticles of the present invention includes a heating step in which the silver oxalate-amine complex is heated by irradiation with microwaves to reduce the silver oxalate-amine complex.
  • the amine complex silver is decomposed by a reduction reaction by heating by microwave irradiation without using a reducing agent, whereby silver is decomposed. Can be generated.
  • microwave irradiation can be performed in a short time.
  • the maximum heating temperature in the heating step is preferably in the range of 80 to 160 ° C, more preferably 100 to 130 ° C.
  • the microwave irradiation time in the heating step depends on the synthesis scale and the irradiation amount per unit time, but is preferably within 30 minutes, more preferably within 5 minutes, and even more preferably within 3 minutes. When the irradiation time exceeds 30 minutes, short-chain ligands are particularly likely to be detached, so that generated particles are likely to aggregate and dispersion stability may be lowered. In addition, the longer the irradiation time, the lower the productivity.
  • the microwave irradiation time is preferably short from the viewpoint of productivity, and irradiation may be terminated immediately after the reduction reaction is completed, but it is usually performed for 1 minute or longer.
  • amine complex silver composed of silver oxalate and amine has very high viscosity at room temperature. For this reason, stirring is particularly difficult when synthesizing a large volume of 100 mmol or more, and when heat transfer heating such as an oil bath or a heater is used, the viscosity decreases due to the temperature rise and sufficient stirring is performed. In the initial stage of heating (until the system temperature is close to 90 ° C.) until it becomes possible, the heating unevenness becomes particularly large. Therefore, a reduction reaction occurs in the vicinity of the wall surface of the reaction vessel, but the central part of the reaction vessel is difficult to warm, so that nucleation of particles becomes uneven in the system, and coarse particles are likely to be generated.
  • the microwave irradiation enables the heating of the vicinity of the wall and the central part at the same time without using heat transfer from the wall surface of the reaction vessel. Also, the inside of the system can be heated uniformly. That is, the combination of silver oxalate and alkylamine and / or alkoxyamine is optimal in that silver nanoparticles having a narrow particle size distribution can be produced in a short time using a simple method of microwave irradiation.
  • the generated silver atoms aggregate to form silver nanoparticles, but since amine molecules are coordinated to the silver atoms generated by the above thermal decomposition method, the amine molecules coordinated to the silver atoms It is presumed that the movement of silver atoms when aggregation occurs due to the action is controlled. As a result, it is possible to produce silver nanoparticles that are very fine and have a narrow particle size distribution.
  • silver nanoparticles having an average particle diameter of 1 ⁇ m or less can be obtained by performing the heating step.
  • the particle diameter of the silver nanoparticles is nanometer size, a melting point drop occurs and the silver nanoparticles can be fired at a low temperature.
  • a fine conductive pattern having a line width of, for example, 5 ⁇ m or less can be formed by using a printing method.
  • the average particle diameter of the obtained silver nanoparticles is preferably 1 to 200 nm. If the average particle diameter of the silver nanoparticles is 200 nm or less, the dispersibility of the silver nanoparticles is unlikely to change over time.
  • the obtained silver nanoparticles may contain particles having an average particle diameter of more than 200 nm and 1 ⁇ m or less. Further, the obtained silver nanoparticles may contain nano-sized particles having an average particle diameter of 1 to 200 nm and submicron-sized particles having an average particle diameter of more than 200 nm and 1 ⁇ m or less. By using nano-sized particles and sub-micron-sized particles together, the nano-sized particles have a lower melting point around the sub-micron-sized particles, thereby forming a better conductive path than when using only sub-micron-sized particles. Can be made. Furthermore, the silver nanoparticles obtained in the heating step may contain micron-sized particles having an average particle diameter of more than 1 ⁇ m, and are removed after the heating step, if necessary.
  • the average particle diameter of the silver nanoparticles can be measured by a dynamic light scattering method, a small angle X-ray scattering method, or a wide angle X-ray diffraction method.
  • the “average particle diameter” refers to a dispersion median diameter.
  • the dispersed median diameter is calculated by obtaining a dispersed particle diameter with a dynamic light scattering method (Dynamic Light Scattering) using the particle diameter standard as a volume standard.
  • alkylamine and / or alkoxyamine molecules adhere to the surface of the silver nanoparticles obtained in the heating step by a relatively weak bond, and a protective film is formed on the surface of the silver nanoparticles.
