WO2015133474A1 - 伝導性フィラー、伝導性フィラーの製造方法及び伝導性ペースト - Google Patents
伝導性フィラー、伝導性フィラーの製造方法及び伝導性ペースト Download PDFInfo
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- WO2015133474A1 WO2015133474A1 PCT/JP2015/056216 JP2015056216W WO2015133474A1 WO 2015133474 A1 WO2015133474 A1 WO 2015133474A1 JP 2015056216 W JP2015056216 W JP 2015056216W WO 2015133474 A1 WO2015133474 A1 WO 2015133474A1
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
- B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
- B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
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- 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
- B22F1/052—Metallic powder characterised by the size or surface area of the particles characterised by a mixture of particles of different sizes or by the particle size distribution
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- 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
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- 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
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- 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
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
- B22F1/142—Thermal or thermo-mechanical treatment
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/17—Metallic particles coated with metal
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
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- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/62—Metallic pigments or fillers
- C09C1/627—Copper
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- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/66—Copper alloys, e.g. bronze
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
- C09D161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09D161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/26—Thermosensitive paints
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/4417—Methods specially adapted for coating powder
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/56—After-treatment
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
- C23C8/20—Carburising
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- 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
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
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Definitions
- the present invention relates to a conductive filler such as electrical conductivity (conductive) and thermal conductivity, a method for producing the conductive filler, and a conductive paste.
- a conductive filler such as electrical conductivity (conductive) and thermal conductivity
- a method for producing the conductive filler and a conductive paste.
- a conductive paste formed by mixing an inorganic filler such as silver powder and a binder resin has high conductivity and thermal conductivity.
- Patent Document 1 discloses a conductive paste using silver fine particles.
- the silver fine particles can be fired at a low temperature.
- Patent Document 1 the silver fine particles of Patent Document 1 have problems that they have high conductivity, but are high in cost and insufficient in migration resistance.
- the conductive paste using copper powder as a metal filler solves the above-mentioned problems.
- a copper oxide film may be formed by reaction with oxygen. Therefore, in the conductive paste using copper powder as a metal filler, the electric resistance is increased and sufficient conductivity may not be obtained.
- An object of the present invention is to provide a conductive filler, a method for producing the conductive filler, and a conductive paste, which can effectively improve conductivity and thermal conductivity.
- the conductive filler according to the present invention is a nanoparticle comprising copper powder and at least one transition metal or transition metal compound belonging to Groups 8 to 10 of the periodic table, which is disposed on the surface of the copper powder. It is a composite particle containing a precipitate of a size.
- the nano-sized precipitate is also present inside the copper powder.
- the average particle size of the copper powder is in the range of 1.0 ⁇ m to 25 ⁇ m.
- the average particle diameter of the copper powder is preferably in the range of 1.0 ⁇ m to 10 ⁇ m.
- the average particle diameter of the copper powder is preferably in the range of 3.0 ⁇ m to 25 ⁇ m.
- the flake powder is produced by flattening a spherical powder having an average particle size in the range of 1.0 ⁇ m to 10 ⁇ m.
- a film of the nano-sized precipitate is formed on the surface of the copper powder, and the film thickness of the nano-sized precipitate is 100 nm. It is as follows.
- the nano-sized precipitate is a particle, and the particle size of the nano-sized precipitate is 100 nm or less.
- the content of the transition metal or the transition metal compound is preferably in the range of 0.1 to 6.0% by weight in 100% by weight of the composite particles.
- the transition metal is cobalt.
- the transition metal compound is at least one of the transition metal oxide and the transition metal carbide. More preferably, it is at least one of cobalt oxide and cobalt carbide.
- the copper powder is made of pure copper.
- the conductive paste according to the present invention includes the conductive filler according to the present invention and a binder resin.
- the binder resin is preferably at least one resin selected from the group consisting of epoxy resins, polyester resins, urethane resins, phenol resins, and imide resins.
- the conductive paste of the present invention may be an electrically conductive paste, that is, a conductive paste, or a heat conductive paste.
- the method for producing a conductive filler according to the present invention is a method for producing a conductive filler constituted according to the present invention, and is a periodic table group 8 to group 10 which is a material of copper and nano-sized precipitates.
- a conductive filler which is a composite particle.
- the step of preparing the composite metal powder is performed by an atomizing method.
- the method for producing a conductive filler according to the present invention preferably further includes a step of adding and mixing a sintering inhibitor before the step of heat-treating the composite metal powder.
- the step of bringing the carbon source into contact with the surface of the composite metal powder is performed by bringing the composite metal powder into contact with a carbon-containing gas at 250 to 400 ° C.
- the heat treatment is preferably performed at a temperature of 400 ° C. to 700 ° C. in an inert gas atmosphere.
- the step of obtaining the conductive filler by removing at least a part of carbon adhering to the surface of the composite metal powder includes the composite metal powder and a binder resin. Are mixed until at least a part of the carbon adhering to the surface of the composite metal powder is removed.
- the composite metal powder and the binder resin are mixed by kneading for 20 minutes to 1 hour.
