WO2010004852A1 - 導電性ペースト用銅粉及び導電性ペースト - Google Patents
導電性ペースト用銅粉及び導電性ペースト Download PDFInfo
- Publication number
- WO2010004852A1 WO2010004852A1 PCT/JP2009/061241 JP2009061241W WO2010004852A1 WO 2010004852 A1 WO2010004852 A1 WO 2010004852A1 JP 2009061241 W JP2009061241 W JP 2009061241W WO 2010004852 A1 WO2010004852 A1 WO 2010004852A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- copper powder
- conductive paste
- atm
- particle
- copper
- Prior art date
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 239000002245 particle Substances 0.000 claims abstract description 98
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 37
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 9
- 239000010703 silicon Substances 0.000 claims abstract description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011574 phosphorus Substances 0.000 claims abstract description 6
- 229910052709 silver Inorganic materials 0.000 claims abstract description 6
- 239000004332 silver Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 44
- 229910052738 indium Inorganic materials 0.000 claims description 36
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 6
- 238000000889 atomisation Methods 0.000 abstract description 4
- 230000003647 oxidation Effects 0.000 description 33
- 238000007254 oxidation reaction Methods 0.000 description 33
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 18
- 239000001301 oxygen Substances 0.000 description 18
- 229910052760 oxygen Inorganic materials 0.000 description 18
- 239000010949 copper Substances 0.000 description 17
- 238000009826 distribution Methods 0.000 description 17
- 229910052802 copper Inorganic materials 0.000 description 16
- 230000009467 reduction Effects 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- 239000007789 gas Substances 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 10
- 239000004020 conductor Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 239000000654 additive Substances 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 239000003985 ceramic capacitor Substances 0.000 description 5
- 239000010419 fine particle Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000009689 gas atomisation Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000007650 screen-printing Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000009692 water atomization Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- RIRXDDRGHVUXNJ-UHFFFAOYSA-N [Cu].[P] Chemical compound [Cu].[P] RIRXDDRGHVUXNJ-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- 239000011162 core material Substances 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/10—Alloys based on copper with silicon as the next major constituent
-
- 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
- H01B1/026—Alloys based on copper
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/228—Terminals
- H01G4/232—Terminals electrically connecting two or more layers of a stacked or rolled capacitor
- H01G4/2325—Terminals electrically connecting two or more layers of a stacked or rolled capacitor characterised by the material of the terminals
-
- 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
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/08—Inorganic dielectrics
- H01G4/12—Ceramic dielectrics
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/30—Stacked capacitors
-
- 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
Definitions
- the present invention relates to a copper powder for conductive paste and a conductive paste using the same.
- the present invention particularly relates to copper powder suitable for conductive pastes for forming various electrical contact members for forming conductive circuits by screen printing additive method and forming external electrodes of multilayer ceramic capacitors, and conductive paste using the same.
- conductive paste using the same.
- Copper powder has been used as a conductive material for conductive pastes for forming various electrical contact members such as for forming conductive circuits by screen printing additive method and for forming external electrodes of multilayer ceramic capacitors because of its ease of handling. Widely used.
- the conductive paste can be obtained, for example, by blending and kneading a resin such as an epoxy resin and various additives such as a curing agent thereof with copper powder.
- the copper powder used may be a wet reduction method in which a copper salt-containing solution or the like is precipitated with a reducing agent, a vapor phase reduction method in which the copper salt is heated and vaporized and reduced in the gas phase, or a molten copper metal is not used. It can be produced by an atomizing method or the like in which it is rapidly cooled with a refrigerant such as active gas or water to form a powder.
- the atomizing method has an advantage that the residual concentration of impurities in the obtained copper powder can be reduced as compared with a wet reduction method that is generally widely used. Have. Moreover, it has the advantage that the pore from the surface of the particle
- Copper powder is suitable for the conductive material of the conductive paste because of its high conductivity.
- the particle size becomes finer, it has a drawback of inferior oxidation resistance.
- a measure of coating the particle surface with silver having oxidation resistance (Patent Document 1), a measure of coating with an inorganic oxide (Patent Document 2), and the like have been adopted.
- Patent Documents 1 and 2 depend on the coating technique, a large amount of components that impair the conductivity are required as components other than copper. Not only that, there arises a problem that the coating is peeled off from the copper particles as the core material. Also, in reducing the variation in shape and particle size, it is desired that the constituent particles are uniformly homogeneous and the concentration of oxygen contained is low, and such copper powder is still satisfactory. There is nothing to be found.
