WO2013035366A1 - Procédé pour produire des nanoparticules de cuivre ayant une stabilité de dispersion élevée - Google Patents

Procédé pour produire des nanoparticules de cuivre ayant une stabilité de dispersion élevée Download PDF

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WO2013035366A1
WO2013035366A1 PCT/JP2012/058171 JP2012058171W WO2013035366A1 WO 2013035366 A1 WO2013035366 A1 WO 2013035366A1 JP 2012058171 W JP2012058171 W JP 2012058171W WO 2013035366 A1 WO2013035366 A1 WO 2013035366A1
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copper
copper nanoparticles
raw material
base
solution
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PCT/JP2012/058171
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Japanese (ja)
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英也 川▲崎▼
隆一 荒川
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学校法人関西大学
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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
    • B22F1/0545—Dispersions or suspensions of nanosized particles
    • 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
    • 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 a method for producing copper nanoparticles having high dispersion stability, and more particularly, to a method for simply producing copper nanoparticles having high dispersion stability even when no dispersant is used.
  • the metal particle size When the metal particle size is reduced to a diameter of about 1 nm to 5 nm, electrons are confined in that region, so that it takes discrete energy levels instead of a continuous band structure of bulk metal (so-called quantum size). effect). In addition, as the particle size decreases, the band gap energy increases, and the metal nanoparticles emit light specific to the particle size.
  • Metal nanoparticles exhibiting properties different from bulk metals in the above optical properties, magnetic properties, electrical properties, etc. are expected to be applied in various technical fields. For example, by utilizing the property that the surface area increases and the melting point decreases when the particle size is reduced, an electronic circuit made of fine metal wiring is produced on a substrate using a fine wiring printing ink containing metal nanoparticles. Research is ongoing. Application of metal nanoparticles to catalyst materials is also expected.
  • a circuit pattern is printed on the substrate using fine wiring printing technology, and the organic matter is removed by heating at a low temperature. Wake up. Thereby, the metal fine wiring with high heat and electrical conductivity can be formed.
  • the ink material silver nanoparticles are mainly used (for example, Patent Document 1), but the silver in the fine wiring is ionized by oxidation and moves on the insulator of the substrate to induce a short circuit. Easy (so-called migration phenomenon).
  • Such a migration tendency is in the order of Ag + > Pb 2+ ⁇ Cu 2+ > Sn 2+ > Au + , and gold is desirable in that it does not easily cause a migration phenomenon, but is expensive. Therefore, copper is attracting attention because it is less likely to cause a migration phenomenon than silver and has a relatively low cost.
  • bulk copper that has been used as a metal wiring has drawbacks such as being easily oxidized and lowering conductivity, being difficult to disperse, and having a high firing temperature.
  • copper nanoparticles have a lower sintering temperature than bulk copper, and are expected as materials capable of forming fine metal wiring on a substrate such as paper or plastic that is weak against heat.
  • Non-Patent Document 1 describes that crystalline copper nanoparticles having a particle size of about 50 nm can be obtained by circulating a copper component in an ethylene glycol solvent for 2 hours.
  • Non-Patent Document 2 a solution in which a copper compound, a nickel compound and a base are dissolved in ethylene glycol is rapidly heated to the boiling point using a heater to obtain copper-nickel composite particles having a particle size of several hundred nm.
  • copper nanoparticles having a particle size of several hundreds of nanometers are obtained in the vicinity of the boiling point of about 165 ° C. in a state where hydration water of a copper compound and a nickel compound is contained. .
  • conventional copper nanoparticles are surface-treated with a dispersant (a component that suppresses aggregation of copper nanoparticles and improves dispersibility), but these may not be completely removed during low-temperature heating. May affect the electrical conductivity of the metal microwiring. Furthermore, in the case of using for other applications not involving heating, a step of removing the surface treatment agent is required.
