WO2023223586A1 - 銅粉及びその製造方法 - Google Patents
銅粉及びその製造方法 Download PDFInfo
- Publication number
- WO2023223586A1 WO2023223586A1 PCT/JP2022/045684 JP2022045684W WO2023223586A1 WO 2023223586 A1 WO2023223586 A1 WO 2023223586A1 JP 2022045684 W JP2022045684 W JP 2022045684W WO 2023223586 A1 WO2023223586 A1 WO 2023223586A1
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- WO
- WIPO (PCT)
- Prior art keywords
- copper powder
- copper
- less
- particles
- value
- Prior art date
Links
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 260
- 238000004519 manufacturing process Methods 0.000 title claims description 21
- 239000002245 particle Substances 0.000 claims abstract description 144
- 229910052802 copper Inorganic materials 0.000 claims description 87
- 239000010949 copper Substances 0.000 claims description 87
- 239000002002 slurry Substances 0.000 claims description 29
- 239000002994 raw material Substances 0.000 claims description 27
- 238000009826 distribution Methods 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 239000000314 lubricant Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 8
- 238000000889 atomisation Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 description 33
- 239000011248 coating agent Substances 0.000 description 32
- 238000000576 coating method Methods 0.000 description 32
- 238000005259 measurement Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 230000001186 cumulative effect Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 4
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 4
- 239000005642 Oleic acid Substances 0.000 description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 4
- 229920002799 BoPET Polymers 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 3
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 3
- 229940112669 cuprous oxide Drugs 0.000 description 3
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000012756 surface treatment agent Substances 0.000 description 3
- 229940116411 terpineol Drugs 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 2
- 239000005750 Copper hydroxide Substances 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- 239000001856 Ethyl cellulose Substances 0.000 description 2
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- -1 aliphatic amines Chemical class 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910001956 copper hydroxide Inorganic materials 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229920001249 ethyl cellulose Polymers 0.000 description 2
- 235000019325 ethyl cellulose Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 238000009689 gas atomisation Methods 0.000 description 2
- 238000009499 grossing Methods 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 238000009692 water atomization Methods 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 1
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 1
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 235000021357 Behenic acid Nutrition 0.000 description 1
- 238000005169 Debye-Scherrer Methods 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 229910025794 LaB6 Inorganic materials 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000010296 bead milling Methods 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003985 ceramic capacitor Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/06—Metallic powder characterised by the shape of the particles
- B22F1/065—Spherical particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/06—Metallic powder characterised by the shape of the particles
- B22F1/068—Flake-like particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/0425—Copper-based alloys
-
- 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
- B22F2301/00—Metallic composition of the powder or its coating
- B22F2301/10—Copper
Definitions
- the present invention relates to copper powder and a method for producing the same.
- Copper is a highly conductive metal and a highly versatile material, so it is widely used industrially as a conductive material.
- copper powder which is an aggregate of copper particles, is widely used as a raw material for manufacturing various electronic components, such as the external and internal electrodes of multilayer ceramic capacitors (hereinafter also referred to as "MLCC"), and wiring for various substrates. It's being used.
- MLCC multilayer ceramic capacitors
- Patent Document 1 discloses that in flaky copper powder obtained by plastically deforming copper powder particles into flakes, the weight cumulative particle diameter D50 measured by laser diffraction scattering particle size distribution measuring method is 10 ⁇ m or less, and the laser diffraction scattering method A flake-like product in which the standard deviation SD/D 50 of the particle size distribution measured by a particle size distribution measurement method is 0.55 or less, and the weight cumulative particle size D 90 / weight cumulative particle size D 10 is 4.5 or less. Copper powder is listed. This document states that the flaky copper powder makes it possible to control the viscosity of the conductive paste and impart appropriate thixotropic properties to the conductive paste.
- Patent Document 2 describes a flaky copper powder made of flaky copper particles having an average thickness D of 0.2 ⁇ m or more.
- This flaky copper powder has a 50% diameter D 50 of 1 to 30 ⁇ m in particle size distribution and an aspect ratio (D 50 /average thickness D) of 5 to 70.
- This document states that this flaky copper powder is suitable as a filler for conductive paste.
- Patent Document 3 states that in flaky copper powder consisting of flaky copper particles with an average thickness D of 0.2 ⁇ m or more, the 50% diameter D 50 in the particle size distribution is 1 to 30 ⁇ m, and is defined as D 50 /D.
