WO2010001496A1 - 微小金属粒子含有組成物及びその製造方法 - Google Patents
微小金属粒子含有組成物及びその製造方法 Download PDFInfo
- Publication number
- WO2010001496A1 WO2010001496A1 PCT/JP2008/064256 JP2008064256W WO2010001496A1 WO 2010001496 A1 WO2010001496 A1 WO 2010001496A1 JP 2008064256 W JP2008064256 W JP 2008064256W WO 2010001496 A1 WO2010001496 A1 WO 2010001496A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- metal
- containing composition
- reaction
- minutes
- ratio
- Prior art date
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/102—Metallic powder coated with organic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
- H05K1/092—Dispersed materials, e.g. conductive pastes or inks
- H05K1/097—Inks comprising nanoparticles and specially adapted for being sintered at low temperature
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/11—Treatments characterised by their effect, e.g. heating, cooling, roughening
- H05K2203/1131—Sintering, i.e. fusing of metal particles to achieve or improve electrical conductivity
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
Definitions
- the present invention relates to a metal-containing composition that exhibits good conductivity even when fired at a low temperature, and a method for producing the same.
- nanometer-sized fine metal particles have been used in various fields.
- a conductive paste containing metal nanoparticles is used to depict fine electrical wiring by printing techniques such as inkjet, and sintering is performed at a low temperature specific to nanometer-sized particles.
- Attempts have been made to make it possible to form a conductive film on a substrate having low heat resistance such as paper by taking advantage of the properties, and there is an increasing demand for pastes having properties suitable for these purposes.
- the metal nanoparticles are required to have good dispersibility in a paste dispersion medium, and in the process of heat-treating the paste after coating, it can withstand even a substrate with low heat resistance. Sintered by a heat treatment at a low temperature of about 200 ° C. and exhibits good conductivity. Secondly, since the handleability when producing the dispersion composition and the ink composition is good and it is possible to cope with various compositions and production methods constituting these compositions, It is mentioned that the nanoparticles exist stably in a dry powder state and can be redispersed in various solvents as required.
- metal nanoparticles have been prepared by various methods.
- the surface of the metal nanoparticles is fused to each other during or after the reaction.
- the independence of individual particles is widely secured by attaching a relatively large molecular weight to the surface.
- the dispersion is applied on the substrate and then fused, it is necessary to heat the substrate at a high temperature for a long time in the process of volatilizing the organic material that coats the surroundings.
- Patent Document 1 In order to solve such a problem, in Patent Document 1, by using a molecule that vaporizes at a low temperature as a protective agent, even when heat-treated at a low temperature of 150 ° C., a comparison of 6.8 to 9.5 ⁇ ⁇ cm, etc. Has succeeded in providing a metal film exhibiting a good volume resistivity. However, the resistance value was still higher than 1.6 ⁇ ⁇ cm, which is the resistance value of bulk silver.
- the particles provided by the disclosed particle production method need to be subjected to solid-liquid separation by centrifugation, and as a result, requires a lot of time for separation and recovery.
- a production method capable of solid-liquid separation in a short time is desired.
- Patent Document 2 is an example of means for achieving solid-liquid separation in a simple and short time as described above.
- silver nanoparticles can be produced by mixing a silver nitrate aqueous solution with a mixed solution of an iron (II) sulfate aqueous solution and a sodium citrate aqueous solution. More specifically, at the time of the reaction, silver nanoparticles produced by high concentrations of iron ions, sodium ions, etc. derived from the raw material rapidly agglomerate, so that an aggregate of silver nanoparticles protected with citrate ions is formed. It is formed.
- the aggregate since the aggregate becomes a state in which the particle surface is protected after the reaction, it can be separated from the reaction solvent by a commonly used solid-liquid separation means such as a filter press, and pure water is added to the cake of the aggregate.
- a commonly used solid-liquid separation means such as a filter press
- pure water is added to the cake of the aggregate.
- the present invention has been conceived in view of the conventional problems as described above, and the object thereof is that the metal component can be easily separated from the reaction solution and has been conventionally obtained by heat treatment at a high temperature. Is to provide a metal-containing composition obtained by heat treatment at a low temperature, and a method for producing such a metal-containing composition.
- the organic component constituting the surface of the metal particles is a specific one, so that sufficient electrical conductivity is exhibited even at low temperature heat treatment, and the separation and recovery capability It was found that excellent particles can be obtained. They can be obtained by a production method in which a metal salt aqueous solution is reacted with a reducing solution obtained by mixing water, aqueous ammonia, an organic substance having a molecular weight of 200 or less, and a reducing agent, followed by filtration and washing.
- the metal-containing composition of the present invention is a metal-containing composition containing fine metal particles having an average particle diameter of less than 100 nm, and the true density after heating the metal-containing composition at 150 ° C. in the atmosphere for 60 minutes. was a [rho 0.99, the metal-containing composition and 200 [rho a true density after heating for 60 minutes at 200 ° C. in air, the true density ratio the ratio ( ⁇ 200 / ⁇ 150) and said [rho 200 and the [rho 0.99 upon the [rho f, wherein said [rho f is 1.10 or less.
- the ratio ( ⁇ 200 / ⁇ M ) is 0.8 or more.
- Another preferred embodiment of the metal-containing composition of the present invention is characterized in that an organic substance having a molecular weight of 200 or less is attached to the surface of the fine metal particles.
- the method for producing a metal-containing composition of the present invention includes a reducing liquid preparation step in which water, ammonia water, an organic substance having a molecular weight of 200 or less and a reducing agent are mixed to prepare a reducing liquid, and a metal salt is added to the reducing liquid. It has the reaction process which adds and reacts aqueous solution, The filtration and washing
- the metal-containing composition of the present invention contains fine metal particles and has a composition configuration with little difference in true density after heat treatment at 150 ° C. and 200 ° C., the sintered state equivalent to high-temperature heat treatment Can be easily obtained even by low-temperature heat treatment.