- a carbon source is contacted by a CVD method to grow a carbon allotrope from the surface of the composite metal powder;
- the composite metal powder obtained by growing the carbon allotrope from the surface is further subjected to a heat treatment at a temperature of 650 ° C. to 950 ° C. in an inert gas atmosphere, and is attached to the surface of the composite metal powder.
- the carbon allotrope is removed together with carbon.
- the conductive filler and conductive paste according to the present invention at least one transition metal belonging to Groups 8 to 10 of the periodic table or a nano-sized precipitate that is a compound of a transition metal is disposed on the surface of the copper powder. Has been. Therefore, it is possible to provide a conductive filler and a conductive paste that exhibit high conductivity and high thermal conductivity.
- FIG. 1 is a diagram showing a heat profile as an example of a method for producing a conductive filler according to the present invention.
- FIG. 2 is a view showing a heat profile as another example of the method for producing a conductive filler according to the present invention.
- FIG. 3 is a diagram showing an FE-SEM photograph of the composite particles obtained in Example 1 at a magnification of 20000 times.
- FIG. 4 is a view showing an FE-SEM photograph of the composite particles obtained in Example 3 at a magnification of 80000 times.
- FIG. 1 is a diagram showing a heat profile as an example of a method for producing a conductive filler according to the present invention.
- FIG. 2 is a view showing a heat profile as another example of the method for producing a conductive
- FIG. 7 is a diagram showing an EDS element mapping image of C by a transmission electron microscope at the site of FIG.
- FIG. 8 is a diagram showing an EDS element mapping image of O by a transmission electron microscope at the site of FIG.
- FIG. 9 is a diagram showing an EDS element mapping image of Co by the transmission electron microscope at the site of FIG.
- FIG. 10 is a diagram showing an EDS element mapping image of Cu by a transmission electron microscope at the site of FIG.
- FIG. 11 is a view showing a STEM-BF image of the composite particles (conductive filler) obtained in Example 2.
- the scale bar of the scale in the figure is 5 nm.
- FIG. 12 is a diagram showing specific resistance measurement results of Examples 4 to 11 and Comparative Example 1.
- the conductive filler according to the present invention is a nanoparticle comprising copper powder and at least one transition metal or transition metal compound belonging to Groups 8 to 10 of the periodic table, which is disposed on the surface of the copper powder. It is a composite particle containing a precipitate of a size. Preferably, the nano-sized precipitate is also present inside the copper powder. More preferably, it is desirable that the nano-sized precipitates are present more on the surface than inside the copper powder.
- the nano-sized precipitate is a substance in which the substance dissolved or dissolved in the copper powder or the solution containing the copper powder at the beginning of the process appears as another solid in the process,
- the shape is preferably particulate or film-like.
- the nano-sized precipitates are present in the copper powder or on the copper powder surface, and the particle size or film thickness is preferably 200 nm or less.
- the particle size or film thickness of the nano-sized precipitate is more preferably 100 nm or less, and further preferably 25 nm or less. Further, when the density of nano-sized precipitates increases on the surface of the copper particles, the nano-sized precipitates change from dot-shaped particles to dendritic and sea-island films.
- nano-sized precipitates are observed with a transmission electron microscope (TEM). Although it is difficult to observe all nano-sized precipitates with a transmission electron microscope, nano-sized precipitates having a particle size or film thickness of 200 nm or less have been confirmed with a transmission electron microscope.
- TEM transmission electron microscope
- Examples of elements that become P-type oxide semiconductors include Group 7 to Group 11 chromium, manganese, iron, cobalt, nickel, palladium, and copper.
- the at least one transition metal belonging to Group 8 to Group 10 of the periodic table that is the nano-sized precipitate is not particularly limited, and examples thereof include iron, cobalt, nickel, and palladium.
- iron, nickel and cobalt are preferable because the oxide is a semiconductor and the catalytic activity is high. Moreover, iron or cobalt is more preferable because it easily precipitates on the surface of the copper powder by heat treatment. More preferably, it is cobalt. A plurality of transition metals may be included.
- the compound of at least one transition metal belonging to Groups 8 to 10 of the periodic table is not particularly limited, and examples thereof include cobalt oxide, cobalt carbide, and nickel oxide.
- at least one of the transition metal oxide and the transition metal carbide is desirable. More preferably, it is at least one of cobalt oxide and cobalt carbide.
- a plurality of transition metals or a transition metal compound may be included, or a layered transition metal oxide containing the above metal or copper may be used.
- the content ratio of the transition metal or the transition metal compound is preferably 0.1 to 6.0% by weight, more preferably 0.1 to 2.0% by weight in 100% by weight of the composite particle. % By weight, more preferably 0.3 to 1.0% by weight.
- the conductive filler and conductive paste excellent in electrical conductivity and thermal conductivity can be provided more reliably according to the present invention.
- the nano-sized precipitate covers 10% or more of the surface of the copper powder.
- the nano-sized precipitates may be scattered as nano-sized particles on the surface of the copper powder, or may form a film.