- the present inventors have found that the above-mentioned problems can be solved when a specific amount of Si and In is contained in the copper powder particles, and the present invention has been completed.
- the copper powder for conductive paste of the present invention is characterized by containing 0.1 atm% to 10 atm% of Si and 0.1 atm% to 10 atm% of In inside the particles.
- the other aspect of this invention is the electrically conductive paste containing the said copper powder for electrically conductive pastes.
- the copper powder for conductive paste of the present invention includes a specific component species other than copper inside the particle, so that the oxidation resistance is remarkably excellent despite the fine particle size without impairing the conductivity. It is a thing.
- the copper powder for conductive paste of the present invention can be used for forming a conductive circuit by the screen printing additive method, As a conductive material of a conductive paste for forming various electrical contact members such as for forming electrodes, it can be used extremely well.
- the copper powder for conductive paste according to the present invention is characterized by containing 0.1 atm% to 10 atm% Si and 0.1 atm% to 10 atm% In inside the particles.
- Copper powder disclosed in typical prior arts including the above-mentioned patent documents that is, various substances or compounds that are inferior in conductivity to copper are coated or adhered to the surface of the copper powder particles as the core material. Copper powder is effective in improving oxidation resistance. However, such copper powder does not have the characteristics required by the present invention, that is, the characteristics that the particle size is fine and the oxidation resistance is excellent without impairing conductivity.
- the Si and In components contained in the copper powder for conductive paste according to the present invention are distributed in the metal phase inside the particles. Particularly preferably, these components are present in the interior of the particle, but are not exposed on the surface of the particle and are concentrated near the particle surface.
- Si and In components are in such a distribution state, in addition to improving the oxidation resistance, there is an advantageous effect that excellent conductivity can be maintained.
- the above distribution state will be described in detail.
- the above-mentioned “concentrated near the particle surface” means that Si and In components are not present on the particle surface and a predetermined depth from the particle surface. This means that it is unevenly distributed.
- the Si and In components are concentrated near the particle surface, the distribution state of the Si component and the distribution state of the In component do not need to match.
- the Si and In components are not substantially present not only in the particle surface but also in the central region of the particle from the viewpoint of further improving the oxidation resistance and further maintaining the conductivity.
- the distribution state of Si and In components in the particle is determined by, for example, cutting the surface of the particle by argon ion sputtering or the like, and performing elemental analysis on the surface generated by cutting or elemental analysis of the cut surface by cutting the particle. It can be measured by the technique of performing.
- the oxidation resistance especially at 600 ° C. to 800 ° C. can be drastically improved.
- an oxidation resistance index of ⁇ (TG / SSA) described later can be realized at 20% / m 2 / cm 3 or less at a temperature level of 600 ° C.
- Such advantageous effects cannot be obtained with a copper powder that individually contains an Si component or an In component.
- the Si content is 0.1 atm% to 10 atm%, preferably 0.5 atm% to 5 atm%, more preferably 1 atm% to 3 atm%. If this content is less than 0.1 atm%, the effect sought by the present invention cannot be expected. When it exceeds 10 atm%, not only the conductivity is impaired, but also an effect commensurate with the addition cannot be obtained.
- the In content is 0.1 atm% to 10 atm%, preferably 0.5 atm% to 5 atm%, and more preferably 1 atm% to 3 atm%. If this content is less than 0.1 atm%, the effect sought by the present invention cannot be expected. If it exceeds 10 atm%, the conductivity is impaired and not only an effect commensurate with the addition cannot be obtained, but also the production cost is uneconomical.
- the copper powder for conductive paste according to the present invention preferably has an Ag content of 0.1 atm% to 10 atm%, more preferably 0.5 atm% to 5 atm%, most preferably 1 atm% to the inside of the particle. Contains 3 atm%.
- Ag is contained within this specific amount, the conductivity can be further improved while maintaining the oxidation resistance of the copper powder for conductive paste. Moreover, manufacturing costs can be reduced.
- Ag is present in the interior of the particle, but is not exposed on the surface of the particle and is concentrated near the particle surface.
- Ag is preferably not substantially present not only on the surface of the particle but also in the central region of the particle from the viewpoint of further improving the oxidation resistance and further maintaining the conductivity.