- the method for producing a metal-containing composition of the present invention is a simple method in which a metal salt aqueous solution is reacted with a reducing solution obtained by mixing water, aqueous ammonia, an organic substance having a molecular weight of 200 or less, and a reducing agent, followed by filtration and washing. It can consist of work processes.
- FIG. 4 is a TEM image taken by redispersing the dry powder of FIG. 3 in a solvent. It is a surface SEM photograph of Example 2 (150) which baked the silver powder of Example 1 at 150 degreeC in air
- Example 3 150
- Example 3 150
- Example 3 150
- Comparative example 2 150
- SEM image of the surface of the comparative example 2 150
- SEM image of the surface of the comparative example 2 200
- the fine metal particles contained in the metal-containing composition in the present invention are nano-order fine metal particles. Therefore, the metal-containing composition of the present invention is also referred to as a metal nanoparticle-containing composition.
- the metal nanoparticle-containing composition also includes a powder composed of metal nanoparticles, a dispersion liquid in which metal nanoparticles are dispersed, and the like.
- agglomeration refers to a state in which the surfaces of the particles do not come into contact but are simply approached to form an aggregate of two or more particles. It means that what was two or more particles becomes one particle.
- the metal nanoparticle-containing composition of the present invention has a true density after heating at 150 ° C. for 60 minutes in the atmosphere as ⁇ 150 and a true density after heating at 200 ° C. in the atmosphere for 60 minutes as ⁇ 200 ( 1)
- the true density ratio ⁇ f represented by the formula is 1.10 or less.
- ⁇ f ⁇ 200 / ⁇ 150 (1)
- the true density ratio ⁇ f means that as the value approaches 1.00, there is less change in the sinterability due to the temperature difference. In other words, if the absolute value of the true density at 200 ° C. shows a value close to that of a bulk metal, the same behavior occurs at higher temperatures even at lower temperatures. In other words, it means that low temperature sintering is excellent. Conversely, when the true density ratio ⁇ f exceeds 1.10, it means that the difference between the ⁇ 150 value after the 150 ° C. heat treatment and the ⁇ 200 value after the 200 ° C. heat treatment is large, and the true density at 200 ° C.
- the value of the true density ratio ⁇ f is preferably 1.05 or less, and more preferably 1.02 or less.
- the ratios ( ⁇ 150 / ⁇ M ) and ( ⁇ 200 / ⁇ M ) of ⁇ 150 and ⁇ 200 and the density ⁇ M of the bulk metal particles contained in the metal-containing composition are ( ⁇ 150 / ⁇ M ), respectively. It is characterized by being 0.80 or more. This ratio is an index indicating how close the metal after heating is to a pure metal. At this temperature, organic components adhering to the surface are easily detached, and the residue is composed of pure metal. It is 1 ideally.
- the density in the bulk state refers to the weight per 1 cm 3 in a state where the metal elements constituting the fine metal particles are stably present at room temperature.
- the metal element any one or both of a simple substance and a compound including gold, silver or copper, and any combination thereof can be used.
- this ratio is less than 0.80, it means that the organic component remains on the surface of the metal nanoparticle, which may not be detached, and the area where the surface of the metal nanoparticle is exposed is Since it is small, the sintering (bonding) property at a low temperature of the particles is inferior, and the conductivity may be inferior.
- These ratios are preferably 0.90 or more, and more preferably 0.95 or more. When such a value is exhibited, if the true density is close to the density in the bulk state when fired, conductivity comparable to the metal in the bulk state can be obtained.
- an organic substance having a group having an affinity for metal is disposed on the surface of the metal nanoparticle.
- examples include linear fatty acids that function as protective agents.
- those having a molecular weight of 200 or less are preferred from the viewpoint of easiness of evaporation during firing. More preferably, it is good that it is 150 or less.
- the difference between the metal nanoparticles according to the present invention and many conventional metal nanoparticles is the ease of separation of the particles.
- a conventionally well-known method for synthesizing metal nanoparticles the form immediately after synthesis is in a state in which metal nanoparticles are dispersed in a reaction solvent.
- solid-liquid separation has been performed by a complicated or long-time method such as decantation or centrifugation for a long time, there has been an industrial problem.
- the metal nanoparticle-containing composition of the present invention exists in a state in which metal nanoparticles are aggregated at the time of production by appropriately adjusting the structure of the organic substance present on the surface of the metal fine particles, so that it is conventionally in the order of microns. Separation can be performed using existing equipment such as filter paper and filter press that has been used to collect the particles. Furthermore, since the metal nanoparticle-containing composition obtained in the present invention can exist stably even in a dry state, it is less bulky and is very advantageous in terms of transportation and storage.
- the metal nanoparticles are derived from hydrophobicity.
- COO ⁇ is hydrophobic toward the particle surface side and hydrophobic toward the outside (water side in the reaction). It is considered that the C chain is located.
- water is used as a reaction solvent, hydrophobic particles gather to form a coarse aggregate, which facilitates solid-liquid separation such as a filter press.
- the metal nanoparticle-containing composition of the present invention is stably present in a state where particles are aggregated in a dry powder state separated into a solid and a liquid, and dispersed again when redispersed in an appropriate dispersion medium. Is possible. Although the mechanism is not clear, it is considered that aggregation after reaction and redispersion in a dispersion medium are possible by the influence of multiple adsorption of organic substances on the surface of the metal nanoparticles functioning as a protective agent.
- the conductive paste of the present invention is obtained by concentrating or diluting the above-described metal nanoparticle-containing composition with a dispersion medium as necessary. As a result, electrical wiring and conductive films can be produced on various substrate materials by low-temperature heat treatment.