- a flaky copper powder having an aspect ratio of 5 to 70 and a value of SD/(D 90 /D 10 ) of 0.1 or less is described.
- SD is the standard deviation of the thickness of 100 particles measured by electron microscopy
- D90 is the 90% diameter in the particle size distribution
- D10 is the 10% diameter in the particle size distribution.
- an object of the present invention is to provide a copper powder and a method for producing the same that can produce an electrode with high density and continuity without the need for mixing.
- the present invention has a tap density of 4.2 g/cm 3 or more and 5.5 g/cm 3 or less when tapped 400 times according to JIS Z2512:2012,
- the tap density when tapped 100 times according to JIS Z2512:2012 is 4.1 g/cm 3 or more and 5.5 g/cm 3 or less
- the present invention provides copper powder having a value of standard deviation SD ( ⁇ m) of particle thickness/average particle diameter D 50 ( ⁇ m) of 0.08 or more and 0.26 or less.
- the present invention provides raw material copper that has an SD value of particle size distribution of 1.00 or more, a value of (D 90 ⁇ D 10 )/D 50 of 1.00 or more, and is made of an aggregate of spherical copper particles.
- a method for producing copper powder comprising the step of subjecting the slurry to a flattening treatment using a media mill device to transform the spherical copper particles into flat copper particles,
- the present invention provides a method for producing copper powder, in which the flattening treatment is performed in an inert atmosphere while maintaining the water content in the slurry at 0.3% by mass or less.
- FIG. 1 is a scanning electron microscope image of the copper powder obtained in Example 1.
- FIG. 2 is a scanning electron microscope image of the copper powder obtained in Comparative Example 2.
- the present invention relates to copper powder mainly containing flat copper particles. Copper powder and copper particles consist of copper and inevitable impurities.
- One of the characteristics of the copper powder of the present invention is that the copper powder has high density and high fluidity.
- the high density and fluidity of the copper powder means that the particles in the coating film of the paste prepared using the copper powder of the present invention are highly dense, and the coating film is highly continuous, that is, without interruption. It means that it can form a coating film.
- the degree of compactness can be evaluated by the tap density of the copper powder.
- the copper powder of the present invention has a tap density (hereinafter also referred to as "400 tap density”) when tapped 400 times according to JIS Z2512:2012 of 4.2 g/cm 3 or more and 5.5 g/cm 3 or less. It is preferably 4.3 g/cm 3 or more and 5.5 g/cm 3 or less, more preferably 4.3 g/cm 3 or more and 5.4 g/cm 3 or less.
- the 400 tap density of the copper powder is within the above range, the denseness of the copper powder increases.
- flat copper particles may be manufactured, for example, according to the method described below.
- the degree of fluidity can be evaluated by the tap density when tapped 100 times (hereinafter also referred to as "100 tap density") according to JIS Z2512:2012.
- the copper powder of the present invention has a 100 tap density of 4.1 g/cm 3 to 5.5 g/cm 3 , preferably 4.2 g/cm 3 to 5.4 g/cm 3 , and 4.2 g/cm 3 to 5.4 g/cm 3 . More preferably, it is .2 g/cm 3 or more and 5.3 g/cm 3 or less.
- the fluidity of the copper powder becomes high, and the copper powder can be used to form a coating film.
- the density of the copper powder in the coating film increases.
- copper particles having smooth and flat surfaces may be manufactured, for example, according to the method described below. Note that, depending on the type of copper powder, the 100-times tap density is the same value as the 400-times tap density, or a value smaller than that.
- the copper powder of the present invention has a specific relationship between the standard deviation SD ( ⁇ m) of the thickness of the copper particles constituting the powder and the average particle diameter D 50 ( ⁇ m).
- the value of standard deviation SD ( ⁇ m)/average particle diameter D 50 ( ⁇ m) is 0.08 or more and 0.26 or less, preferably 0.09 or more and 0.25 or less, and 0.09 or more and 0.25 or less. More preferably, it is 10 or more and 0.24 or less.
- the standard deviation SD ( ⁇ m)/average particle diameter D 50 ( ⁇ m) is within the above range, the copper particles constituting the copper powder have suppressed variations in the thickness of the particles with respect to the particle size. .