- the state of Ag distribution in the particles can be measured by the same method as the method for measuring the state of Si and In component distribution described above. Note that the distribution state of Ag does not have to coincide with the distribution state of Si and In.
- the copper powder for conductive paste according to the present invention preferably contains P (phosphorus) inside the particles in addition to Si and In, preferably 0.01 atm% to 0.5 atm%, more preferably 0.05 atm% to 0.3 atm%. contains.
- P phosphorus
- the copper paste for conductive paste is remarkably excellent in oxidation resistance and excellent in conductivity even though the particle size is fine. Furthermore, the characteristics that the variation in the shape and particle size of the particles is small and the concentration of the contained oxygen is low are improved.
- the coexistence of Si and In is particularly preferable even if the concentration of P is high because the effect of improving oxidation resistance is not inhibited.
- P is present inside the particle, it is not exposed on the surface of the particle and is concentrated near the particle surface.
- P is not substantially present not only in the particle surface but also in the central region of the particle from the viewpoint of further improving the oxidation resistance and further maintaining the conductivity.
- the state of distribution of P in the particles can be measured by a method similar to the method for measuring the state of distribution of Si and In components described above. Note that the distribution state of Ag does not have to coincide with the distribution state of Si and In.
- the copper powder for conductive paste according to the present invention contains any of Si, In, Ag, and P, the variation in particle shape and particle size is small, and the oxidation resistance is drastically despite the fine particle size. In addition to being excellent, the conductivity is further improved.
- the ratio of Si, In, Ag and P contained therein is measured by the method described in the examples described later.
- the copper powder for conductive paste according to the present invention preferably has Si / In (atm ratio) of 0.5 to 5, more preferably 1 to 4.
- Si / In atm ratio
- the particle size can be made fine and the oxidation resistance can be improved without dropping the conductivity or increasing the production cost. Variations in particle shape and particle size can be reduced, and the feature that the concentration of oxygen contained can be reduced can be maintained in a well-balanced manner.
- the Si / P (atm ratio) is preferably 4 to 200, more preferably 10 to 100.
- the ratio of Si / P is within such a range, the particle size can be made fine, oxidation resistance can be improved, conductivity can be increased, and variation in particle shape and particle size can be reduced. It is easy to balance the feature that the concentration of oxygen contained can be reduced.
- the In / P (atm ratio) is preferably 4 to 200, more preferably 10 to 100.
- the ratio of In / P is within such a range, the particle size can be made fine, oxidation resistance can be improved, conductivity can be increased, and variation in particle shape and particle size can be reduced. It is easy to balance the feature that the concentration of oxygen contained can be reduced.
- the copper powder for conductive paste according to the present invention is produced by a wet reduction method, the above-described advantageous effects can be expected to some extent.
- the copper powder for conductive paste according to the present invention was manufactured by the atomizing method. It is preferable.
- the atomization method includes the gas atomization method and the water atomization method.
- the gas atomization method may be selected if the particle shape is to be leveled.
- the water atomization method may be selected to reduce the size of the particles.
- the copper powder for electrically conductive paste which concerns on this invention is manufactured by the high voltage
- the copper powder obtained by the high-pressure atomizing method is preferable because the particles become more even or finer.
- the high pressure atomizing method is a method of atomizing with a water pressure of about 50 MPa to 150 MPa in the water atomizing method, and a method of atomizing with a gas pressure of about 1.5 MPa to 3 MPa in the gas atomizing method.
- the copper powder for conductive paste according to the present invention further includes Ni, Al, Ti, Fe, Co, Cr, Mg, Mn, Mo, W, Ta, Zr, Nb, B, Ge, Sn, Zn, Bi, etc. Of these, at least one elemental component may be contained. By including these element components, various properties required for the conductive paste can be improved. Such characteristics include, for example, improving the sinterability by lowering the melting point of the copper powder.
- the amount of these elements added to copper is appropriately set based on the conductive characteristics according to the type of element to be added, other various characteristics, and the like. The addition amount is usually about 0.001% by mass to 2% by mass.
- the copper powder for conductive paste according to the present invention is not particularly limited in the shape of the particles, and can be selected according to the application.
- shapes such as a granular shape, a plate shape, a flake shape, a dendrite shape, a needle shape, and a rod shape can be employed.