- a polar solvent is preferably selected, and examples thereof include water, alcohol, polyol, glycol ether, 1-methylpyrrolidinone, pyridine, terpineol, texanol, butyl carbitol, and butyl carbitol acetate. .
- a method for producing the metal nanoparticle-containing composition of the present invention will be described.
- a reducing liquid preparation step, a silver reaction step, and a filtration / washing step are performed to obtain the above-described metal nanoparticle-containing composition.
- a liquid preparation process for adjusting the raw material liquid and the reducing liquid, a temperature raising process for raising the temperature, a reaction process for adding the raw material liquid to the reducing liquid and advancing the reaction, metal particles in the liquid (particularly silver particles) can be produced by performing a ripening step for growing the liquid, a filtration / washing step for removing excess organic substances by filtration / water washing, and a drying step for removing water in the liquid by drying.
- the reducing liquid used in the reducing liquid preparation step includes water, aqueous ammonia, an organic substance that functions as a protective agent, and a reducing agent.
- the molecular weight of the organic material is 200 or less. This is because ammonia water acts as a stabilizer for dissolving acid in water.
- the organic substance that functions as the protective agent preferably has an affinity group on the particle surface, and examples include linear fatty acids. Further, the molecular weight is preferably 150 or less from the viewpoint of easy evaporation during firing.
- the reducing agent may be any one that can be reduced to a metal. Hydrazine hydrate, hydrazine, borohydride alkali salt (NaBH 4 etc.), lithium aluminum hydride (LiAlH 4 ), ascorbic acid, primary amine, secondary amine, tertiary amine etc. can do.
- an aqueous metal salt solution is added to the reducing solution and reacted with the reducing solution.
- the temperature in the reaction vessel is preferably raised to a range of 40 ° C. to 80 ° C. for reaction.
- the metal salt aqueous solution added to the reaction vessel is kept at the same temperature as the reaction vessel. If the temperature in the reaction vessel is lower than 40 ° C., the degree of supersaturation of the metal increases and nucleation is promoted, so that the number of fine particles tends to increase. Above 80 ° C., nucleation is suppressed, but particle growth and particle aggregation tend to be promoted.
- the metal salt aqueous solution it is preferable to add all at once from the viewpoint of realizing a uniform reaction in the solution. If not added all at once, the solution becomes heterogeneous, and nucleation and particle aggregation occur simultaneously. As a result, nonuniform metal particles having a large particle size distribution may be obtained. Therefore, “added all at once” as used herein is particularly limited as long as the reaction factor such as the concentration or pH of the reducing agent or protective agent does not substantially change depending on the addition timing of the aqueous metal salt solution. It is not something.
- the product obtained in the reaction process is washed with water.
- the method of the filtration / water washing step is not particularly limited, but from the industrial viewpoint, there is a method of solid-liquid separation by passing the reaction liquid through the filter cloth rather than centrifugation or decantation.
- a filter press or the like can be used as the apparatus.
- a reaction tank having a shape and structure that can provide uniform stirring. This is because the metal nanoparticles are obtained by a reduction reaction, but the size of the particles to be obtained is very small, and therefore the local concentration and pH distribution greatly affect the particle size distribution.
- each manufacturing process is demonstrated along the flow of reaction about one Embodiment of the manufacturing method of the fine silver particle of this invention.
- the reaction is preferably performed in an inert gas atmosphere such as nitrogen, and in order to remove dissolved oxygen in the solution, it is preferable to perform nitrogen aeration treatment.
- a reducing liquid in which a reducing substance is dissolved
- a liquid II in which a metal salt (particularly a silver salt) as a raw material is dissolved
- the reducing solution is obtained by dissolving the above reducing agent in pure water, adding a protective agent and ammonia water, respectively, and mixing until uniform.
- the raw material liquid is obtained by dissolving metal salt crystals in pure water.
- ⁇ Temperature raising process> After each solution is prepared, the temperature of the solution is raised to a reaction temperature by using a water bath or a heater. At this time, it is preferable to heat the reducing solution and the reaction solution in the same manner because there is an effect of preventing non-uniformity of the reaction during the reaction and the uniformity of the particles can be maintained. At this time, the target temperature to be raised (later reaction temperature) is in the range of 40 to 80 ° C.
- ⁇ Filtering and washing process The obtained slurry is subjected to solid-liquid separation using a filter press, and the obtained cake is washed. As the determination of the end of the cleaning process, it is preferable to perform cleaning until the electric conductivity is equal to that of pure water as a cleaning liquid.
- Example 1 Preparation of metal nanoparticle containing composition A 24 L reaction tank was used for the reaction tank. In order to ensure the uniformity of stirring, baffle plates were arranged at equal intervals inside the wall surface. For stirring, a stirring rod provided with two turbine blades was installed at the center of the reaction vessel. The reaction vessel was equipped with a thermometer for monitoring the temperature. A nozzle was provided so that nitrogen could be supplied to the solution from below.
- the rotation speed of the stirring bar was adjusted to 338 rpm. And temperature adjustment was performed so that the solution temperature in a reaction tank might be 60 degreeC.
- hexanoic acid special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.
- hexanoic acid special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.
- 114.5 g of a 50% hydrazine hydrate (Otsuka Chemical Co., Ltd.) aqueous solution was added as a reducing agent, and this was used as a reducing solution.
- a silver nitrate aqueous solution in which 162 g of silver nitrate crystals (special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 438 g of water was prepared, and this was used as a raw material liquid.
- the temperature of the aqueous silver nitrate solution was adjusted to 60 ° C., the same as the solution in the reaction vessel.