- oxidation can be prevented by including a small amount of transition metal.
- the nano-sized precipitate film acts as a passive film, and can more effectively prevent copper from being oxidized.
- the nano-sized precipitate is not particularly limited, but is desirably a precipitate having a particle size or a film thickness of 100 nm or less. More preferably, it is a precipitate having a particle size or film thickness of 25 nm or less.
- the copper powder can be obtained, for example, by pulverizing by the atomizing method.
- the average particle diameter of the copper powder is not particularly limited, but is preferably 0.5 ⁇ m to 50 ⁇ m, more preferably 1.0 ⁇ m to 10 ⁇ m, and still more preferably 1.0 ⁇ m to 5 ⁇ m.
- the average particle diameter means an average volume particle diameter, and can be measured by a laser diffraction / scattering particle diameter distribution measuring apparatus.
- the average volume particle size is calculated by the software of the apparatus assuming that the particle shape is spherical.
- a product number “MT3300II” manufactured by Microtrack Co., Ltd. can be used.
- the said copper powder may be spherical, it is desirable to have a flake shape with an aspect ratio larger than 1. Therefore, after atomization, it is preferable to flatten the copper powder by a ball mill process, a process using a cold spray method, an aerosol deposition method, or a thermal spray method applied to powder processing.
- flake powder When using flake powder, it is better if the spherical powder is processed into flakes. It is preferable to use flake powder having an average major axis diameter of 3.0 ⁇ m to 25 ⁇ m obtained by flaking spherical powder having an average particle diameter of 1.0 ⁇ m to 10 ⁇ m with a ball mill, a bead mill or the like.
- the average particle diameter of the copper powder is within the above preferred range, a conductive paste excellent in electrical conductivity and thermal conductivity can be provided more reliably according to the present invention.
- the copper powder is preferably made of pure copper.
- the conductive filler of the present invention can be obtained by various production methods.
- the copper powder be cleaned with an etching solution or the like before carbon described later is attached to the surface.
- Cobalt oxide and cobalt carbide are semiconductors and conduct electricity. Since such semiconducting conductivity is smaller than that of a metal such as copper, the precipitate on the surface of the copper powder is preferably nano-sized.
- a passivation layer having a film thickness of 3 to 50 ⁇ is formed of a material as a corrosion-resistant passivation film.
- the film thickness of the film-like nano-sized precipitate is desirably several tens of atomic layers or more.
- Cobalt oxide can take several valences, but the most stable valences are +2 and +3, and also +4. Therefore, it has been studied that not only hopping electrical conduction between Co 2+ and Co 3+ but also hopping electrical conduction between Co 3+ and Co 4+ occurs. There is a possibility that the characteristics of the transition metal compound having such characteristics are related to the conductivity.
- the values measured in various studies are measurements under bulk or micron size conditions. Under nano-size conditions and in the direction of cobalt oxide layer, semiconducting conductivity and quantum dot-like conductivity are further increased. There is a good possibility.
- carbon or a carbon allotrope may adhere to the nano-sized precipitate.
- a composite metal powder comprising copper and at least one transition metal belonging to Groups 8 to 10 of the periodic table serving as a nanosized precipitate material
- Preparing the composite metal powder contacting the surface of the composite metal powder with a carbon source, attaching carbon to the surface of the composite metal powder, and applying heat treatment to the composite metal powder.
- the method for preparing the composite metal powder is not particularly limited, but it is desirable to obtain the composite metal powder by the atomizing method as described above. In this case, a composite metal powder in which an additive is added to copper can be easily produced.
- the content ratio of the transition metal or the transition metal compound is preferably 0.1 to 6.0% by weight, more preferably 0.1 to 2% in 100% by weight of the composite metal powder. 0.0% by weight, more preferably 0.3 to 1.0% by weight.
- the conductive filler and conductive paste excellent in electrical conductivity and thermal conductivity can be provided more reliably according to the present invention.
- step 2-A described later Sintering inhibitor addition step It is desirable to add a sintering inhibitor, which is a finer particle, to the composite metal powder as a pretreatment in step 1-A described later. Thereby, aggregation of composite metal powders in a heat treatment step (step 1-B) described later can be more effectively prevented.
- a sintering inhibitor which is a finer particle
- examples of such fine particles include Aerosil, carbon black, and ketjen black.
- the amount of fine particles added is desirably 0.05 to 2.0% by weight with respect to the composite metal powder. More preferably, the content is 0.1% by weight to 2.0% by weight. If the subsequent process is a method in which powder is spread on the setter and the film thickness of the powder spread is as thin as the diameter of the particles, this process may be omitted.
- step 1-A shown in FIG. 1 carbon is adhered to the surface of the composite metal powder by bringing a carbon source into contact with the surface of the composite metal powder. In this process, carbon is attached, but no carbon allotrope is produced. In this step, the blackening of the color due to the adhesion of the carbon allotrope is not observed, and the composite metal powder has a copper color. Thereby, aggregation of the composite metal powders in the heat treatment step (step 1-B) described later can be suppressed.