- the copper powder for a conductive paste is granular in order to improve dispersibility in the paste component.
- Granular means a shape having an aspect ratio (a value obtained by dividing an average major axis by an average minor axis) of about 1 to 1.25.
- a shape having an aspect ratio of about 1 to 1.1 is called a spherical shape.
- a state where the shapes are not aligned is called an indefinite shape.
- the granular copper powder has little entanglement between particles. Therefore, it is very preferable to use granular copper powder as the conductive material of the conductive paste because the dispersibility in the paste is improved.
- the copper powder for conductive paste according to the present invention has a variation in particle size distribution. This is very preferable because the dispersibility of the conductive paste in the paste when used as a conductive material or the like can be improved.
- SD and D 50 can be measured by, for example, a laser diffraction / scattering particle size distribution measuring apparatus.
- SD is 10 to 20 ⁇ m, particularly 13 to 18 ⁇ m, and D 50 is 20 to 30 ⁇ m. Is preferred.
- the copper powder for conductive paste according to the present invention has a primary particle number average particle size of 0.01 ⁇ m to 50 ⁇ m, which makes it suitable for a conductive material of a conductive paste for forming a fine conductor circuit.
- the primary particle number average particle diameter can be measured, for example, by image analysis of a scanning electron microscope observation photograph.
- the initial oxygen concentration (immediately after production) is set to 30 ppm to 2500 ppm, so that the conductivity can be reliably ensured. This is preferable.
- the oxygen concentration is measured by the method described in the examples described later.
- the copper powder for conductive paste according to the present invention has a difference of [weight change rate (TG (%)) / specific surface area (SSA)] at 250 ° C. and 800 ° C. using a thermogravimetric / differential thermal analyzer (hereinafter referred to as ⁇ (Referred to as (TG / SSA)) is preferably 1% / m 2 / cm 3 to 60% / m 2 / cm 3 , more preferably 1% / m 2 / cm 3 to 25% / m 2 / cm 3 It is.
- the weight change rate TG (%) is a value based on the weight of the copper powder at 30 ° C.
- ⁇ (TG / SSA) is defined by (TG / SSA) 800 ⁇ (TG / SSA) 250 .
- the weight change rate TG and the specific surface area SSA are measured by the method described in Examples described later.
- the oxidation resistance of the copper powder can be evaluated.
- the temperature range of 250 ° C. to 800 ° C. is a heating temperature range when a main conductive paste such as a conductive paste for firing an external electrode of a ceramic capacitor is used. Therefore, it is very important that the copper powder has oxidation resistance in this region.
- this ⁇ (TG / SSA) is in the above preferred range, the oxidation resistance of the copper powder is sufficiently exhibited, and high conductivity can be ensured.
- the value of (DELTA) (TG / SSA) of copper powder can be made into said preferable range by setting the quantity of Si and In contained in particle
- the copper powder for conductive paste of the present invention is a predetermined atomizing method after adding a predetermined amount of molten Si to the Si component in the form of a mother alloy or a compound or the In component in the form of an ingot or shot metal. It can be manufactured by pulverizing with.
- Si and In added to the molten copper or copper alloy capture oxygen in the copper particles and suppress oxidation within a range that does not impair the conductivity of the copper particles. Is done.
- the conductivity can be further improved while ensuring the oxidation resistance of the copper powder.
- the addition of the P component may be performed by adding a predetermined amount of the P component to the molten copper in the form of a mother alloy or a compound, as with the Si component.
- the yield of the contents of Si, In and P may be low, so that the net amount in the target copper powder is less than that of Si and In. In the case of 1, it is necessary to add 1 to 10 times the amount, and in the case of P, it is necessary to add 1 to 100 times the amount.
- the target copper powder can be successfully produced.
- the copper powder obtained by the atomizing method may be reduced.
- This reduction treatment it is possible to further reduce the oxygen concentration on the surface of the copper powder which is easily oxidized.
- the reduction treatment is preferably gas reduction from the viewpoint of workability.
- the gas for reduction treatment For example, a reducing gas such as hydrogen gas, ammonia gas, or butane gas can be used.
- the above reduction treatment is preferably performed at a temperature of 150 ° C. to 300 ° C., more preferably at a temperature of 170 ° C. to 210 ° C.
- the reason for this is that if the temperature of the reduction treatment is within the above range, reduction of the reduction treatment due to the reduction of the reduction rate can be prevented, and the aggregation and sintering of copper powder can occur. This is because it can be suppressed.