- Example 1 a sample fired at 150 ° C. is referred to as Example 1 (150), and a sample fired at 200 ° C. is referred to as Example 1 (200).
- Example 1 is a calcined powder.
- Example 2 Preparation, application and baking of paste A silver paste having a silver concentration of 60% by mass was prepared by kneading 6.0 g of the silver powder obtained in (1) of Example 1 and 4.0 g of terpineol. The silver paste obtained here was used as a coating film on a slide glass using an applicator. Moreover, this coating film was baked for 60 minutes at 150 degreeC and 200 degreeC, respectively in the heating furnace in air
- volume resistance measurement The volume resistance of the fired film obtained in (1) was measured using Loresta (registered trademark) manufactured by Mitsubishi Chemical Corporation.
- Example 3 Preparation, application and firing of paste A silver paste having a silver concentration of 50% by mass was prepared by kneading 5.0 g of the silver powder obtained in (1) of Example 1 and 5.0 g of terpineol. This silver paste was used as a coating film on a slide glass using an applicator. The coating film was dried at 100 ° C. in the atmosphere for 60 minutes to evaporate the solvent in the coating film, and then baked at 150 ° C. in the atmosphere for 30 minutes. Similarly, Example 3 (150) was fired at 150 ° C., and Example 3 is a film obtained by firing the paste. (2) Volume resistance measurement The volume resistance of the fired film obtained in (1) was measured in the same manner as in (2) of Example 2.
- Comparative Example 1 Silver powder coated with oleylamine was prepared. First, 50 mg of silver acetate was dissolved in 2.0 g of oleylamine, and the solution was poured into 50 ml of refluxing hexane. Hold in that state for 2 days. Looking at the state after the reaction, fine particles were dispersed in the reaction solvent, and solid-liquid separation by suction filtration was impossible. Therefore, centrifugation was performed to remove the reaction solvent. Thereafter, it was washed twice with methanol and dried to obtain a dry powder. The silver powder obtained as Comparative Example 1 is a powder having a production method different from that of the example. The obtained silver powder was subjected to the operations (2) to (3) in the same manner as in Example 1. Table 1 shows the results obtained in the examples and comparative examples.
- Example 2 The operation of Example 2 was performed using the silver nanopowder of Comparative Example 1.
- Example 1 is a silver powder obtained by firing the metal-containing composition itself of the present invention
- Example 2 is a film obtained by firing Example 1 into a film
- Example 3 These are the films
- Comparative Example 1 is a silver powder obtained by firing a metal-containing composition itself having a manufacturing method different from that of Example 1
- Comparative Example 2 is a film obtained by firing Comparative Example 1 into a film by baking.
- the specific surface area was measured by the BET method using 4S-U2 manufactured by Yuasa Ionics. Further, the TAP density was measured using the measuring method described in JP-A-2007-263860.
- N, O, and C in the powder before and after firing in Example 1 and Comparative Example 1 were measured. Further, the amount of C remaining in the fired film of Example 3 was measured.
- N and O were measured by an oxygen-nitrogen simultaneous analyzer (LECO, TC-436 type) by melting in an inert gas-infrared absorption method.
- C was measured by a combustion method using a carbon / sulfur analyzer (Horiba, EMIA-220V).
- the amount of C contained in the metal nanoparticle-containing composition is less than 0.30 in terms of a reduction ratio (C amount after firing / C amount before firing) before and after firing at 150 ° C. for 60 minutes. Is preferable, more preferably less than 0.20, and still more preferably less than 0.15.
- the reduction ratio of the amount of C is 0.30 or more, it is considered that the conductivity of the fired film is deteriorated due to the low removal rate of C by firing.
- the rate of decrease in the amount of C before and after firing is lower. From this, the lower limit of the decreasing rate of the C amount before and after firing cannot be defined.
- the mass% of C means the ratio of the mass of C with respect to the mass of the whole powder.
- Table 1 shows the firing temperature, firing time, BET, TAP density, mass ratio of N, O, C, true density and true density ratio ⁇ f and ⁇ 150 / ⁇ M in the powder state of Example 1 and Comparative Example 1. , ⁇ 200 / ⁇ M.
- Table 2 shows values of firing temperature, firing time and volume resistivity in Examples 2, 3 and Comparative Example 2.
- the values shown in parentheses for the mass ratio of C are the reduction ratios before and after firing at 150 ° C. and 200 ° C. for 60 minutes (the amount of C after firing / the amount of C before firing).
- FIG. 3 is an SEM photograph of the metal-containing composition of the present invention that has been filtered, washed and then dried.
- the arrow in the figure is 600 nm. Obviously nanometer size and observable microparticles are clustered. From this, it can be seen that the metal-containing composition of the present invention is an aggregate of extremely small nanometer-sized primary particles.
- FIG. 4 is a TEM image taken by redispersing the dry powder of FIG. 3 in a solvent. Between the arrows is 50 nm. The primary particle diameter obtained from this was 14 nm, and it can be seen that in the dry powder state, the primary particles aggregate and exist as aggregates.
- FIG. 1 is a graph showing the relationship between the true density ratio ⁇ f of a metal-containing composition and the volume resistance when firing a paste using the same as a film.
- the triangle is a sample (Comparative Example 2) obtained by firing the silver powder of Comparative Example 1 at 200 ° C. for 60 minutes in the atmosphere
- the square is a sample obtained by firing the silver powder of Example 1 at 200 ° C. for 60 minutes in the atmosphere (Example 2 (200 )
- Rhombuses are those obtained by firing the example at 150 ° C. for 60 minutes in the atmosphere (Example 2 (150)).
- the circles are those obtained by drying the silver powder of Example 1 at 100 ° C.
- Example 3 Since squares, circles, and rhombuses are volume resistances of the fired films (Examples 2 and 3) using the metal-containing composition of Example 1, the true density ratio ⁇ f has the same value of 1.01. .