- the particle size and thickness of the copper particles become uniform, when a coating film is formed using copper powder made of such an aggregate of copper particles, the formation of gaps between the copper particles is suppressed, and the copper Particles come to exist continuously. As a result, the continuity of the copper particles in the coating is increased.
- the average particle diameter D 50 of the copper particles can be determined by laser diffraction scattering particle size distribution measuring method.
- the standard deviation SD of the thickness of copper particles is determined by mixing copper powder, a solvent, and a resin to form a resin composition, forming a coating film, and then drying the coating film.
- the thickness can be determined by a method of measuring using a scanning electron microscope.
- the average particle diameter D50 of the copper particles is preferably 2.0 ⁇ m or more and 5.0 ⁇ m or less, and 2.5 ⁇ m or more. It is more preferably 4.8 ⁇ m or less, and even more preferably 3.0 ⁇ m or more and 4.5 ⁇ m or less. From the same viewpoint, the average thickness of the copper particles is preferably 0.20 ⁇ m or more and 2.00 ⁇ m or less, more preferably 0.30 ⁇ m or more and 1.80 ⁇ m or less, and 0.40 ⁇ m or more and 1.70 ⁇ m or less.
- the average thickness of copper particles is measured by mixing copper powder, a solvent, and a resin to form a resin composition, forming a coating film, and then drying the coating film. It can be determined by measuring the thickness of the particles. The measurement targets more than 300 copper particles. The cross section is observed using a scanning electron microscope at a magnification of 2000 times.
- the average value of the aspect ratio (hereinafter also referred to as "plane aspect ratio"), which is the value of the length of the copper particle on the plate surface/breadth axis of the particle, is 1.25 or more and 3.00 or less. It is preferably 1.27 or more and 2.50 or less, and even more preferably 1.30 or more and 2.00 or less.
- the copper powder of the present invention is composed of copper particles having a plane aspect ratio as described above, when a coating film is composed of copper powder containing the copper particles, the copper in the coating film is The compactness and continuity of the powder are further improved.
- flat refers to a shape having a pair of plate surfaces forming the main surface of the particle and side surfaces intersecting these plate surfaces.
- the plate surface and the side surface may each independently be a flat surface, a curved surface, or an uneven surface.
- the plate surface is flat.
- the average value of the aspect ratio (hereinafter also referred to as "side aspect ratio"), which is the long side/short side value in the thickness plane of the copper particles, that is, the side surface, is preferably 2.0 or more. Since the copper powder of the present invention is composed of copper particles having such a side aspect ratio, when a coating film is composed of copper powder containing the copper particles, the density of the copper powder in the coating film is reduced. The quality and continuity are further improved.
- the side aspect ratio can be measured by the same method as the measurement of the standard deviation SD of the thickness of the copper particles described above.
- mainly containing flat copper particles means that the content ratio of copper particles having the above-mentioned side aspect ratio satisfying the above-mentioned range is, for example, 70% or more on a number basis.
- the proportion of spherical particles is preferably 30% or less, more preferably 28% or less, and 25% or less on a number basis. is even more preferable.
- the proportion of copper particles having an average plane aspect ratio of 1.25 or more is preferably 30% or more, more preferably 35% or more, and 40% or more based on the number of particles.
- the above is more preferable, and it is particularly preferable that all the copper particles have an average planar aspect ratio of 1.25 or more. This ensures that the above-mentioned effects of the copper powder of the present invention are achieved.
- the plane aspect ratio is determined by the following method. Copper powder is observed using a scanning electron microscope (hereinafter also referred to as "SEM"), and for 300 or more arbitrary particles in the observation field, the major axis D on the plate surface and the perpendicular bisector of the major axis D are the particles.
- SEM scanning electron microscope
- D/d which is the length across the axis, that is, the ratio to the short axis d.
- An appropriate value for the SEM magnification is selected depending on the particle size of the copper particles. Generally, a magnification is selected such that 300 to 600 particles are observed in the field of view.
- the copper powder of the present invention preferably has a planar aspect ratio within a certain range, regardless of the particle size of the copper particles constituting it.
- the planar aspect ratio is in the range of 1.25 or more and 3.00 or less. It is preferable because it results in a copper powder with high properties, and it is particularly preferable that the plane aspect ratio is 1.25 or more and 2.50 or less, especially 1.25 or more and 2.00 or less.
- the copper powder of the present invention may contain copper particles other than copper particles having an average plane aspect ratio of 1.25 or more.