  • a dispersant a component that suppresses aggregation of copper nanoparticles and improves dispersibility
  • An object of the present invention is to provide a method for easily producing monodispersed copper nanoparticles having an average particle diameter of 10 nm or less that are useful as an ink material, a light emitting material, a catalyst material, and the like, even when no dispersant is used. .
  • the present inventor according to a specific production method for performing a temperature raising step up to 120 ° C. in a state where a copper compound, a base and a polyol coexist in a short time, The inventors have found that the above object can be achieved and have completed the present invention.
  • the present invention relates to the following method for producing copper nanoparticles and copper nanoparticles.
  • a method for producing copper nanoparticles comprising a step of heating a solution in which a copper compound and a base are dissolved in a polyol solvent at a solution temperature of 120 ° C. or higher, and when preparing the solution at 120 ° C. or higher, the copper compound, the base, and A method for producing copper nanoparticles, characterized by having a temperature raising step up to 120 ° C. in a state where a polyol coexists, wherein the temperature raising time is within 5 minutes. 2.
  • item 1 which heats up the raw material solution C which melt
  • Item 2. The raw material solution B in which a base is dissolved in a polyol solvent and the raw material solution C in which a copper compound is dissolved in a polyol solvent are prepared, and both solutions are mixed after the temperature is raised to 120 ° C or higher. Manufacturing method. 11.
  • the method for producing copper nanoparticles of the present invention is a production method having a step of heating a solution in which a copper compound and a base are dissolved in a polyol solvent at a solution temperature of 120 ° C. or higher, and when preparing the solution at 120 ° C. or higher.
  • the temperature raising time is set to 5 minutes or less.
  • copper nanoparticles are obtained by heating a solution in which a copper compound and a base are dissolved in a polyol solvent at a solution temperature of 120 ° C. or more.
  • a solution temperature 120 ° C. or more.
  • by setting the temperature raising time within 5 minutes uniform and rapid nucleation in the solution is possible, and the copper nanoparticles are aggregated. Therefore, monodispersed copper nanoparticles having an average particle size of 10 nm or less can be easily produced. Further, by containing a base in the solution, monodispersed copper nanoparticles can be produced even when a dispersant is not used.
  • the copper compound used in the present invention is not limited as long as it dissolves in a polyol solvent and generates copper ions.
  • the Cu (acac) 2 is acetylacetone copper (II).
  • chloride is preferable because copper ions are easily reduced and copper nanoparticles are easily obtained.
  • the content of the copper compound in the solution in which the copper compound and the base are dissolved in the polyol solvent is not limited, but is preferably 1 to 100 mM, preferably about 1 to 80 mM in terms of copper ion. More preferred is about 20 to 50 mM.
  • the concentration of the copper compound is too low, not only copper nanoparticles are hardly obtained, but also a by-product generated by a side reaction of the polyol solvent due to a relatively high proportion of the polyol solvent (for example, the solvent is ethylene glycol). If so, the amount of polyethylene glycol or the like) may increase. When the concentration of the copper compound is too high, the produced copper nanoparticles may aggregate to cause bulk copper to precipitate.
  • the concentration of the copper compound is too low, not only copper nanoparticles are hardly obtained, but also a by-product generated by a side reaction of the polyol solvent due to a relatively high proportion of the polyol solvent (for example, the solvent is ethylene glycol). If so, the amount of polyethylene glycol or the like) may increase.
  • the concentration of the copper compound is too high, the produced copper nanoparticles may aggregate to cause bulk copper to precipitate.
  • the polyol solvent used in the present invention is not limited as long as it can dissolve a copper compound and a base and acts as a copper ion reducing agent. Therefore, in this invention, since a polyol solvent acts as a reducing agent of copper ions, it is not necessary to add a reducing agent separately.
  • ethylene glycol and propylene glycol as the polyol solvent.
  • ethylene glycol is used, ethylene glycol is dehydrated by heating, and the copper ions in the solution are reduced by the electrons released when the resulting acetaldehyde is oxidized to diacetyl. It is believed that copper nanoparticles are produced.