- the true density ratio of the metal-containing composition of Comparative Example 1 is 1.15, and the fired film (Comparative Example 2) prepared by applying the paste and firing at 200 ° C. for 60 minutes.
- the volume resistance is higher than that in the case of firing in the atmosphere at 150 ° C. (Example 2 or 3). That is, in the comparative example, the true density ratio ⁇ f and the volume resistance were higher than those in the example. Further, when Example 2 and Example 3 are compared, Example 3 (when dried in air at 150 ° C. for 60 minutes) is more than Example 3 (after drying in air at 100 ° C. for 60 minutes and then in air at 150 ° C.). In the case of baking for 30 minutes, the volume resistance was better.
- Example 3 Since the firing time at 150 ° C. is shorter in Example 3, it is considered that a certain degree of particle sintering has progressed during drying at 100 ° C. for 60 minutes. This result also shows that the metal-containing composition of the present invention is excellent in low-temperature sinterability.
- FIG. 5 is a surface SEM photograph in the case where the paste using the powder of Example 1 is used as a film and baked in air at 150 ° C. for 60 minutes (Example 2 (150)), and FIG. 6 is the powder of Example 1. It is the surface SEM photograph at the time of making paste the film
- the arrows in FIGS. 5 and 6 indicate 600 nm.
- Example 7 is a surface SEM photograph in the case where the paste using the powder of Example 1 was applied and dried in air at 100 ° C. for 60 minutes and then baked in air at 150 ° C. for 30 minutes (Example 3). .
- the arrow in FIG. 7 indicates 300 nm.
- the lump in the photograph is a lump of about several hundred nm, and it was found that the fired film was composed of sintered submicron size lump.
- FIG. 8 is a baking in which a paste using the powder of Comparative Example 1 is applied and baked in air at 150 ° C. for 60 minutes (Comparative Example 2 (150)), and FIG. It is a SEM image of a film
- the horizontal axis is the ratio of the density ⁇ M in the bulk state to ⁇ 150 or ⁇ 200 of the metal-containing composition of Example 1, and the vertical axis is the volume resistance.
- the triangle is the case where the silver powder of Comparative Example 1 is baked at 200 ° C. for 60 minutes in the atmosphere (Comparative Example 2 (200)), and the square is the silver powder of Example 1 at 200 ° C. in the atmosphere. This is the case when firing for 60 minutes (Comparative Example 1 (200)), and the diamond shape is when the silver powder of Example 1 is fired at 150 ° C. for 60 minutes in the atmosphere (Example 2 (150)).
- the sample (square) fired at 200 ° C. for 60 minutes in the atmosphere had a ratio with the density in the bulk state close to 1.00 and the smallest volume resistance.
- the sample (diamonds) fired at 150 ° C. for 60 minutes in the atmosphere had a ratio with the density in the bulk state of about 0.98, although not as much as when fired at 200 ° C.
- the volume resistance was higher than in the case of firing at 200 ° C.
- the ratio to the density in the bulk state was about 0.87, and the volume resistance was higher than that in the case where the example was fired at 150 ° C. (diamonds).
- the fact that the ratio to the density in the bulk state is close to 1.00 indicates that the fired product of the metal-containing composition is closer to bulk silver. This shows that the protective agent that had adhered to the metal surface evaporated and the sintering of the metal particles proceeded even at low temperatures.
- the metal nanoparticle-containing composition of the present invention is excellent in sinterability at low temperature, and as a result, a sintered film having a low resistance value can be obtained even at low temperature firing.