  • the protective coating prevents aggregation of silver nanoparticles and is excellent in storage stability because the silver nanoparticles coated with the protective coating constitute inorganic colloidal particles.
  • the alkylamine and / or alkoxyamine forming the protective film can be easily removed by heating or the like, silver nanoparticles that can be sintered at a low temperature can be produced.
  • the dispersion containing silver nanoparticles obtained as described above contains a metal salt counterion, a residue of a dispersant, etc. Concentration tends to be high. The liquid in such a state is likely to precipitate due to aggregation of silver nanoparticles due to high electrical conductivity. Or, even if it does not precipitate, if the counter ion of the metal salt, excessive dispersant or the like more than the amount necessary for dispersion remains, there is a possibility that the conductivity is deteriorated. Therefore, after the heating step, it is preferable to carry out a washing step of washing the dispersion containing silver nanoparticles to remove excess residues.
  • a cleaning method in the above-described cleaning step for example, a dispersion containing silver nanoparticles having at least a part of the surface coated with an organic component is allowed to stand for a certain period of time, and after removing the supernatant liquid, silver nanoparticles are precipitated.
  • a solvent for example, water, methanol, methanol / water mixed solvent, etc.
  • washing methods include a method of performing centrifugation instead of the above standing, a method of desalting with an ultrafiltration device, an ion exchange device, and the like.
  • the weight ratio of silver atoms to the entire nonvolatile content of the silver nanoparticles is preferably 90% by weight or more.
  • the non-volatile content refers to components other than the solvent, and includes, in addition to silver nanoparticles, organic components that coat silver nanoparticles, polymer dispersants, and the like. When the weight ratio of silver atoms is 90% by weight or more, a conductive pattern having a high silver content can be formed.
  • the obtained silver nanoparticles are mixed with optional components such as water, organic solvents, dispersants, oligomer components, surfactants, thickeners, surface tension modifiers, etc., and have appropriate viscosity and adhesion depending on the purpose of use.
  • a silver nanoparticle dispersion provided with functions such as drying, surface tension, and printability can be obtained, and, for example, a conductive ink used in printed electronics technology can be obtained.
  • Such a silver nanoparticle dispersion is applied onto a substrate using a printing method such as an inkjet method, a flexo method, screen printing, gravure offset printing, or a dispenser, and further baked to form a conductive pattern. can do.
  • the conductive pattern for example, wiring constituting an electronic circuit formed on the electronic circuit board can be cited.
  • the method for performing the firing is not particularly limited, and for example, a conventionally known gear oven or the like can be used.
  • the firing temperature is preferably less than 140 ° C, and more preferably 120 ° C or less.
  • the volume resistance value of the conductive pattern can be controlled by the firing temperature and time, the silver nanoparticles obtained in the present invention sinter (neck) the silver nanoparticles even when fired at a temperature of less than 140 ° C.
  • a conductive pattern having excellent conductivity can be formed, it can be formed on a substrate that is relatively weak against heat.
  • the lower limit of the firing temperature is not necessarily limited, and is preferably a temperature at which a conductive pattern can be formed on a substrate and an organic component or the like can be removed by evaporation or decomposition. Further, the firing time is not particularly limited, and can be appropriately adjusted according to the firing temperature.
  • the volume resistance value of the conductive pattern obtained by the present invention is preferably 110 ⁇ ⁇ cm or less, more preferably 100 ⁇ ⁇ cm or less, and further preferably 50 ⁇ ⁇ cm or less.
  • the volume resistance value is calculated based on the following formula (1).
  • the film thickness of the conductive pattern after the firing step is, for example, 0.1 to 5 ⁇ m, preferably 0.1 to 1 ⁇ m.
  • Example 1 9.0 g of 3-methoxypropylamine (manufactured by Wako Pure Chemical Industries, Ltd., first grade reagent, carbon number: 4) and 0.2 g of a polymer dispersant (manufactured by Big Chemie Japan, “DISPERBYK-102”) are mixed. Then, the mixture was thoroughly stirred with a magnetic stirrer to prepare an amine mixture. Next, 3.0 g (10 mmol) of silver oxalate was added while stirring. After the addition of silver oxalate, stirring was continued at room temperature to change the silver oxalate to a viscous white substance, and stirring was terminated when the change was found to be apparently finished (mixing step) .