- a reduction treatment temperature of 170 ° C. to 210 ° C. is more preferable because aggregation of copper powder and sintering can be reliably suppressed while efficiently reducing the oxygen concentration.
- the classification can be easily performed by separating coarse particles and fine particles from the copper powder using an appropriate classifier so that the target particle size is at the center.
- classification is preferably performed so that the coefficient of variation (SD / D 50 ) described above is 0.2 to 0.6.
- the copper powder for conductive paste of the present invention can be obtained by blending various additives such as a resin such as an epoxy resin and its curing agent into the copper powder thus obtained and performing operations such as kneading.
- the contained conductive paste is manufactured.
- the composition of such a conductive paste is well known in the art and need not be specifically described.
- this conductive paste although the copper powder contained therein has a fine particle size, the oxidation resistance and conductivity are balanced, and there is little variation in particle shape and is contained. The oxygen concentration is low. Therefore, this conductive paste is very suitably used for forming various electrical contact members such as forming a conductor circuit by a screen printing additive method and forming an external electrode of a multilayer ceramic capacitor.
- the copper powder for conductive paste of the present invention is used for internal electrodes of multilayer ceramic capacitors, chip components such as inductors and resistors, single plate capacitor electrodes, tantalum capacitor electrodes, resin multilayer substrates, ceramic (LTCC) multilayer substrates, flexible Printed circuit boards (FPC), antenna switch modules, modules such as PA modules and high-frequency active filters, PDP front and back plates, electromagnetic shielding films for PDP color filters, crystalline solar cell surface electrodes and rear lead electrodes, conductive adhesives It can also be used for EMI shield, RF-ID, membrane switch such as PC keyboard, anisotropic conductive film (ACF / ACP), etc.
- chip components such as inductors and resistors, single plate capacitor electrodes, tantalum capacitor electrodes, resin multilayer substrates, ceramic (LTCC) multilayer substrates, flexible Printed circuit boards (FPC), antenna switch modules, modules such as PA modules and high-frequency active filters, PDP front and back plates, electromagnetic shielding films for PDP color filters, crystalline solar cell surface electrode
- Example 1 The chamber and raw material melting chamber of a gas atomizer (Nisshin Giken Co., Ltd., NEVA-GP2 type) were filled with nitrogen gas, and then the raw material was heated and dissolved in a carbon crucible installed in the melting chamber to obtain a melt. Specifically, 1.77 g of metal silicon (NIKSIL manufactured by Nippon Metal Chemical Co., Ltd.) and 7.20 g of metal indium were added to the molten metal in which electrolytic copper was melted to obtain 800 g of molten metal. Stir and mix.
- a gas atomizer NiKSIL manufactured by Nippon Metal Chemical Co., Ltd.
- the molten metal was sprayed from a nozzle having a diameter of ⁇ 1.5 mm at 1250 ° C. and 3.0 MPa to obtain copper powder containing silicon and indium inside the particles. Thereafter, the obtained copper powder was sieved with a 53 ⁇ m test sieve, and the product under the sieve was used as the final copper powder.
- the characteristics of the obtained copper powder are shown in Table 2. In this copper powder, Si and In were not exposed on the surface of the particle and were unevenly distributed in the vicinity of the particle surface.
- Example 2 to 14 In addition to metallic silicon and metallic indium, silver bullion and copper-phosphorus mother alloy (phosphorus grade 15 mass%) were added as shown in Table 1, and the same operation as in Example 1 was performed to obtain copper powder. Obtained.
- Example 8 A copper powder was obtained in the same manner as in Example 1 except that the addition amounts of metallic silicon, metallic indium, and copper-phosphorus mother alloy (phosphorus grade 15% by mass) were added as shown in Table 1.
- TG / DTA differential thermothermal gravimetric simultaneous measurement apparatus
- SII TG / DTA6300 high temperature type
- Air flow rate 200 mL / Minutes
- specific surface area was determined from the particle size distribution measured with a particle size measuring device (manufactured by Nikkiso, Microtrac MT-3000 type).
- TG / SSA was calculated arithmetically from both measured values. The results are shown in Table 3. The table also shows the value of ⁇ (TG / SSA), which is the difference between TG / SSA at 250 ° C. and TG / SSA at 800 ° C.