- the metal nanoparticle-containing composition of the present invention is excellent in low-temperature sinterability, and a low-resistance circuit wiring can be produced by printing on a substrate such as paper or PET.
- the metal particles according to the present invention are used for forming electrodes for FPDs, solar cells, organic EL, wiring for RFID, wiring for embedding fine trenches, via hole contact holes, etc., and coloring materials for painting cars and ships.
- Carrier for adsorbing biochemical substances in medical, diagnostic and biotechnology fields, antibacterial paint using antibacterial action, catalyst, low temperature sinterability and excellent conductivity, conductive adhesive and resin as a substitute for solder Can be used in various applications such as conductive pastes, flexible printed circuits using the same, high-flexibility shields, and capacitors.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Composite Materials (AREA)
- Dispersion Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Powder Metallurgy (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Conductive Materials (AREA)
- Non-Insulated Conductors (AREA)
Abstract
Description
ρf=ρ200/ρ150・・・(1)
反応の原液を調整する本工程では、原料液として液を二種類用意する。一方は還元性を有する物質を溶解させた液I(後には還元液と称する)であり、もう一方は原料である金属塩(特に銀塩)が溶解された液II(後には原料液と称する)である。還元液は、上述の還元剤を純水に溶解させるとともに、保護剤およびアンモニア水をそれぞれ添加し、均一になるまで混合することによって得る。また、原料液は金属塩の結晶を純水に溶解させることによって得られる。
液をおのおの準備した後に、ウオーターバスもしくはヒーターを用いて液を昇温し、反応温度まで上昇させる。このとき、還元液と反応液を同様に加熱しておけば、反応時において反応の不均一が防止される効果があり、粒子の均一性を保つことができるので好ましい。このときに昇温させる目的の温度(後の反応温度)は、40~80℃の範囲である。
液がともに目的温度まで上昇すれば、還元液と原料液を混合する。添加は突沸に注意した上で、一度に行うことが反応の均一性の面から好ましい。
反応液を混合した後、10~30分程度攪拌を続け、反応を完結させる。このときの反応は、サンプリングした反応液に対し、ヒドラジンを滴下することにより、未還元の反応が生じるかどうか確認することによって、終点を判断する。
得られたスラリーはフィルタープレスを用いて固液分離を行い、得られたケーキに対して洗浄を行う。洗浄工程終了の判断としては、洗浄液である純水と同等の電気伝導度となるまで洗浄を行うのが好ましい。
洗浄後のケーキを、真空中で40℃で12時間乾燥させることで、乾燥した金属粒子凝集体が得られる。
(実施例1)
(1)金属ナノ粒子含有組成物の作製
反応槽には24L反応槽を使用した。攪拌の均一性を担保するため、壁面内側には等間隔に邪魔板を配置した。また攪拌のために、タービン羽根を2枚備えた攪拌棒を反応槽の中心に設置した。反応槽には温度をモニターするための温度計を設置した。また溶液に下部より窒素を供給できるようにノズルを配設した。
上記で得られた粉末を角形の灰分測定用灰皿上に約2mmの厚みで敷き詰め、加熱炉(ヤマト科学製マッフル炉FO310)内で、大気中150℃、200℃でそれぞれ60分間焼成した。これらを区別するために、150℃で焼成したサンプルを実施例1(150)とし、200℃で焼成したサンプルを実施例1(200)とする。実施例1は焼成した粉末である。
前記焼成工程で得られた粉末を、Quantachrome社製ULTRAPYCNOMETER1000を用いて真密度を測定した。また、この測定で得られた値を用いて前記ρf、(ρ200/ρM)及び(ρ150/ρM)の値を算出した。なお、ρMは公知の文献から引用した。
(1)ペーストの作製、塗布及び焼成
実施例1の(1)で得られた銀粉末6.0gとターピネオール4.0gを混練することで銀濃度60質量%の銀ペーストを作製した。ここで得られた銀ペーストをスライドガラス上にアプリケーターを用いて塗布膜とした。また、該塗布膜を大気中加熱炉内で150℃、200℃でそれぞれ60分間焼成した。実施例2も同じく150℃で焼成したものを実施例2(150)、200℃で焼成したものを実施例2(200)と表す。実施例2は共にペーストを焼成した膜である。
前記(1)で得られた焼成膜の体積抵抗を三菱化学株式会社製ロレスタ(登録商標)を用いて測定した。
(1)ペーストの作製、塗布及び焼成
実施例1の(1)で得られた銀粉末5.0gとターピネオール5.0gを混練することで銀濃度50質量%の銀ペーストを作製した。この銀ペーストをスライドガラス上にアプリケーターを用いて塗布膜とした。該塗布膜を大気中100℃で60分間乾燥させ、塗布膜中の溶媒を蒸発させた後、大気中150℃で30分間焼成を行った。
実施例3も同じく150℃で焼成したものを実施例3(150)、実施例3は共にペーストを焼成した膜である。
(2)体積抵抗測定
前記(1)で得られた焼成膜の体積抵抗を実施例2の(2)と同様にして測定した。
オレイルアミンに被覆された銀粉を作製した。まず、50mgの酢酸銀を2.0gのオレイルアミン中に溶解し、その溶液を還流している50mlのヘキサン中に注入した。2日間その状態で保持した。反応後の状態を見ると、反応溶媒中に微粒子が分散しており、吸引濾過による固液分離は不可能であったため、遠心分離を実施して反応溶媒を除去した。その後、メタノールを用いて2回洗浄した後乾燥させて乾燥粉を得た。比較例1として得られた銀粉は実施例とは製造方法が異なる粉である。得られた銀粉について、実施例1と同様に(2)~(3)の操作を行った。実施例及び比較例で得られた結果を表1に示す。
比較例1の銀ナノ粉末を用いて、実施例2の操作を行った。まとめると、実施例1は本発明の金属含有組成物自体を焼成して得た銀粉であり、実施例2は実施例1をペースト化して膜にしたものを焼成した膜であり、実施例3は実施例2の焼成条件を変更した膜である。また比較例1は実施例1と製造方法の異なる金属含有組成物自体を焼成して得た銀粉であり、比較例2は比較例1をペースト化して膜にしたものを焼成した膜である。なお、BET法による比表面積の測定はユアサアイオニクス製の4S-U2を用いて行った。また、TAP密度の測定は、特開2007-263860号公報に記載されている測定法を用いて行った。
Claims (7)
- 平均粒子径が100nm未満の微小金属粒子を含む金属含有組成物であって、
前記金属含有組成物を150℃で60分間加熱した後の真密度をρ150とし、
前記金属含有組成物を200℃で60分間加熱した後の真密度をρ200とし、
前記ρ200と前記ρ150との比(ρ200/ρ150)を真密度比ρfとした際に、
前記ρfが1.10以下である金属含有組成物。 - 前記微小金属粒子のバルク状態の密度をρMとした際に、
前記ρ150と前記ρMとの比(ρ150/ρM)および/または前記ρ200と前記ρMとの比(ρ200/ρM)が0.8以上である請求の範囲第1項に記載された金属含有組成物。 - 前記微小金属粒子の表面には、分子量200以下の有機物が付着している請求の範囲第1項または2項の何れかの請求の範囲に記載された金属含有組成物。
- 前記微小金属粒子は、金、銀、銅のうち少なくとも1種を含む、化合物および/または単体物である請求の範囲第1項乃至3項の何れか1の請求の範囲に記載された金属含有組成物。
- 請求の範囲第1項乃至4項の何れか1の請求の範囲に記載された金属含有組成物を含む導電性ペースト。