  • the obtained mixed solution was transferred to a microwave heating device (“ ⁇ Reactor EX” manufactured by Shikoku Keiki Kogyo Co., Ltd.), the peak temperature in the system was set to 120 ° C. in the output automatic control mode, and the temperature was raised by 30 ° C./min.
  • the mixture was heated to a profile.
  • the synthesis state of the silver nanoparticles was confirmed by blowing carbon dioxide gas, and the heating of the mixed solution was finished in 3 minutes to obtain a suspension of silver nanoparticles (heating process).
  • Example 2 A conductive ink containing silver nanoparticles was obtained in the same manner as in Example 1 except that the amount of raw material used was scaled 10 times. Specifically, 90.0 g of 3-methoxypropylamine, 2.0 g of the polymer dispersant, 30.4 g of silver oxalate, and 100 mL of the solvent during washing were used.
  • Example 3 A conductive ink containing silver nanoparticles was obtained in the same manner as in Example 1 except that the amount of the raw material used was scaled 100 times and the mixture was heated for 5 minutes. Specifically, 900.0 g of 3-methoxypropylamine, 20.0 g of the polymer dispersant, 304.0 g of silver oxalate, and 1000 mL of the solvent during washing were used.
  • Example 4 In the same manner as in Example 3, 304.0 g of silver oxalate was added and stirring was continued at room temperature to finish changing the silver oxalate to a viscous white substance. Then, N-methylpyrrolidone (Wako Pure Chemical Industries, Ltd.) A conductive ink containing silver nanoparticles was obtained in the same manner as in Example 3 except that 580.0 g of Reagent Grade 1 manufactured by KK were added.
  • Example 5 The same procedure as in Example 1 was conducted except that 9.0 g of 3-methoxypropylamine used for preparation of the amine mixture was changed to 9.0 g of pentylamine (manufactured by Wako Pure Chemical Industries, reagent grade 1, carbon number: 5). A conductive ink containing silver nanoparticles was obtained.
  • Example 1 A conductive ink containing silver nanoparticles was obtained in the same manner as in Example 1 except that the heating method of the mixed solution was changed from microwave heating to an oil bath and heated in an oil bath at 120 ° C. for 15 minutes.
  • Example 2 A conductive ink containing silver nanoparticles was obtained in the same manner as in Example 2 except that the heating method of the mixed solution was changed from microwave heating to an oil bath and heated in an oil bath at 120 ° C. for 15 minutes.
  • a conductive ink is applied on a slide glass having a volume resistance value of 25 mm ⁇ 25 mm by spin coating under the condition of 2000 rpm ⁇ 15 seconds, and then heated and baked in a gear oven at 120 ° C. for 30 minutes.
  • the surface resistance value of this film was measured with a resistivity meter ("Loresta", manufactured by Mitsubishi Chemical Analytech Co., Ltd., four deep needle method) to obtain a surface resistance value.
  • the thickness was measured with a laser microscope (manufactured by Keyence Corporation). And based on the following formula
  • Formula: Volume resistance value ( ⁇ ⁇ cm) surface resistance value ( ⁇ / ⁇ ) ⁇ film thickness ( ⁇ m) / 10000
  • Example 1 to 5 rapid heating was possible by using microwaves, and the synthesis time could be greatly shortened.
  • the vicinity of the wall and the center of the reaction vessel were heated at the same time, and the viscous mixed liquid could be heated evenly, so that silver nanoparticles having a small dispersed median diameter were produced. I was able to.
  • the silver nanoparticles obtained in Examples 1 to 5 had good dispersibility and dilutability, and had a low volume resistance when fired at a low temperature (120 ° C.).
  • Example 4 the solvent was added during the synthesis of the complex, so that the viscosity of the mixed solution was reduced and the mixture could be heated more uniformly. Therefore, the dispersion median diameter was smaller than in Example 3 and the dilution was excellent. Silver nanoparticles could be produced.
  • the method for producing silver nanoparticles of the present invention is characterized in that microwaves are irradiated to uniformly heat a highly viscous silver oxalate-amine complex without heating unevenness.
  • the viscosity of the silver oxalate-amine complex can also be reduced by adding a solvent to the silver oxalate-amine complex.