- the copper powders of the examples are excellent in oxidation resistance in the temperature range of 250 to 800 ° C. Particularly, in the temperature range of 600 to 800 ° C., the copper powder of the example (copper powder containing both Si and In inside the particle) is the copper powder of the comparative example (only one of Si or In is contained inside the particle). Compared with the copper powder contained in 1), the oxidation resistance is remarkably superior.
- the copper powder of the example when the copper powder of the example is kept for a long time in an environment that is easy to oxidize, the deterioration of oxidation resistance over time is significantly suppressed as compared with the copper powder of the comparative example.
- the copper powders of Comparative Examples 1, 2, 4, and 5 have a relatively high total content of Si and In of about 2 atm%, whereas the copper powders of the examples contain the total content of Si and In. It can be seen that although the amount is relatively low, about 1 atm%, the deterioration of oxidation resistance with time is suppressed.
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- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Physics & Mathematics (AREA)
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Abstract
Description
(実施例1)
ガスアトマイズ装置(日新技研(株)製、NEVA-GP2型)のチャンバ及び原料溶解室内を窒素ガスで充填した後、溶解室内に設置されたカーボン坩堝で原料を加熱溶解して溶融物とした。具体的には、電気銅を溶解した溶湯中に、金属ケイ素(日本金属化学工業(株)製NIKSIL)を1.77g、及び金属インジウムを7.20g添加して、800gの溶湯とし、充分に攪拌混合した。その後、溶湯を口径φ1.5mmのノズルから1250℃、3.0MPaで噴霧して、ケイ素及びインジウムを粒子内部に含む銅粉を得た。しかる後、得られた銅粉を、53μmテストシーブで篩い、篩下品を最終的な銅粉とした。得られた銅粉の特徴を表2に示す。この銅粉においては、Si及びInが粒子の表面に露出しておらず、かつ粒子表面の近傍に偏在していた。
金属ケイ素、金属インジウムの他、銀地金、及び銅-りん母合金(りん品位15質量%)を表1に示すように添加した以外は実施例1と同様の操作を行って、銅粉を得た。
金属ケイ素、金属インジウム、及び銅-りん母合金(りん品位15質量%)の添加量を表1に示すように添加した以外は実施例1と同様の操作を行って、銅粉を得た。
試料を酸で溶解し、溶液をICPによって分析した。その結果を表2に示す。
(2)酸素濃度
酸素・窒素分析装置(堀場製作所株式会社製「EMGA-520(型番)」)によって分析した。その結果を表2に示す。また、耐酸化性の経時的な劣化を評価するために、山陽精工製のSK-8000を用いて、Air流量8L/分、昇温速度10℃/分で200℃まで昇温し、その後同温度で1時間保持した試料の酸素濃度も測定した。その結果を表5に示す。
(3)Δ(TG/SSA)
40℃~800℃でのTg(%)を、示差熱熱重量同時測定装置(TG/DTA)(SII製、TG/DTA6300高温型)(昇温速度:10℃/分、Air流量:200mL/分)で測定した。一方、比表面積は、粒度測定装置(日機装製、マイクロトラックMT-3000型)で測定した粒度分布から求めた。両者の測定値からTG/SSAを算術的に求めた。その結果を表3に示す。同表には、250℃でのTG/SSAと800℃でのTG/SSAとの差であるΔ(TG/SSA)の値も記載されている。更に、各温度におけるTG/SSAを、比較例8の純銅粉のTG/SSA(表4中[TG/SSA]Cuと記載)で除した値も求めた。その結果を表4に示す。
(4)粒子形状
走査型電子顕微鏡によって観察した。その結果を表2に示す。
(5)D50、SD、SD/D50
0.2gの試料を100mlの純水中に入れ、超音波を3分間照射して分散させた後、粒度分布測定装置(日機装株式会社製「マイクロトラック(商品名)FRA(型番)」)によって、体積累積粒径D50及び標準偏差値SD並びに変動係数(SD/D50)をそれぞれ求めた。その結果を表2に示す。
(6)体積抵抗率
試料15gを筒状容器に入れ、プレス圧40×106Pa(408kgf/cm2)で圧縮成形した測定サンプルを形成し、この測定サンプルについて、ロレスタAP及びロレスタPD-41型(いずれも三菱化学(株)社製)を用いて測定を行った。その結果を表6に示す。