- 請求の範囲第1項乃至4項の何れか1の請求の範囲に記載された金属含有組成物を焼成した金属膜。
- 水とアンモニア水と分子量200以下の有機物と還元剤を混合し還元液を調液する還元液調液工程と、
前記還元液に、金属塩水溶液を添加し反応させる反応工程と、
前記反応工程で得られた生成物を濾過し水で洗浄する濾過・洗浄工程とを有する金属含有組成物の製造方法。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US12/999,819 US20110155968A1 (en) | 2008-06-30 | 2008-08-07 | Fine metal particle-containing composition and method for manufacturing the same |
EP08792313.2A EP2311586A4 (en) | 2008-06-30 | 2008-08-07 | COMPOSITION CONTAINING METAL MICROPARTICLES AND PROCESS FOR PRODUCING THE SAME |
KR1020117000686A KR101525099B1 (ko) | 2008-06-30 | 2008-08-07 | 미소금속입자함유 조성물 및 그 제조 방법 |
CN200880130236.XA CN102076447B (zh) | 2008-06-30 | 2008-08-07 | 含微小金属粒子的组合物及其制造方法 |
JP2010518875A JP5377483B2 (ja) | 2008-06-30 | 2008-08-07 | 微小金属粒子含有組成物及びその製造方法 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2008171771 | 2008-06-30 | ||
JP2008-171771 | 2008-06-30 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2010001496A1 true WO2010001496A1 (ja) | 2010-01-07 |
Family
ID=41465609
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2008/064256 WO2010001496A1 (ja) | 2008-06-30 | 2008-08-07 | 微小金属粒子含有組成物及びその製造方法 |
Country Status (6)
Country | Link |
---|---|
US (1) | US20110155968A1 (ja) |
EP (1) | EP2311586A4 (ja) |
JP (1) | JP5377483B2 (ja) |
KR (1) | KR101525099B1 (ja) |
CN (1) | CN102076447B (ja) |
WO (1) | WO2010001496A1 (ja) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2011181538A (ja) * | 2010-02-26 | 2011-09-15 | Kyoto Elex Kk | 太陽電池素子の電極形成用導電性ペースト |
JP2012031478A (ja) * | 2010-07-30 | 2012-02-16 | Toda Kogyo Corp | 銀微粒子とその製造方法、並びに該銀微粒子を含有する導電性ペースト、導電性膜及び電子デバイス |
JP2020090725A (ja) * | 2020-02-14 | 2020-06-11 | 協立化学産業株式会社 | 複合粒子、銅ペースト組成物、および導電体 |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102470490B (zh) | 2009-07-14 | 2015-08-05 | 同和电子科技有限公司 | 使用金属纳米粒子的接合材料及接合方法 |
WO2011114543A1 (ja) | 2010-03-15 | 2011-09-22 | Dowaエレクトロニクス株式会社 | 接合材およびそれを用いた接合方法 |
JP2011202265A (ja) * | 2010-03-26 | 2011-10-13 | Dowa Electronics Materials Co Ltd | 低温焼結性金属ナノ粒子組成物および該組成物を用いて形成された電子物品 |
US8647535B2 (en) * | 2011-01-07 | 2014-02-11 | International Business Machines Corporation | Conductive metal and diffusion barrier seed compositions, and methods of use in semiconductor and interlevel dielectric substrates |
SG11201502567TA (en) * | 2012-10-29 | 2015-05-28 | Alpha Metals | Sintering powder |
CN103482619B (zh) * | 2013-09-09 | 2016-02-24 | 东南大学 | 一种石墨烯-氧化铜三维泡沫复合材料 |
US9622483B2 (en) | 2014-02-19 | 2017-04-18 | Corning Incorporated | Antimicrobial glass compositions, glasses and polymeric articles incorporating the same |
US11039620B2 (en) | 2014-02-19 | 2021-06-22 | Corning Incorporated | Antimicrobial glass compositions, glasses and polymeric articles incorporating the same |
US11039621B2 (en) | 2014-02-19 | 2021-06-22 | Corning Incorporated | Antimicrobial glass compositions, glasses and polymeric articles incorporating the same |
CN104289727B (zh) * | 2014-10-22 | 2016-08-24 | 苏州正业昌智能科技有限公司 | 一种以改性壳聚糖为还原剂制备纳米银的方法 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH04333504A (ja) * | 1991-05-10 | 1992-11-20 | Sumitomo Metal Mining Co Ltd | 単分散銀微粉の連続製造方法 |
JP2006028637A (ja) | 2004-06-14 | 2006-02-02 | Sumitomo Metal Mining Co Ltd | 銀微粒子コロイド分散液、銀膜形成用塗布液とその製造方法、及び銀膜 |
JP2006183072A (ja) * | 2004-12-27 | 2006-07-13 | Namics Corp | 銀微粒子、その製造方法及び銀微粒子を含有する導電ペースト |
JP2007095510A (ja) | 2005-09-29 | 2007-04-12 | Tokai Rubber Ind Ltd | 導電性ペースト |
JP2007263860A (ja) | 2006-03-29 | 2007-10-11 | Dowa Holdings Co Ltd | 粉体のタップ密度測定方法およびタップ密度測定装置 |
JP2008133527A (ja) * | 2006-10-31 | 2008-06-12 | Toda Kogyo Corp | 銀微粒子及びその製造方法 |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6743395B2 (en) * | 2000-03-22 | 2004-06-01 | Ebara Corporation | Composite metallic ultrafine particles and process for producing the same |
CN1143817C (zh) * | 2001-11-28 | 2004-03-31 | 中国科学院长春应用化学研究所 | 银-金核-壳纳米粒子二维介观分形聚集体的制备方法 |