- shape of such copper particles there is no particular restriction on the shape of such copper particles, and both circular and non-circular shapes can be used.
- the fact that the copper particles are circular means that the circularity coefficient is 0.85 or more when the copper particles are two-dimensionally projected.
- the circularity coefficient is calculated by taking a scanning electron microscope image of a primary copper particle, and assuming that the area of the two-dimensional projected image of the copper particle is S and the perimeter is L, the circularity coefficient of the copper particle is 4 ⁇ S. /L Calculated from the formula 2 .
- the fact that the copper particles have a non-circular shape means that the above-mentioned circularity coefficient is less than 0.85.
- Specific examples of non-circular particles include polyhedral particles such as hexahedrons and octahedrons, spindle-shaped particles, and irregularly shaped particles.
- the copper crystallite size in the copper particles constituting the copper powder is preferably 50 nm or more and 100 nm or less, more preferably 50 nm or more and 90 nm or less, and even more preferably 50 nm or more and 80 nm or less.
- the crystallite size of copper within this range, when a coating film is formed from the copper powder and the coating film is fired, the degree of shrinkage of the copper particles due to the heat during coating can be controlled within an appropriate range. This increases the dimensional stability of the electrode.
- the degree of flattening of the spherical copper particles may be appropriately controlled, for example, in a preferred method for producing copper powder, which will be described later. This is because the crystallite size of copper tends to decrease when external force is applied.
- ⁇ X-ray diffraction measurement conditions> ⁇ Tube: CuK ⁇ rays ⁇ Tube voltage: 40kV ⁇ Tube current: 50mA ⁇ Measurement diffraction angle: 2 ⁇ 20 ⁇ 100° ⁇ Measurement step width: 0.01° ⁇ Collection time: 3sec/step ⁇ Light receiving slit width: 0.3mm ⁇ Divergence vertical restriction slit width: 10mm ⁇ Detector: High-speed one-dimensional X-ray detector D/teX Ultra250
- ⁇ Measurement data analysis conditions> ⁇ Analysis software: Rigaku PDXL2 ⁇ Smoothing processing: Gaussian function, smoothing parameter 10 ⁇ Background removal: Fitting method ⁇ K ⁇ 2 removal: Intensity ratio 0.497 ⁇ Peak search: Second-order differential method ⁇ Profile fitting: FP method ⁇ Crystal size distribution type: Lorentz model ⁇ Scherrer constant: 0.9400
- the content of oxygen element in the copper powder is as low as possible.
- the content of oxygen element in the copper powder is preferably 0.50% by mass or less, more preferably 0.45% by mass or less, and even more preferably 0.40% by mass or less.
- the content of the oxygen element in the copper powder is below this value, the dispersion stability of the paste containing the copper powder of the present invention is improved, and agglomeration and viscosity change can be suppressed.
- the oxygen element content in the copper powder can be achieved, for example, by setting the moisture content in the slurry subjected to the flattening treatment in the copper powder manufacturing method described below to 3000 ppm or less, and performing the flattening treatment in an inert gas atmosphere. Can be done.
- the content of carbon element in the copper powder is also as low as possible. Specifically, it is preferably 0.40% by mass or less, more preferably 0.30% by mass or less, and even more preferably 0.20% by mass or less. If the carbon element content in the copper powder is excessively high, decomposition gas derived from carbon will be generated when the paste containing the copper powder is fired, and this decomposition gas will cause cracks and blisters in the sintered body. This may occur.
- a material powder with a low carbon content may be used as the raw material powder for the copper powder of the present invention. Examples of such raw material powder include copper powder produced by an atomization method such as a gas atomization method or a water atomization method, and copper powder produced by a plasma method.
- the content of carbon element in the copper powder of the present invention is determined by measurement using a combustion-infrared absorption method in an oxygen stream using a carbon and sulfur analyzer CS-844 manufactured by LECO. Specifically, 0.5 g of a sample is placed in a crucible, and the crucible is set in an apparatus for measurement.
- the copper powder of the present invention can be preferably produced by the following method.
- a raw material copper powder consisting of an aggregate of spherical copper particles is prepared. It is preferable to use a raw material copper powder having a wide particle size distribution from the viewpoint of easily obtaining copper powder with high density and fluidity. From this point of view, it is advantageous to use raw material copper powder having a (D 90 ⁇ D 10 )/D 50 value of 1.00 or more, particularly 1.05 or more, especially 1.10 or more. be.