  • the method for producing nanoparticles (hereinafter also referred to as “the method for producing the second silver nanoparticles of the present invention”) can also effectively prevent uneven heating in the heating step, and is highly viscous silver oxalate— It is useful as a method for producing a large amount of silver nanoparticles having a narrow particle size distribution in a short time from an amine complex. Moreover, the coarsening of a particle
  • a heating process may serve as the solvent addition process. That is, the silver oxalate-amine complex may be heated in parallel with the addition of the solvent.
  • a mixing process may serve as the solvent addition process. That is, the amine and silver oxalate may be mixed in parallel with the addition of the solvent.
  • the mixing step also serves as a solvent addition step, it is preferable to use a non-alcohol solvent or an organic solvent compatible with the resulting silver nanoparticles.
  • the heating method is not particularly limited, and heating by an oil bath or the like can also be applied.

Abstract

La présente invention concerne un procédé de production de nanoparticules d'argent capable de produire des nanoparticules d'argent ayant une distribution granulométrique étroite, dans de grandes quantités et en un court laps de temps, à partir d'un complexe oxalate-amine d'argent fortement visqueux. Ce procédé de production de nanoparticules d'argent comprend : une étape de mélange, pour mélanger une amine avec de l'oxalate d'argent afin d'obtenir un complexe oxalate d'argent-amine dans lequel l'amine est coordonnée avec l'oxalate d'argent ; et une étape de chauffage, pour chauffer le complexe oxalate d'argent-amine par irradiation de celui-ci avec des micro-ondes afin de réduire le complexe oxalate d'argent-amine. L'amine comprend au moins un type de composé choisi parmi des alkylamines et/ou des alcoxyamines.
PCT/JP2018/001793 2017-03-06 2018-01-22 Procédé de production de nanoparticules d'argent WO2018163619A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019139160A1 (fr) * 2018-01-15 2019-07-18 三菱マテリアル株式会社 Film conducteur et son procédé de fabrication

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3005683B1 (ja) * 1999-03-05 2000-01-31 大阪大学長 超微粒子の製造方法及び超微粒子
JP2004353038A (ja) * 2003-05-29 2004-12-16 Tokai Rubber Ind Ltd 超微粒子の製法
JP2012162767A (ja) * 2011-02-04 2012-08-30 Yamagata Univ 被覆金属微粒子とその製造方法
JP2013023699A (ja) * 2011-07-15 2013-02-04 Tokyo Institute Of Technology マイクロ波加熱による金属微粒子の製造
JP2014194057A (ja) * 2013-03-29 2014-10-09 Kyocera Chemical Corp 銀微粒子の製造方法及び銀微粒子
JP2016166391A (ja) * 2015-03-10 2016-09-15 新日鉄住金化学株式会社 ニッケル粒子の製造方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI634165B (zh) * 2014-02-13 2018-09-01 日商大阪曹達股份有限公司 金屬奈米微粒子的製造方法
KR102397620B1 (ko) * 2015-02-19 2022-05-16 주식회사 다이셀 은 입자 도료 조성물
CN105312590A (zh) * 2015-10-10 2016-02-10 皖西学院 一种水溶性纳米银溶胶的制备方法
CN105234426B (zh) * 2015-10-16 2017-05-17 上海纳米技术及应用国家工程研究中心有限公司 一种超细纳米银的制备方法
CN105598463B (zh) * 2015-11-27 2018-08-07 深圳市乐普泰科技股份有限公司 银纳米粒子制备方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3005683B1 (ja) * 1999-03-05 2000-01-31 大阪大学長 超微粒子の製造方法及び超微粒子
JP2004353038A (ja) * 2003-05-29 2004-12-16 Tokai Rubber Ind Ltd 超微粒子の製法
JP2012162767A (ja) * 2011-02-04 2012-08-30 Yamagata Univ 被覆金属微粒子とその製造方法
JP2013023699A (ja) * 2011-07-15 2013-02-04 Tokyo Institute Of Technology マイクロ波加熱による金属微粒子の製造
JP2014194057A (ja) * 2013-03-29 2014-10-09 Kyocera Chemical Corp 銀微粒子の製造方法及び銀微粒子
JP2016166391A (ja) * 2015-03-10 2016-09-15 新日鉄住金化学株式会社 ニッケル粒子の製造方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019139160A1 (fr) * 2018-01-15 2019-07-18 三菱マテリアル株式会社 Film conducteur et son procédé de fabrication

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