- a carbon-containing compound having 1 to 30 carbon atoms, preferably 1 to 7 carbon atoms, more preferably 1 to 4 carbon atoms, and still more preferably 1 or 2 carbon atoms can be used.
- Examples of such compounds include carbon monoxide, hydrocarbons, and alcohols.
- the hydrocarbon a saturated hydrocarbon such as methane, ethane, or propane, or an unsaturated hydrocarbon such as ethylene or acetylene can be used as appropriate.
- the alcohol methanol or ethanol can be used as appropriate. These gases may be mixed with an inert gas or supplied at a low pressure.
- the carbon source is preferably a material that is a gas at 300 ° C. or higher.
- the carbon source is preferably brought into contact with the composite metal powder in a temperature atmosphere of 250 to 400 ° C.
- step 1-B shown in FIG. 1 the composite metal powder is heat treated. Thereby, nanosized deposits can be arranged on the surface of the composite metal powder.
- Step 1-B is preferably performed in an inert gas atmosphere.
- the inert gas is not particularly limited, but nitrogen gas and argon gas are preferably used.
- the carbon deposited in the low temperature carbon deposition process may become a carbon allotrope by this heat treatment.
- the carbon allotrope obtained in this step is also referred to as carbon.
- step 1-C shown in FIG. 1 a carbon source is brought into contact with the composite metal powder by the CVD method, and is present on the surface of the composite metal powder and acts as a catalyst. Carbon allotropes are grown from nano-sized precipitates. In this step, the mixed metal powder changes to brown, and further changes to black when a carbon allotrope is attached. This carbon allotrope has an effect of inhibiting the sintering of powder in the subsequent high-temperature heat treatment step. In the present invention, this step may not be performed.
- the carbon source the same carbon material as in step 1-A can be used.
- step 1-C can be performed at a higher temperature than the heat treatment step (step 1-B).
- step 2-B it may be performed at the same temperature as in step 1-B.
- This temperature varies depending on the catalytic activity of the nano-sized precipitate, and the higher the activity, the lower the temperature. Specifically, it can be carried out at a temperature of 400 ° C. to 700 ° C.
- a high-temperature heat treatment step in an inert gas atmosphere after steps 1-A to 1-C. A) can be provided. Also in FIG. 2, in the drawing, the shaded portion is treated in an ethylene gas atmosphere, and the other portions are treated in a nitrogen gas atmosphere.
- step 2-A the crystallinity of the carbon allotrope and nano-sized precipitates is improved, and the conductivity of the carbon allotrope can be improved. Furthermore, since the electroconductivity at the time of knead
- the inert gas is not particularly limited, but nitrogen gas and argon gas are preferably used.
- the high-temperature heat treatment step (step 2-A) is preferably performed at a higher temperature than steps 1-A to 1-C. More preferably, it is in the range of 650 ° C. to 950 ° C.
- the step 2-A may be performed separately from the CVD processing steps 1-A to 1-C, or may be omitted as in the step 1-C.
- nano-sized precipitates are arranged on the surface of the composite metal powder. Therefore, copper oxidation can be suppressed.
- the nano-sized precipitates are present on the surface more than the inside of the composite metal powder. This process makes it possible to exist more on the surface.
- Carbon allotrope removal step Next, at least a part of the carbon or carbon allotrope adhering to the surface of the composite metal powder is obtained from at least the composite metal powder subjected to the treatments in Steps 1-A and 1-B. By removing, a conductive filler is obtained. This step may be before paste blending described later, or after blending. The carbon or carbon allotrope may be completely removed from the surface of the composite metal powder. In that case, the electrical conductivity of the conductive filler obtained can be further enhanced.
- the removal of the carbon or carbon allotrope can be performed, for example, by mixing the composite metal powder and the binder resin until at least a part of the carbon or carbon allotrope attached to the surface of the composite metal powder is removed. it can.
- the mixing method of the composite metal powder, the binder resin, and the composite metal powder, the resin, and other additives can be mixed and then kneaded using a dissolver or a three roll mill.
- a dissolver or a three roll mill it is desirable to knead the gap between the rolls larger than the primary particle size of the filler.
- the kneading conditions are preferably carried out by kneading the mixture several times through a three-roll mill. After the particles are milled by a dry apparatus such as a jet mill, carbon can be removed and reduced by air classification.
- the mixing is carried out by mixing for 3 minutes to 1 hour after mixing the composite metal powder having the nano-sized precipitates adhered thereto and the binder resin. More preferably, it is carried out by kneading for 20 minutes to 1 hour.
- the mixing is performed by passing the composite metal powder having the nano-sized precipitate attached thereto and the binder resin, and then passing the mixture through a three-roll mill a predetermined number of times and kneading.
- the conductive filler is obtained by removing the carbon allotrope grown in the carbon allotrope generation step by (5) thermal CVD method in the (7) carbon allotrope removal step.
- the conductive filler may be obtained without performing the carbon allotrope production step by (5) thermal CVD method of the production method as an example of the conductive filler, that is, without growing the carbon allotrope.