  • the reaction solvent may be a polyol solvent alone, or a high-polarity polar solvent (for example, dimethylformamide, N-methylpyrrolidone, ethylene glycol monomethyl ether, etc.) may be used by mixing with the polyol solvent.
  • a high-polarity polar solvent for example, dimethylformamide, N-methylpyrrolidone, ethylene glycol monomethyl ether, etc.
  • the content of the polyol solvent in the solvent is preferably 60% by weight or more, and more preferably 90% by weight or more.
  • the base used in the present invention for example, at least one selected from the group consisting of metal hydroxide, ammonia and tetramethylammonium hydroxide is preferable.
  • the metal hydroxide include sodium hydroxide, potassium hydroxide, lithium hydroxide and the like. Among these, sodium hydroxide is particularly preferable.
  • the content of the base in the raw material solution is not limited, but is preferably 0.01M or more, more preferably about 0.1 to 0.5M, and most preferably about 0.2 to 0.3M.
  • the base used in the present invention has the effect of promoting the reduction of copper ions by promoting the interaction (complexation) between the polyol solvent and copper ions in the raw material solution.
  • a reaction of Cu 2+ + 2OH ⁇ ⁇ Cu (OH) 2 occurs to produce a pale white precipitate.
  • this precipitation does not occur in the raw material solution used in the present invention.
  • a polyol solvent molecule having two or more hydroxyl groups having high coordination ability in the molecule acts as a chelating agent to form a copper complex.
  • copper complex for example, [Cu (OH) 4] 2-, [Cu (OCH 2 CH 2 O) 2] 2- , and the like.
  • the hydroxyl group tends to be negatively charged and the coordination ability is further increased, and the polyol solvent molecules and copper ions strongly interact to suppress the formation of copper hydroxide. Conceivable.
  • copper nanoparticles are obtained by heating a solution (raw material solution) in which a copper compound and a base are dissolved in a polyol solvent at a solution temperature of 120 ° C. or more, but the copper compound, the base and the polyol coexist in particular.
  • a solution raw material solution
  • the temperature raising time needs to be within 5 minutes.
  • the temperature raising step up to 120 ° C. in the state where the three components of the copper compound, the base and the polyol coexist is set within a short time of 5 minutes (preferably within 3 minutes, more preferably within 2 minutes), or It is necessary to adjust the heating method and the order of addition of each component so that the temperature raising step up to 120 ° C. in the state where the three components coexist is not included.
  • a mode in which a raw material solution A in which a copper compound and a base are dissolved in a polyol solvent is heated to 120 ° C. or higher at a temperature rising rate of 60 ° C./min or higher (hereinafter also referred to as “first mode”)
  • second mode A mode in which a raw material solution B in which a base is dissolved in a polyol solvent is heated to 120 ° C. or higher, and a copper compound is added to the raw material solution B after the temperature increase
  • second mode A mode in which the raw material solution C in which a copper compound is dissolved in a polyol solvent is heated to 120 ° C.
  • microwave irradiation As a means for performing such rapid temperature increase, for example, microwave irradiation can be mentioned. Heating by irradiation with microwaves is internal heat generation due to rotation and vibration of dipoles in the molecule, so that uniform and rapid heating can be performed as compared with a heating method using a conventional oil bath or the like. Therefore, nucleation is performed uniformly and rapidly in the solution, and monodispersed copper nanoparticles can be efficiently produced.
  • the microwave frequency is preferably about 2.45 GHz, and the output is preferably in the range of 100 to 300 W, more preferably in the range of 200 to 300 W.
  • the microwave is irradiated, a change is observed in which the characteristic blue color of the raw material solution before irradiation disappears in about a few minutes (about 5 minutes), once becomes colorless, and gradually becomes yellow. This is probably because reduction of copper ions, nucleus growth of copper atoms, and generation of copper nanoparticles occur in a short time.