Claims (8)
- 粒子内部にSi(ケイ素)を0.1atm%~10atm%、かつIn(インジウム)を0.1atm%~10atm%含有することを特徴とする導電性ペースト用銅粉。
- 粒子内部にAg(銀)を0.1atm%~10atm%含有することを特徴とする請求項1に記載の導電性ペースト用銅粉。
- Si/In(atm比)が0.5~5であることを特徴とする請求項1又は2に記載の導電性ペースト用銅粉。
- 粒子内部にP(りん)を0.01atm%~0.5atm%含有することを特徴とする請求項1~3の何れかに記載の導電性ペースト用銅粉。
- Si/P(atm比)が4~200であることを特徴とする請求項4に記載の導電性ペースト用銅粉。
- In/P(atm比)が4~200であることを特徴とする請求項4又は5に記載の導電性ペースト用銅粉。
- アトマイズ法により製造されたものであることを特徴とする請求項1~6の何れかに記載の導電性ペースト用銅粉。
- 請求項1~7の何れかに記載の導電性ペースト用銅粉を含有することを特徴とする導電性ペースト。
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Cited By (7)
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JP2010037653A (ja) * | 2008-07-11 | 2010-02-18 | Mitsui Mining & Smelting Co Ltd | 導電性ペースト用銅粉及び導電性ペースト |
WO2011145378A1 (ja) * | 2010-05-19 | 2011-11-24 | 三井金属鉱業株式会社 | 導電性ペースト用銅粉及び導電性ペースト |
JP2012079933A (ja) * | 2010-10-01 | 2012-04-19 | Fujifilm Corp | 配線材料、配線の製造方法、及びナノ粒子分散液 |
EP2444978A3 (en) * | 2010-10-20 | 2013-03-06 | Hitachi Cable, Ltd. | Solar cell conductor and method of manufacturing the same |
JP2013058722A (ja) * | 2011-09-08 | 2013-03-28 | Samsung Electro-Mechanics Co Ltd | 外部電極用導電性ペースト、これを用いた積層セラミック電子部品及びその製造方法 |
JP2016176133A (ja) * | 2015-03-23 | 2016-10-06 | 株式会社村田製作所 | 銅粉末および該銅粉末を用いた導電性ペースト |
CN110114174A (zh) * | 2016-12-28 | 2019-08-09 | 同和电子科技有限公司 | 铜粉及其制造方法 |
Families Citing this family (1)
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JP5785433B2 (ja) * | 2011-04-28 | 2015-09-30 | 三井金属鉱業株式会社 | 低炭素銅粒子 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS58104970A (ja) * | 1981-12-16 | 1983-06-22 | Matsushita Electric Ind Co Ltd | 導電性ペイント |
JPH0773730A (ja) * | 1993-06-29 | 1995-03-17 | Asahi Chem Ind Co Ltd | 導電性粉末 |
JPH0920942A (ja) * | 1995-06-27 | 1997-01-21 | Internatl Business Mach Corp <Ibm> | チップ及びパッケージの相互接続用銅合金ならびにその製造法 |
JP2000273506A (ja) * | 1999-03-19 | 2000-10-03 | Asahi Chem Ind Co Ltd | 新規な銅合金粉末とその製造方法 |
JP2003064433A (ja) * | 2001-08-20 | 2003-03-05 | Hohoemi Brains Inc | 装飾用銅合金 |
JP2004169081A (ja) * | 2002-11-19 | 2004-06-17 | Mitsui Mining & Smelting Co Ltd | 金属粉及びその製造方法 |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2702796B2 (ja) * | 1990-02-23 | 1998-01-26 | 旭化成工業株式会社 | 銀合金導電性ペースト |
CN1051862C (zh) * | 1991-04-20 | 2000-04-26 | 旭化成工业株式会社 | 高温烧结用糊剂及其应用 |
JP4914065B2 (ja) * | 2005-12-21 | 2012-04-11 | 大研化学工業株式会社 | 積層セラミックコンデンサ電極用ニッケル粉末、電極形成用ペースト及び積層セラミックコンデンサ |
JP5405814B2 (ja) * | 2007-12-28 | 2014-02-05 | 三井金属鉱業株式会社 | 導電性ペースト用銅粉及び導電性ペースト |
JP5155743B2 (ja) * | 2008-03-04 | 2013-03-06 | 三井金属鉱業株式会社 | 導電性ペースト用銅粉及び導電性ペースト |
JP2010013730A (ja) * | 2008-06-05 | 2010-01-21 | Mitsui Mining & Smelting Co Ltd | 導電性ペースト用銅粉及び導電性ペースト |