- the temperature in the (3) low-temperature carbon deposition step is set to be equal to or lower than the activation temperature of the carbon allotrope production catalyst.
- the temperature is preferably 250 ° C to 400 ° C.
- the (4) heat treatment step it may be performed in an inert gas.
- the carbon allotrope is reduced by setting the temperatures of (3) the low temperature carbon deposition step, (4) the heat treatment step, and (5) the carbon allotrope production step by the thermal CVD method to be all lower than the activation temperature of the carbon allotrope production catalyst. You don't have to grow.
- the amount of the sintering inhibitor added is preferably 0.5 to 2.0% by weight.
- the conductive paste according to the present invention includes a conductive filler and a binder resin. It does not specifically limit as binder resin, The appropriate
- thermosetting resin As the binder resin used for the conductive paste, polyester resin, acrylic resin, butyral resin, or the like can be used.
- Thermoplastic resins such as thermoplastic polyimide can also be used.
- thermosetting resin it is desirable to use a thermosetting resin.
- thermosetting resin various epoxy resins, polyester resins, urethane resins, phenol resins, thermosetting polyimides and the like can be used as the thermosetting resin, and a curing agent may be contained.
- the conductive paste when using a thermoplastic resin, you may make the conductive paste contain the hardening
- curing agents include amine-based epoxy curing agents, acid anhydride-based epoxy curing agents, isocyanate-based curing agents, and imidazole-based curing agents. These resins may contain a solvent.
- the blending ratio of the binder resin is not particularly limited, but is preferably 10 to 35 parts by mass with respect to 100 parts by mass of the conductive filler.
- the amount of these resins added is 10 to 35 parts by mass with respect to 100 parts by mass of the conductive filler in a weight ratio after the paste is dried or cured. It is desirable. More preferably, it contains 10 to 20 parts by mass of the thermosetting resin or thermoplastic resin.
- the binder resin may be used alone or in combination of two or more.
- an inorganic filler other than a carbon material such as silica or calcium carbonate may be added to the conductive paste in order to adjust the thixotropy.
- various coupling agents may be added to improve adhesion.
- the method for producing the conductive paste is not particularly limited. In addition to the conductive filler and the binder resin, other additives such as the additive, a solvent, and a reducing agent may be mixed as appropriate. That's fine.
- the conductive paste according to the present invention can be manufactured by using a binder resin for removing carbon or carbon allotrope in the above-described conductive filler manufacturing method. In that case, the removed carbon or carbon allotrope may remain in the binder resin.
- This production method is preferable because the removal of carbon or carbon allotrope and the mixing with the binder resin can be performed in the same process, and the process can be simplified.
- the conductive paste can also be obtained by once isolating the conductive filler from the binder resin and separately mixing it with the binder resin. In that case, the viscosity may be low for the first binder resin separation.
- a binder consisting only of a solvent may be used.
- the conductive filler, the resin, and other additives can be mixed and then kneaded using a dissolver or a three-roll mill.
- a three-roll mill it is desirable that the roll gap be larger than the primary particle size of the filler and kneading. Thereby, a more uniform conductive paste can be obtained.
- the conductive paste of the present invention can be suitably used as various electrically conductive pastes used for forming conductive adhesives, conductive patterns, and the like, that is, conductive pastes.
- the said conductive filler is a structure which has arrange
- composite metal powder was prepared with the composition shown in the column of composite metal powder composition in Table 1 below.
- Table 1 the kind of additive to the copper and the content ratio of the additive to the copper in 100% by weight of the composite metal powder are shown.
- the composition of the composite metal powder constituting the composite particles A, C, D and G is 99.0% by weight of copper and 1.0% by weight of cobalt.
- the composition of the composite metal powder constituting the composite particle B is 96.3% by weight of copper and 3.7% by weight of cobalt.
- the composition of the composite metal powder constituting the composite particle E is 98.2% by weight of copper, 0.9% by weight of cobalt and 0.9% by weight of iron.
- the composition of the composite metal powder constituting the composite particle F is 99.4% by weight of copper, 0.3% by weight of cobalt, and 0.3% by weight of iron.
- composite particles that are conductive fillers A to G were created as follows. That is, 6 g of composite metal powder is put into a cylindrical quartz cell having an inner diameter of 26 mm and a length of 120 mm, and the composite metal powder is placed on the composite metal powder in a rotary kiln using a rotary cylindrical quartz tube having an inner diameter of 32 mm and a length of 700 mm. Ethylene was contacted as a carbon source to obtain composite particles A to G in which nano-sized precipitates were arranged on the surface of the composite metal powder.
- the conditions for obtaining the composite particles A to G are shown in Table 1 above.
- the added amount of Aerosil indicates the added amount with respect to 100% by weight of the composite metal powder.
- the added amount of Aerosil was set to 1.00% by weight.
- composite particles F having the composition shown in Table 1 and not subjected to the high temperature heat treatment step from the low temperature carbon adhesion step are referred to as composite particles F.