  • the frequency of the microwave is an example, and the frequency is appropriately adjusted according to the amount of the raw material solution A so as to ensure a predetermined rate of temperature increase.
  • the microwave irradiation time including heating and heating is preferably about 10 to 120 minutes, more preferably about 30 to 60 minutes.
  • irradiation time is too short, there exists a possibility that a copper nanoparticle may not fully be obtained.
  • irradiation time is too long, since the viscosity of a reaction solution increases, there exists a possibility that it may become difficult to handle.
  • the heating temperature after raising the temperature to 120 ° C. or higher is not limited, a temperature lower than the boiling point is preferable because by-products generated by side reactions increase at temperatures near the boiling point of the solvent used.
  • ethylene glycol used as the solvent, it is preferably about 120 to 195 ° C, more preferably about 175 to 185 ° C.
  • propylene glycol is used, it is preferably about 120 to 185 ° C, more preferably about 170 to 180 ° C.
  • An inert atmosphere is used as the atmosphere during the heating and heating of the raw material solution A.
  • an inert atmosphere such as a nitrogen atmosphere or an argon atmosphere is preferable.
  • the end point of heating may be a point when the copper nanoparticles reach the target average particle diameter.
  • the average particle diameter of the copper nanoparticles is preferably 10 nm or less, and particularly preferably about 2 to 5 nm.
  • the solution temperature of the raw material solution A can be raised to 120 ° C. or more in a short time (within 5 minutes). .
  • a copper nanoparticle can be obtained also by utilizing a microreactor.
  • dissolved the base in the polyol solvent is heated up to 120 degreeC or more, and a copper compound is added to the raw material solution B after the said temperature rising.
  • the addition rate of the copper compound may be adjusted depending on the amount and temperature of the raw material solution B, but in any case, the temperature of the raw material solution obtained by adding the copper compound is not less than 120 ° C or temporarily less than 120 ° C. Even if it becomes, it is necessary to add so that it may become the conditions which can be heated up to 120 degreeC or more within 5 minutes.
  • a copper compound to add what was melt
  • the explanation of the concentration of each component and the heating temperature (heating temperature of the raw material solution at 120 ° C. or higher) in the raw material solution after adding the copper compound is the same as in the first aspect.
  • dissolved the copper compound in the polyol solvent is heated up to 120 degreeC or more, and a base is added to the raw material solution C after the said temperature rising.
  • the addition rate of the base may be adjusted depending on the amount and temperature of the raw material solution C, but in any case, the temperature of the raw material solution obtained by the addition of the base is not less than 120 ° C or temporarily becomes less than 120 ° C. However, it is necessary to add such that the temperature can be raised to 120 ° C. or more within 5 minutes.
  • a base dissolved in a polyol solvent may be used as necessary.
  • the explanation of the concentration of each component in the raw material solution after adding the base and the heating temperature are the same as in the first aspect.
  • a raw material solution B in which a base is dissolved in a polyol solvent and a raw material solution C in which a copper compound is dissolved in a polyol solvent are prepared, and both solutions are heated to 120 ° C. or higher.
  • each solution that has been heated to 120 ° C. or higher in advance is mixed. Therefore, the temperature of the raw material solution after mixing both solutions can be maintained at 120 ° C. or higher, and 120 in a state where the three components coexist. Does not include the temperature raising step up to °C.
  • the explanation of the concentration of each component and the heating temperature (heating temperature of the raw material solution at 120 ° C. or higher) in the raw material solution after mixing both solutions is the same as in the first aspect.
  • the copper nanoparticles obtained by the production method of the present invention exhibit high dispersion stability and can maintain monodispersity even when re-dispersed in various dispersion media.
  • the dispersion medium include ethylene glycol, N, N-dimethylformamide, ethanol, water and the like.
  • the copper nanoparticles obtained by the production method of the present invention are considered to have a small particle size and a lower melting point than bulk copper.
  • the average particle size is preferably 10 nm or less, more preferably 2 to 5 nm.