- Such raw material copper powder can be easily formed by, for example, an atomizing method such as a gas atomizing method and a water atomizing method, or a plasma method.
- the method is not limited to these methods, and copper hydroxide can be precipitated by reacting a copper salt aqueous solution with an alkaline agent, and the copper hydroxide can be primarily reduced to cuprous oxide in the liquid. It is also possible to use a wet reduction method in which copper oxide is secondarily reduced to metallic copper in a liquid.
- the upper limit of the value of (D 90 ⁇ D 10 )/D 50 is preferably about 2.00.
- D 10 , D 50 and D 90 are volume cumulative particle diameters at a cumulative volume of 10% by volume, 50% by volume and 90% by volume, respectively, measured by laser diffraction scattering particle size distribution measurement method.
- the raw material copper powder has a particle size distribution SD value of 1.00 or more from the viewpoint of easily obtaining copper powder with high density and fluidity. From this viewpoint, it is more preferable that the SD value of the particle size distribution of the raw material copper powder is 1.10 or more, and even more preferably 1.15 or more. The upper limit of the SD value of the particle size distribution is preferably about 3.00.
- raw copper powder and an organic solvent are mixed to prepare a slurry.
- the organic solvent it is preferable to use an aliphatic alcohol having 1 or more and 22 or less carbon atoms, and it is more preferable to use a saturated aliphatic monohydric alcohol having 1 or more and 10 or less carbon atoms.
- a monohydric alkyl alcohol having 1 to 4 carbon atoms examples include methanol, ethanol, n-propanol, sec-propanol, n-butanol, sec-butanol, tert-butanol, and the like.
- One kind of alcohol can be used alone or two or more kinds can be used in combination.
- the blending ratio of the raw material copper powder and the organic solvent is preferably 10% by mass or more and 90% by mass or less, particularly 30% by mass or more and 70% by mass or less, based on the total mass of both.
- the water content in the slurry is 0.3% by mass or less.
- the oxygen element content in the copper powder can be controlled to the above-mentioned 0.5% by mass or less, the dispersion stability of the copper powder is improved, and agglomeration and viscosity change can be suppressed.
- Copper powder having the characteristics described above can be easily obtained. If the amount of water in the slurry is too high, the surface of the flat copper particles will be oxidized and roughened by the water, and the smoothness of the surface will likely be impaired. The reason for this is that fine particles of copper oxide such as cuprous oxide are formed on the surface of the copper particles. Flat copper particles whose surfaces are not smooth tend to have reduced fluidity.
- the slurry is subjected to flattening treatment using a media mill device to transform the spherical copper particles into flat copper particles.
- a media mill device a bead mill, a ball mill, and a vibration mill can be used.
- this flattening treatment if other conditions are constant, the longer the treatment time, the more flat copper particles with a larger planar aspect ratio can be obtained. It is sufficient.
- the flattening process is performed under an inert atmosphere such as nitrogen or argon gas while maintaining the water content in the slurry at 3000 ppm or less.
- an inert atmosphere such as nitrogen or argon gas
- the oxygen element content in the copper powder can be controlled to the above-mentioned 0.5% by mass or less, the dispersion stability of the copper powder is improved, and agglomeration and changes in hardness can be suppressed.
- Copper powder having the characteristics described above can be obtained.
- the media to be loaded into a ball mill or vibration mill can be made of ceramics, glass, metal, etc. There are no restrictions, but ceramics are preferred because they are strong and do not become a source of impurities due to breakage or abrasion during the grinding process. is more preferably zirconia.
- the diameter of the media used is preferably 0.03 mm or more and 5 mm or less, more preferably 0.05 mm or more and 2.5 mm or less.
- a lubricant such as a fatty acid.
- a lubricant When a lubricant is used, small-sized copper particles become difficult to crush, making it difficult to obtain a flat copper powder that satisfies the above-mentioned properties.
- the use of a lubricant is not completely excluded, and if necessary, a lubricant may be included in the raw copper powder at a ratio of 0.1% by mass or more and 1.0% by mass or less.
- lubricants examples include oleic acid, lauric acid, myristic acid, palmitic acid, stearic acid, and behenic acid.