- Resitop PL-5208 manufactured by Gunei Chemical Industry Co., Ltd., which is a known resol type phenolic resin used as a resin binder for ordinary conductive paste, was used.
- the solid content of PL-5208 was 63%.
- Example 1 the obtained composite particles A and C were observed by FE-SEM (scanning electron microscope) photographs.
- the field emission scanning electron microscope used was S-4800 / hitachi.
- Samples were prepared from the cured product obtained by curing the paste obtained in Example 2 by FIB, and STEM-HAADF images, BF images, and EDS mapping images were obtained by FE-TEM / EDS.
- JEM-ARM200F / JOEL was used as the transmission electron microscope.
- FIG. 3 is an FE-SEM photograph at a magnification of 20000 times of a portion where the carbon allotrope of the composite particle A obtained in Example 1 is not generated.
- FIGS. 4 and 5 are FE-SEM photographs at a magnification of 80000 times and a magnification of 100000 times, respectively, of the part where the carbon allotrope of the composite particle C obtained in Example 3 is not generated.
- the composite particle surface has black and white contrast, and the white part is dot-like. It can be seen that oxygen and carbon light elements are present in the form of dots on the surface because of the contrast white portions.
- the composite particle surface has black and white contrast and is dendritic. Since there is a white portion with contrast, it can be seen that light elements such as oxygen and carbon are present on the surface in the form of dendrites.
- FIG. 6 is a TEM photograph of the composite particles in the paste obtained in Example 2, and the scale bar of the scale in the figure is 25 nm.
- the surface of the composite particle has a nano-sized layer of 10 to 20 nm and a nano-sized particle of 10 to 20 nm composed of cobalt, oxygen and a small amount of carbon. I understand.
- FIG. 11 is a STEM-BF image of the composite particle B obtained in Example 2, and the scale bar of the scale in the figure is 5 nm.
- FIG. 11 shows that there is crystallinity near the surface of the composite particle. Moreover, it turns out that the composition layer different from the inside is formed.
- the specific resistance was measured by applying a conductive paste on an epoxy substrate to a width of 2 mm, a length of 100 mm and a thickness of 40 to 100 ⁇ m, thermosetting for 30 minutes, and then using a four-terminal method with a low resistance digital multimeter.
- R is the resistance value of the digital multimeter
- S is the cross-sectional area of the coating film made of a conductive paste
- L is the distance between the electrodes.