  • the coefficient of variation of the particle diameter is preferably 20% or less.
  • the melting point is considered to be about 150 to 250 ° C.
  • the copper nanoparticles obtained by the production method of the present invention are generally (1)
  • the average particle diameter of the copper nanoparticles is 10 nm or less
  • the copper nanoparticles are composed of a central part and a protective layer around the central part, the central part is composed of a single crystal of copper, and the protective layer is composed of an organic component derived from the polyol solvent. It is the copper nanoparticle characterized by this.
  • the organic component is derived from a polyol solvent, and is preferably at least one of polyethylene glycol and polypropylene glycol in the present invention.
  • the copper nanoparticles of the present invention are considered to have a melting point of about 150 to 250 ° C., they are useful as an ink material for forming metal fine wiring on a substrate such as paper or plastic that has a low sintering temperature and is susceptible to heat. .
  • copper nanoparticles having an average particle size of about 2 mm have been shown to sinter and grow at a low temperature of about 150 ° C. (see FIG. 11).
  • the copper nanoparticles of the present invention can also be used as a catalyst material (catalyst or catalyst support).
  • the nanosize-specific light emission is exhibited by the quantum size effect, it can also be used as a light-emitting material.
  • copper nanoparticles are obtained by a step of heating a solution in which a copper compound and a base are dissolved in a polyol solvent at a solution temperature of 120 ° C. or more.
  • the copper compound, the base and the polyol coexist.
  • a heating step up to 120 ° C. in the state by setting the heating time within 5 minutes, uniform and rapid nucleation in the solution is possible. Therefore, monodispersed copper nanoparticles having an average particle diameter of 10 nm or less can be easily produced. Further, by containing a base in the solution, monodispersed copper nanoparticles can be produced even when a dispersant is not used.
  • FIG. 3 is a diagram showing a procedure for preparing copper nanoparticles in Example 1.
  • 2 is a diagram showing an ultraviolet-visible absorption spectrum of copper nanoparticles obtained in Example 1.
  • FIG. 2 is a diagram showing a fluorescence spectrum of copper nanoparticles obtained in Example 1.
  • FIG. It is a figure which shows the blue light emission obtained when the copper nanoparticle obtained in Example 1 is irradiated with ultraviolet light. Note that (a) is water, (b) is ethylene glycol, (c) is N, N-dimethylformamide, and (d) is ethanol as a dispersion medium.
  • 2 is a diagram showing a TEM observation image of copper nanoparticles obtained in Example 1.
  • FIG. 3 is a view showing a particle size distribution of copper nanoparticles obtained in Example 1. It is a figure which shows the infrared spectroscopy measurement result of the copper nanoparticle obtained in Example 1.
  • FIG. It is a figure which shows the ultraviolet visible absorption spectrum (After reduction
  • restoration ( after reduction
  • FIG. It is the figure which compared each ultraviolet visible absorption spectrum of the copper nanoparticle obtained in the case of Example 1 (base 2 ml), Example 2 (base 1 ml), and the comparative example 1 (base 0 ml). It is a figure which shows the ultraviolet visible absorption spectrum of the copper nanoparticle obtained in Example 3. It is a figure which shows the TEM observation image after about 150 degreeC low-temperature baking of the copper nanoparticle in Example 1.
  • FIG. 4 is a diagram showing a TEM observation image of copper nanoparticles obtained in Example 4.
  • FIG. 4 is a diagram
  • UV-vis ultraviolet-visible absorption
  • Fluorescence (PL) spectrum was measured using a JASCO FP-6200 with 2 ml of sample in a four-sided quartz cell. As a sample, an ethanol dispersion of copper nanoparticles obtained in operation 2 described later was used.
  • Infrared spectroscopy (IR) measurement was performed using JASCO's FT / IR-4200. As a sample for IR measurement, a dry powder of copper nanoparticles obtained in operation 3 described later was used.