- a surface treatment agent may be attached to the surface of the copper powder. By attaching a surface treatment agent to the surface of the copper powder, excessive aggregation of the copper powder can be suppressed.
- the surface treatment agent is not particularly limited, and fatty acids, aliphatic amines, silane coupling agents, titanate coupling agents, aluminate coupling agents, etc. can be used. By using these, it is possible to interact with the particle surface and improve the compatibility with the organic solvent contained in the paste, thereby improving the fluidity of the paste and preventing oxidation of the particle surface.
- the circulation tank and the media mill device are connected by outbound piping and return piping, and the slurry is circulated between the circulation tank and the media mill device.
- the water content in the slurry is maintained at 0.3% by mass or less, that no lubricant is present, and that an inert atmosphere is maintained in the circulation tank, the media mill device, and each piping.
- a copper paste containing the copper powder is prepared.
- the copper paste may be prepared by mixing the copper powder of the present invention with a binder, a solvent, a glass frit, and the like. By doing so, a high-temperature firing type copper paste can be obtained.
- a resin-cured copper paste can be prepared by mixing the copper powder of the present invention with a binder, a solvent, and, if necessary, a curing agent.
- binder examples include, but are not limited to, liquid epoxy resin, acrylic resin, phenol resin, unsaturated polyester resin, and the like.
- solvent examples include terpineol, ethyl carbitol, carbitol acetate, butyl cellosolve, butyl carbitol acetate, and the like.
- curing agent examples include 2-ethyl-4-methylimidazole.
- curing accelerator examples include tertiary amines, tertiary amine salts, imidazoles, phosphines, and phosphonium salts.
- the tap density when tapped 400 times according to JIS Z2512:2012 is 4.2 g/cm 3 or more and 5.5 g/cm 3 or less
- the tap density when tapped 100 times according to JIS Z2512:2012 is 4.1 g/cm 3 or more and 5.5 g/cm 3 or less
- ⁇ 3> The copper powder according to ⁇ 2>, which contains 30% or more of particles having an aspect ratio of 1.25 or more based on the number of particles.
- ⁇ 4> The copper powder according to any one of ⁇ 1> to ⁇ 3>, wherein the content of oxygen element is 0.5% by mass or less.
- ⁇ 5> The copper powder according to any one of ⁇ 1> to ⁇ 4>, having an average particle diameter D 50 of 2.0 ⁇ m or more and 5.0 ⁇ m or less.
- ⁇ 6> The copper powder according to any one of ⁇ 1> to ⁇ 5>, wherein the copper crystallite size is 50 nm or more and 80 nm or less.
- ⁇ 7> The copper powder according to any one of ⁇ 1> to ⁇ 6>, wherein the content of carbon element is 0.40% by mass or less.
- ⁇ 9> The manufacturing method according to ⁇ 8>, wherein the raw material copper powder is manufactured by an atomization method.
- ⁇ 11> The method for producing copper powder according to any one of ⁇ 8> to ⁇ 10>, wherein the flattening treatment is performed in the absence of a lubricant.
- Example 1 MA-C03K, which is an atomized copper powder manufactured by Mitsui Mining and Mining Co., Ltd., was used as the raw material copper powder.
- the average particle diameter D50 of this raw material powder was 3.08 ⁇ m, and the carbon content was 100 ppm. Further, the value of (D 90 ⁇ D 10 )/D 50 was 1.13, and the SD value of particle size distribution was 1.27.
- 100 kg of methanol and 100 kg of raw copper powder were mixed to form a slurry, and this slurry was supplied to a Star Mill (registered trademark) model LMZ10 manufactured by Ashizawa Finetech Co., Ltd., which is a media dispersion mill.
- the mill was filled with zirconia beads having a diameter of 0.1 mm.
- the mill was operated for 300 minutes at a circumferential speed of 12 m/sec to flatten the raw copper powder by plastic deformation.
- the surface treatment was performed by adding 0.1 kg of oleic acid to the treated slurry and stirring for 30 minutes.
- the copper slurry thus obtained was subjected to solid-liquid separation, and the obtained copper powder was dried and collected.
- the water content in the slurry was maintained at 3000 ppm or less, and the inside of the mill was kept in a nitrogen atmosphere. Furthermore, no lubricant was present in the slurry during the bead milling process.
- the slurry was circulated between the circulation tank and the mill.
- FIG. 1 shows a SEM image of the copper powder obtained in this example.