- the thermosetting was performed at 170 ° C. in an atmosphere containing oxygen.
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Abstract
Description
本発明に係る伝導性フィラーの他の特定の局面では、上記銅粉の平均粒径が、1.0μm~25μmの範囲にある。球状粉の場合は、上記銅粉の平均粒径が、1.0μm~10μmの範囲にあることが好ましい。またフレーク粉の場合は、上記銅粉の平均粒径が、3.0μm~25μmの範囲にあることが好ましい。フレーク粉は平均粒径が、1.0μm~10μmの範囲にある球状粉を扁平加工することにより作製される。
本発明に係る伝導性フィラーは、好ましくは、上記複合粒子100重量%中、上記遷移金属又は遷移金属の化合物の含有量が、0.1~6.0重量%の範囲にある。
なお、すべてのナノサイズの析出物を透過型電子顕微鏡で観察することは難しいが、実際に透過型電子顕微鏡により粒径又は膜厚が200nm以下のナノサイズの析出物が確認できている。
本発明に係る伝導性フィラーの一例としての製造方法では、銅と、ナノサイズの析出物の材料となる周期表第8族~第10族に属する少なくとも1種の遷移金属とを含む複合金属粉を用意する工程と、上記複合金属粉の表面に炭素源を接触させることにより、上記複合金属粉の表面に炭素を付着させる工程と、上記複合金属粉に熱処理を施すことにより、上記複合金属粉の表面に上記ナノサイズの析出物を析出させる工程と、上記複合金属粉の表面に付着した炭素の少なくとも一部を除去することにより、伝導性フィラーを得る工程とを備える。
上記複合金属粉を用意する方法としては、特に限定されないが、前述したようにアトマイズ法により複合金属粉を得ることが望ましい。この場合、容易に銅に添加物を加えた複合金属粉を作ることができる。
後述する工程1-Aの前処理として、複合金属粉にさらに小さな微粒子である焼結阻害剤を添加することが望ましい。これにより、後述する熱処理工程(工程1-B)における複合金属粉同士の凝集をより一層効果的に防止することができる。そのような微粒子としてはアエロジル、カーボンブラック、ケッチェンブラックなどが挙げられる。微粒子の添加量は複合金属粉に対し、0.05~2.0重量%であることが望ましい。より好ましくは、0.1重量%~2.0重量%である。この後の工程が、セッターに粉体を敷き詰めて処理する方法であって、敷き詰める粉体の膜厚が粒子の径と同程度に薄い場合は、この工程は省かれる場合がある。
以下、図1を参照して、詳細を説明する。図中、斜線部分では、エチレンガス雰囲気下において、その他の部分については、窒素ガス雰囲気下で処理を行っている。
次に図1に示す工程1-Bにおいて、複合金属粉に熱処理を施す。これにより、上記複合金属粉の表面にナノサイズの析出物を配置することができる。
次に、図1に示す工程1-Cにおいて、CVD法により複合金属粉に炭素源を接触させ、複合金属粉の表面に存在し、触媒として作用するナノサイズの析出物から炭素同素体を成長させる。この工程においては、合金属粉は茶色に変化する、さらに炭素同素体を付着させると黒色へと変化する。この炭素同素体は、後の高温熱処理工程で粉体の焼結阻害効果がある。なお、本発明においては、本工程を行わなくともよい。炭素源としては、工程1-Aと同じ炭素材料を用いることができる。図1に示すように、工程1-Cは、熱処理工程(工程1-B)より、高い温度下で行うことができる。もっとも、図2に示すように、工程1-Bと同じ温度で行ってもよい。この温度はナノサイズの析出物の触媒活性により異なり、活性の高いものほど低温で行うことができる。具体的には、400℃~700℃の温度下で行うことができる。
さらに、本発明においては、図2に示すヒートプロファイルの他の例のように、工程1-A~1-Cの後に不活性ガス雰囲気中で高温熱処理工程(工程2-A)を設けることができる。図2においても、図中、斜線部分では、エチレンガス雰囲気下において、その他の部分については、窒素ガス雰囲気下で処理を行っている。
次に、少なくとも上記工程1-A及び工程1-Bの処理を施した複合金属粉から、複合金属粉の表面に付着している炭素又は炭素同素体の少なくとも一部を取り除くことで、伝導性フィラーを得る。本工程は、後述するペースト配合前であってもよいし、配合後であってもよい。なお、上記炭素又は炭素同素体は、複合金属粉の表面から完全に取り除いてもよい。その場合には得られる伝導性フィラーの電気伝導性をより一層高めることができる。
本発明に係る伝導性ペーストは、伝導性フィラーと、バインダー樹脂とを含む。バインダー樹脂としては、特に限定されず、従来より導電性ペーストや熱伝導性ペーストに用いられる適宜のバインダー樹脂を用いることができる。このような樹脂としては、エポキシ樹脂、ポリエステル樹脂、ウレタン樹脂、フェノール樹脂及びイミド樹脂からなる群から選択された少なくとも1種を好適に用いることができる。これらの樹脂や溶剤を用いた場合には、熱硬化型や熱乾燥型のペーストとすることができる。もっとも、上記バインダー樹脂は、導電性ペーストや熱伝導性ペースト等の利用目的に応じて適宜選択すればよい。
高圧水アトマイズ法により、銅と、表1に示す銅への添加物とからなる複合金属粉を製造し、風力分級機により平均粒径3μmの複合金属粉に分級した。得られた複合金属粉の平均粒径は、2.95μm~3.15μmであった。
上記のようにして得られた複合金属粉のいずれかを用い、アエロジルを混合し分散した後に、伝導性フィラーである複合粒子A~Gを以下の要領で作成した。 すなわち、内径26mm及び長さ120mmの円筒状の石英セル中に、6gの複合金属粉を投入し、内径32mm及び長さ700mmのロータリー円筒型石英管を用いたロータリーキルン内において、複合金属粉上に炭素源としてエチレンを接触させ、複合金属粉表面にナノサイズの析出物が配置された複合粒子A~Gを得た。