JP2005081501A (ja) * | 2003-09-09 | 2005-03-31 | Ulvac Japan Ltd | 金属ナノ粒子及びその製造方法、金属ナノ粒子分散液及びその製造方法、並びに金属細線及び金属膜及びその形成方法 |
KR101328908B1 (ko) * | 2005-10-14 | 2013-11-28 | 토요잉크Sc홀딩스주식회사 | 금속 미립자 분산체의 제조 방법, 상기 방법으로 제조된금속 미립자 분산체를 이용한 도전성 잉크, 및 도전성 피막 |
US7919015B2 (en) * | 2006-10-05 | 2011-04-05 | Xerox Corporation | Silver-containing nanoparticles with replacement stabilizer |
KR101004553B1 (ko) * | 2007-10-24 | 2011-01-03 | 도와 일렉트로닉스 가부시키가이샤 | 미소 은 입자 함유 조성물, 그 제조방법, 미소 은 입자의 제조방법 |
-
2008
- 2008-08-07 US US12/999,819 patent/US20110155968A1/en not_active Abandoned
- 2008-08-07 KR KR1020117000686A patent/KR101525099B1/ko active IP Right Grant
- 2008-08-07 JP JP2010518875A patent/JP5377483B2/ja active Active
- 2008-08-07 EP EP08792313.2A patent/EP2311586A4/en not_active Withdrawn
- 2008-08-07 WO PCT/JP2008/064256 patent/WO2010001496A1/ja active Application Filing
- 2008-08-07 CN CN200880130236.XA patent/CN102076447B/zh active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH04333504A (ja) * | 1991-05-10 | 1992-11-20 | Sumitomo Metal Mining Co Ltd | 単分散銀微粉の連続製造方法 |
JP2006028637A (ja) | 2004-06-14 | 2006-02-02 | Sumitomo Metal Mining Co Ltd | 銀微粒子コロイド分散液、銀膜形成用塗布液とその製造方法、及び銀膜 |
JP2006183072A (ja) * | 2004-12-27 | 2006-07-13 | Namics Corp | 銀微粒子、その製造方法及び銀微粒子を含有する導電ペースト |
JP2007095510A (ja) | 2005-09-29 | 2007-04-12 | Tokai Rubber Ind Ltd | 導電性ペースト |
JP2007263860A (ja) | 2006-03-29 | 2007-10-11 | Dowa Holdings Co Ltd | 粉体のタップ密度測定方法およびタップ密度測定装置 |
JP2008133527A (ja) * | 2006-10-31 | 2008-06-12 | Toda Kogyo Corp | 銀微粒子及びその製造方法 |
Non-Patent Citations (1)
Title |
---|
See also references of EP2311586A4 |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2011181538A (ja) * | 2010-02-26 | 2011-09-15 | Kyoto Elex Kk | 太陽電池素子の電極形成用導電性ペースト |
JP2012031478A (ja) * | 2010-07-30 | 2012-02-16 | Toda Kogyo Corp | 銀微粒子とその製造方法、並びに該銀微粒子を含有する導電性ペースト、導電性膜及び電子デバイス |
JP2020090725A (ja) * | 2020-02-14 | 2020-06-11 | 協立化学産業株式会社 | 複合粒子、銅ペースト組成物、および導電体 |
Also Published As
Publication number | Publication date |
---|---|
CN102076447A (zh) | 2011-05-25 |
US20110155968A1 (en) | 2011-06-30 |
EP2311586A1 (en) | 2011-04-20 |
KR20110030556A (ko) | 2011-03-23 |
JPWO2010001496A1 (ja) | 2011-12-15 |
KR101525099B1 (ko) | 2015-06-02 |
JP5377483B2 (ja) | 2013-12-25 |
EP2311586A4 (en) | 2015-06-03 |
CN102076447B (zh) | 2014-12-17 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5377483B2 (ja) | 微小金属粒子含有組成物及びその製造方法 | |
JP4344001B2 (ja) | 微小銀粒子含有組成物、その製造方法、微小銀粒子の製造方法および微小銀粒子を有するペースト | |
JP5176824B2 (ja) | 銀被覆銅微粒子とその分散液及びその製造方法 | |
JP5898400B2 (ja) | 銅微粒子とその製造方法及び銅微粒子分散液 | |
EP2649621B1 (en) | Stable dispersions of monocrystalline nanometric silver particles | |
TWI389750B (zh) | A fine particle dispersion liquid, and a method for producing a fine particle dispersion liquid | |
JP6168837B2 (ja) | 銅微粒子およびその製造方法 | |
JPWO2018190246A1 (ja) | 銅粒子混合物及びその製造方法、銅粒子混合物分散液、銅粒子混合物含有インク、銅粒子混合物の保存方法及び銅粒子混合物の焼結方法 | |
JP5424545B2 (ja) | 銅微粒子及びその製造方法、並びに銅微粒子分散液 | |
JP5176060B2 (ja) | 銀粒子分散液の製造法 | |
JP2011063828A (ja) | 銅−ニッケルナノ粒子とその製造方法 | |
JP7361464B2 (ja) | AgPdコアシェル粒子およびその利用 | |
JP5232016B2 (ja) | 配線形成用材料 | |
JP6626572B2 (ja) | 金属接合材料及びその製造方法、並びにそれを使用した金属接合体の製造方法 | |
JP5124822B2 (ja) | 複合金属粉体およびその分散液の製造法 | |
JP2021147684A (ja) | 銅および酸化銅含有微粒子及びその製造方法 | |
JP2009215503A (ja) | 非極性炭化水素を溶媒とする分散性に優れた銀インク | |
JP5445659B2 (ja) | 銀被覆銅微粒子とその分散液及びその製造方法 | |
JP5239700B2 (ja) | 金属微粒子分散液を用いた塗膜形成方法及びそれを用いた塗膜 | |
JP5139846B2 (ja) | ケトンとの親和性に優れた銀微粉および銀インク |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 200880130236.X Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 08792313 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2010518875 Country of ref document: JP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2008792313 Country of ref document: EP |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20117000686 Country of ref document: KR Kind code of ref document: A |