JP2010037653A (ja) * | 2008-07-11 | 2010-02-18 | Mitsui Mining & Smelting Co Ltd | 導電性ペースト用銅粉及び導電性ペースト |
JP2010196105A (ja) * | 2009-02-24 | 2010-09-09 | Mitsui Mining & Smelting Co Ltd | 導電性ペースト用銅粉及び導電性ペースト |
-
2009
- 2009-06-19 CN CN2009801144572A patent/CN102015164B/zh not_active Expired - Fee Related
- 2009-06-19 KR KR1020107022969A patent/KR20110041432A/ko active IP Right Grant
- 2009-06-19 JP JP2010519712A patent/JPWO2010004852A1/ja active Pending
- 2009-06-19 WO PCT/JP2009/061241 patent/WO2010004852A1/ja active Application Filing
- 2009-06-25 TW TW098121454A patent/TW201005758A/zh unknown
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS58104970A (ja) * | 1981-12-16 | 1983-06-22 | Matsushita Electric Ind Co Ltd | 導電性ペイント |
JPH0773730A (ja) * | 1993-06-29 | 1995-03-17 | Asahi Chem Ind Co Ltd | 導電性粉末 |
JPH0920942A (ja) * | 1995-06-27 | 1997-01-21 | Internatl Business Mach Corp <Ibm> | チップ及びパッケージの相互接続用銅合金ならびにその製造法 |
JP2000273506A (ja) * | 1999-03-19 | 2000-10-03 | Asahi Chem Ind Co Ltd | 新規な銅合金粉末とその製造方法 |
JP2003064433A (ja) * | 2001-08-20 | 2003-03-05 | Hohoemi Brains Inc | 装飾用銅合金 |
JP2004169081A (ja) * | 2002-11-19 | 2004-06-17 | Mitsui Mining & Smelting Co Ltd | 金属粉及びその製造方法 |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2010037653A (ja) * | 2008-07-11 | 2010-02-18 | Mitsui Mining & Smelting Co Ltd | 導電性ペースト用銅粉及び導電性ペースト |
WO2011145378A1 (ja) * | 2010-05-19 | 2011-11-24 | 三井金属鉱業株式会社 | 導電性ペースト用銅粉及び導電性ペースト |
JP5932638B2 (ja) * | 2010-05-19 | 2016-06-08 | 三井金属鉱業株式会社 | 導電性ペースト用銅粉及び導電性ペースト |
JP2012079933A (ja) * | 2010-10-01 | 2012-04-19 | Fujifilm Corp | 配線材料、配線の製造方法、及びナノ粒子分散液 |
US8551369B2 (en) | 2010-10-01 | 2013-10-08 | Fujifilm Corporation | Wiring material, method of manufacturing wiring, and nano-particle dispersion |
EP2444978A3 (en) * | 2010-10-20 | 2013-03-06 | Hitachi Cable, Ltd. | Solar cell conductor and method of manufacturing the same |
JP2013058722A (ja) * | 2011-09-08 | 2013-03-28 | Samsung Electro-Mechanics Co Ltd | 外部電極用導電性ペースト、これを用いた積層セラミック電子部品及びその製造方法 |
JP2016176133A (ja) * | 2015-03-23 | 2016-10-06 | 株式会社村田製作所 | 銅粉末および該銅粉末を用いた導電性ペースト |
CN110114174A (zh) * | 2016-12-28 | 2019-08-09 | 同和电子科技有限公司 | 铜粉及其制造方法 |
EP3560637A4 (en) * | 2016-12-28 | 2020-09-02 | Dowa Electronics Materials Co., Ltd. | COPPER POWDER AND METHOD FOR MANUFACTURING THEREOF |
US11692241B2 (en) | 2016-12-28 | 2023-07-04 | Dowa Electronics Materials Co., Ltd. | Copper powder and method for producing same |
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KR20110041432A (ko) | 2011-04-21 |
CN102015164B (zh) | 2013-06-12 |
CN102015164A (zh) | 2011-04-13 |
JPWO2010004852A1 (ja) | 2011-12-22 |
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