上記のようにして得た複合粒子A~Gのいずれかと、バインダー樹脂としてのフェノール樹脂と、溶剤としてのBCA(ブチルセロソルブアセテート)又はエトキシエトキシエタノールとを下記の表2に示す割合で混合した。なお、混合は、ペイント用のガラスミュラー(glass muller)を用いて、表2に示す混練時間をかけて混練分散した。これによって、表2に示す実施例2,4~11及び比較例1の導電性ペーストを得た。なお、比較例1では、低温炭素付着工程から高温熱処理工程を施さなかった複合粒子Fと、フェノール樹脂及びBCAとを混合した。
(評価方法)
微細構造解析:
実施例1及び実施例3では、それぞれ得られた複合粒子A,Cを、FE-SEM(走査型電子顕微鏡)写真により観察した。電界放出形走査電子顕微鏡はS-4800/hitachiを用いた。
比抵抗は、導電性ペーストをエポキシ基板上に幅2mm、長さ100mm、厚さ40~100μmに塗布し、30分間熱硬化させた後、低抵抗デジタルマルチメーターで四端子法を用い測定した。比抵抗は、比抵抗=R×S/L(Ω・cm)で求められる。Rはデジタルマルチメーターの抵抗値であり、Sは導電性ペーストからなる塗膜の断面積であり、Lは電極間の距離である。なお、熱硬化については、酸素を含む大気中で170℃の温度で行った。
Claims (23)
- 銅粉と、前記銅粉の表面に配置されており、かつ周期表第8族~第10族に属する少なくとも1種の遷移金属又は遷移金属の化合物からなるナノサイズの析出物とを含む、複合粒子である、伝導性フィラー。
- 前記ナノサイズの析出物が、前記銅粉の内部にも存在している、請求項1に記載の伝導性フィラー。
- 前記銅粉の平均粒径が、1.0μm~25μmの範囲にある、請求項1又は2に記載の伝導性フィラー。
- 前記銅粉の表面に、前記ナノサイズの析出物の膜が形成されており、前記ナノサイズの析出物の膜の膜厚が、100nm以下である、請求項1~3のいずれか1項に記載の伝導性フィラー。
- 前記ナノサイズの析出物が、粒子であり、前記ナノサイズの析出物の粒子の粒径が、100nm以下である、請求項1~3のいずれか1項に記載の伝導性フィラー。
- 前記複合粒子100重量%中、前記遷移金属又は遷移金属の化合物の含有量が、0.1~6.0重量%の範囲にある、請求項1~5のいずれか1項に記載の伝導性フィラー。
- 前記遷移金属が、コバルトである、請求項1~6のいずれか1項に記載の伝導性フィラー。
- 前記遷移金属の化合物が、前記遷移金属の酸化物と、前記遷移金属の炭化物のうち少なくとも一方である、請求項1~6のいずれか1項に記載の伝導性フィラー。
- 前記遷移金属の化合物が、酸化コバルトと、コバルトカーバイドのうち少なくとも一方である、請求項8に記載の伝導性フィラー。
- 前記銅粉が、純銅からなる、請求項1~9のいずれか1項に記載の伝導性フィラー。
- 請求項1~10のいずれか1項に記載の伝導性フィラーと、バインダー樹脂とを含む、伝導性ペースト。
- 前記バインダー樹脂が、エポキシ樹脂、ポリエステル樹脂、ウレタン樹脂、フェノール樹脂及びイミド樹脂からなる群から選択された少なくとも1種の樹脂である、請求項11に記載の伝導性ペースト。
- 前記伝導性フィラー100質量部に対し、前記バインダー樹脂を10~35質量部含む、請求項11又は12に記載の伝導性ペースト。
- 前記伝導性ペーストが電気伝導性ペーストである、請求項11~13のいずれか1項に記載の伝導性ペースト。
- 前記伝導性ペーストが熱伝導性ペーストである、請求項11~13のいずれか1項に記載の伝導性ペースト。
- 請求項1~10のいずれか1項に記載の伝導性フィラーの製造方法であって、
銅と、ナノサイズの析出物の材料となる周期表第8族~第10族に属する少なくとも1種の遷移金属又は遷移金属の化合物とを含む、複合金属粉を用意する工程と、
前記複合金属粉の表面に炭素源を接触させることにより、前記複合金属粉の表面に炭素を付着させる工程と、
前記複合金属粉に熱処理を施すことにより、前記複合金属粉の表面にナノサイズの析出物を析出させる工程と、
前記複合金属粉の表面に付着した炭素の少なくとも一部を除去することにより、複合粒子である伝導性フィラーを得る工程とを備える、伝導性フィラーの製造方法。 - 前記複合金属粉を用意する工程が、アトマイズ法により行われる、請求項16に記載の伝導性フィラーの製造方法。
- 前記複合金属粉に熱処理を施す工程の前に、焼結阻害剤を添加し混合する工程をさらに備える、請求項16又は17に記載の伝導性フィラーの製造方法。
- 前記複合金属粉の表面に炭素源を接触させる工程が、250~400℃で複合金属粉を炭素含有ガスに接触させることにより行われる、請求項16~18のいずれか1項に記載の伝導性フィラーの製造方法。
- 前記熱処理が、不活性ガス雰囲気下、400℃~700℃の温度で行われる、請求項16~19のいずれか1項に記載の伝導性フィラーの製造方法。
- 前記複合金属粉の表面に付着した炭素の少なくとも一部を除去することにより伝導性フィラーを得る工程が、前記複合金属粉と、バインダー樹脂とを、前記複合金属粉の表面に付着した炭素の少なくとも一部が取り除かれるまで混合することにより行われる、請求項16~20のいずれか1項に記載の伝導性フィラーの製造方法。
- 前記複合金属粉と、バインダー樹脂との混合が、20分間~1時間、混練することにより行われる、請求項21に記載の伝導性フィラーの製造方法。
- 前記複合金属粉に熱処理を施す工程の後に、CVD法により炭素源を接触させ、前記複合金属粉の表面から炭素同素体を成長させる工程と、前記表面から炭素同素体を成長させた複合金属粉に、不活性ガス雰囲気下、650℃~950℃の温度で、熱処理を行う、高温熱処理工程をさらに備え、
前記複合金属粉の表面に付着した炭素と共に前記炭素同素体を除去する、請求項16~22のいずれか1項に記載の伝導性フィラーの製造方法。
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KR102694708B1 (ko) * | 2021-08-20 | 2024-08-13 | 삼성전기주식회사 | 도전성 페이스트 및 이를 이용한 적층형 세라믹 부품 |
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