  • Example 1 (Preparation of copper nanoparticles and various samples in the first embodiment) Copper (II) chloride and sodium hydroxide were dissolved in ethylene glycol, respectively, to prepare 38 mM copper solution and 0.5 M sodium hydroxide solution. When 2 ml of 0.5 M sodium hydroxide solution was added to 2 ml of 38 mM copper solution, the solution changed from light blue-green to dark blue with complex formation. The content of copper chloride in this raw material solution is 19 mM in terms of copper ion, and the content of sodium hydroxide is 0.25M.
  • the mixture was heated and heated by irradiation with microwaves (output: 250 W) in a nitrogen atmosphere. Specifically, the raw material solution was heated to 185 ° C. at a rate of temperature increase of 100 ° C./min by microwave irradiation, and then the microwave output was adjusted and heating was continued for 30 minutes while maintaining 185 ° C. As a result, the dark blue solution turned reddish brown, and a copper nanoparticle dispersion (19 mM) was obtained.
  • FIG. 2 shows an ultraviolet-visible absorption spectrum of the copper nanoparticles obtained in Example 1
  • FIG. 3 shows a fluorescence spectrum.
  • the peak after reduction is the peak of the copper nanoparticles
  • the peak before reduction is also shown for reference.
  • FIG. 5 A high-resolution TEM observation image of the copper nanoparticles is shown in FIG.
  • the sample in which the copper paste was redispersed in ethanol showed high dispersion stability.
  • FIG. 5 it can be seen that monodisperse copper nanoparticles having a single nanosize (about 2 to 3 nm) are obtained.
  • the copper atom lattice stripes are observed, and thus the obtained copper nanoparticles are single crystals.
  • the particle size distribution of the copper nanoparticles is shown in FIG. According to the result of FIG. 6, it can be seen that the average particle diameter is 2.3 ⁇ 0.25 nm.
  • the ultraviolet-visible absorption spectrum of copper nanoparticles (immediately after reduction, 7 days, 14 days and 21 days) is shown in FIG.
  • the peaks around 250 nm and 300 nm observed immediately after the reduction were lost after 7 days.
  • the peak intensity around 220 nm was greatly reduced.
  • no significant change is observed in the peak shape, and it can be seen that the obtained copper nanoparticles do not change greatly with time and maintain stability.
  • Copper nanoparticles are considered to have a small particle size and a lower melting point than bulk copper. When the copper nanoparticles were heated at a low temperature of about 150 ° C., it was found that the particles were sintered and grown (it is recognized from the results in FIG. 11).
  • the copper nanoparticles of the present invention have high dispersion stability and stability over time without using a dispersant or a surfactant. Therefore, the copper nanoparticles of the present invention are useful as an ink material, a catalyst material, a light emitting material, and the like for forming a metal fine wiring.
  • Example 2 and Comparative Example 1 Comparison in base amount
  • the amount of 0.5M sodium hydroxide solution was 1 ml
  • Example 2 was 0 ml (without base).
  • FIG. 9 shows each ultraviolet-visible absorption spectrum of the copper nanoparticles obtained in the case of Example 1 (2 ml), Example 2 (1 ml) and Comparative Example 1 (0 ml).
  • Red-brown copper nanoparticles were obtained in the sample synthesized with 2 ml (Example 1) and 1 ml (Example 2) of the base amount, but in the sample synthesized without adding the base (Comparative Example 1), the temperature was increased by microwave. And even after heating, the color of the solution was light turquoise.
  • the UV-visible absorption spectrum shown in FIG. 9 is compared, in the sample synthesized without adding a base (Comparative Example 1), characteristic strong peaks around 220 nm and 270 nm are not recognized, so that the reduction reaction of copper ions proceeds. In other words, copper nanoparticles are not obtained.
  • Example 3 (Solvent is propylene glycol)
  • solvent is propylene glycol
  • copper nanoparticles were obtained in the same manner as in Example 1 except that the solvent was changed to propylene glycol.
  • the UV-visible absorption spectrum before and after the synthesis is shown in FIG.
  • the ultraviolet-visible absorption spectrum of the propylene glycol solvent sample showed peaks at 215 nm, 237 nm, 278 nm, and 405 nm. Therefore, it turns out that the copper nanoparticle is obtained similarly to Example 1.
  • Example 4 (Example corresponding to the second mode) A 0.5 M sodium hydroxide solution (Solution A) was prepared by adding granular sodium hydroxide to 25 ml of ethylene glycol. Solution A was heated to 185 ° C.
  • solution B 1 ml of a 1.25 M copper solution (solution B) was prepared by adding copper nitrate to ethylene glycol.
  • Solution B was added to Solution A heated to 185 ° C. and continuously heated for 15 minutes with stirring.
  • the temperature of the sample solution once decreased by the addition of the solution B, but increased to 185 ° C. within 1 minute.
  • a copper nanoparticle dispersion was obtained.
  • An electron microscope observation image is shown in FIG.
  • the obtained copper nanoparticles had a size of about 3 nm and a uniform particle size.

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

Abstract

La présente invention porte sur un procédé pour produire facilement des nanoparticules de cuivre monodispersées ayant un diamètre de particules moyen de 10 nm ou moins, même dans les cas où un agent dispersant n'est pas utilisé, lesdites nanoparticules de cuivre étant utiles comme matériau d'encre, comme matériau émetteur de lumière, et comme matériau de catalyseur, et analogues. A cet effet, l'invention porte sur un procédé pour produire des nanoparticules de cuivre, lequel procédé comprend une étape dans laquelle une solution qui est obtenue par dissolution d'un composé de cuivre et d'une base dans un solvant de polyol est chauffée à une température de solution de 120°C ou plus. Ce procédé pour produire des nanoparticules de cuivre est caractérisé en ce que, si le procédé comprend, pendant la préparation de la solution à une température de 120°C ou plus, une étape de chauffage à 120°C dans un état dans lequel le composé de cuivre, la base et le polyol sont coexistants, le temps de chauffage est limité à 5 minutes ou moins.
PCT/JP2012/058171 2011-09-08 2012-03-28 Procédé pour produire des nanoparticules de cuivre ayant une stabilité de dispersion élevée WO2013035366A1 (fr)

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WO2015129466A1 (fr) * 2014-02-27 2015-09-03 学校法人関西大学 Nanoparticules de cuivre et leurs procédé de production, dispersion fluide de nanoparticules de cuivre, nano-encre au cuivre, procédé de conservation de nanoparticules de cuivre et procédé de frittage de nanoparticules de cuivre
WO2016140351A1 (fr) * 2015-03-05 2016-09-09 国立大学法人大阪大学 Procédé de production de particules de cuivre, particules de cuivre et pâte de cuivre
JP2017514988A (ja) * 2014-03-03 2017-06-08 ピー．ブイ．ナノ セル リミテッド ナノ銅製剤
EP3329778A1 (fr) * 2016-11-30 2018-06-06 Univerza v Mariboru Fakulteta za strojnistvo Procédé de synthèse des nanoparticules de cuivre antimicrobien
CN112517921A (zh) * 2020-11-23 2021-03-19 延边大学 一种空心铜纳米片的制备方法及系统

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JPWO2016140351A1 (ja) * 2015-03-05 2017-12-07 国立大学法人大阪大学 銅粒子の製造方法、銅粒子及び銅ペースト
US10625344B2 (en) 2015-03-05 2020-04-21 Osaka University Method for producing copper particles, copper particles, and copper paste
EP3329778A1 (fr) * 2016-11-30 2018-06-06 Univerza v Mariboru Fakulteta za strojnistvo Procédé de synthèse des nanoparticules de cuivre antimicrobien
CN112517921A (zh) * 2020-11-23 2021-03-19 延边大学 一种空心铜纳米片的制备方法及系统
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