- Example 2 In Example 1, the raw material copper powder used had an average particle diameter D 50 of 3.30 ⁇ m, a value of (D 90 ⁇ D 10 )/D 50 of 1.22, and an SD value of particle size distribution of 1.47. . Copper powder was obtained in the same manner as in Example 1 except for the above.
- Example 3 In Example 1, the raw material copper powder used had an average particle diameter D 50 of 2.90 ⁇ m, a value of (D 90 ⁇ D 10 )/D 50 of 1.16, and an SD value of particle size distribution of 1.10. , the mill operation time was 240 minutes. Copper powder was obtained in the same manner as in Example 1 except for the above.
- Example 4 In Example 1, the raw material copper powder used had an average particle diameter D 50 of 2.60 ⁇ m, a value of (D 90 ⁇ D 10 )/D 50 of 1.44, and an SD value of particle size distribution of 1.45.
- the mill operation time was set to 660 minutes, and 250 g of oleic acid was dissolved in the slurry to perform flattening treatment.
- the copper powder thus obtained was subjected to solid-liquid separation, dried and collected. Moreover, oleic acid was not added after the flattening process. Copper powder was obtained in the same manner as in Example 1 except for the above.
- Example 5 In Example 1, the raw material copper powder used had an average particle diameter D 50 of 3.19 ⁇ m, a value of (D 90 - D 10 )/D 50 of 1.07, and an SD value of particle size distribution of 1.10.
- the flattening process was carried out with a mill operating time of 300 minutes.
- Surface treatment was carried out by dissolving 0.1 kg of oleylamine in the treated slurry.
- the copper powder thus obtained was subjected to solid-liquid separation, dried and collected. Copper powder was obtained in the same manner as in Example 1 except for the above.
- Example 4 In Example 4, the atmosphere in the slurry was set to atmospheric, the water content was not maintained below 3000 ppm, and the mill operation time was set to 300 minutes. Copper powder was obtained in the same manner as in Example 4 except for the above.
- Example 2 In Example 1, the raw material copper powder used had an average particle diameter D 50 of 3.10 ⁇ m, a value of (D 90 ⁇ D 10 )/D 50 of 1.20, and an SD value of particle size distribution of 1.37. The atmosphere in the slurry was made into an atmospheric atmosphere so that the water content was not maintained below 3000 ppm. Copper powder was obtained in the same manner as in Example 1 except for the above. FIG. 2 shows an SEM image of the copper powder obtained in this comparative example. Since the moisture content is not controlled, surface irregularities resulting from oxidation can be observed.
- the 400 tap density and the 100 tap density of the copper powders obtained in the Examples and Comparative Examples were measured by the method described above. Further, the standard deviation SD/D 50 of the thickness, the plane aspect ratio, the side aspect ratio, the crystallite size, the content of oxygen element, and the content of carbon element were measured by the above-mentioned methods. Furthermore, coating film density and coating film continuity were evaluated by the following methods. These results are shown in Table 1. Although not shown in the table, the copper powder obtained in the examples contained 70% or more of copper particles having a side surface aspect ratio of 2.0 or more on a number basis.
- the copper powder obtained in each example has better density and continuity than the copper powder of the comparative example.
- the coating film density was improved compared to Example 4 in which a lubricant was used. I understand that.
- the surface of the copper particles constituting the copper powder obtained in Example 1 is smooth, whereas the surface of the copper powder obtained in Comparative Example 2 is smooth. It can be seen that the surface of the copper particles making up the powder is rough. As a result of analysis by the present inventors, it was found that the surface roughness was caused by cuprous oxide-derived unevenness caused by the oxidation of copper.
- a copper powder and a method for producing the same that can produce an electrode with high density and continuity without the need for mixing.
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Abstract
Description
したがって本発明の課題は、混合使用を必要とせずに緻密性及び連続性が高い電極を製造し得る銅粉及びその製造方法を提供することにある。
JIS Z2512:2012に準じて100回タップしたときのタップ密度が4.1g/cm3以上5.5g/cm3以下であり、
粒子の厚みの標準偏差SD(μm)/平均粒径D50(μm)の値が0.08以上0.26以下である、銅粉を提供するものである。
前記原料銅粉と有機溶媒とを混合してスラリーを調製する工程と、
前記スラリーをメディアミル装置による扁平化処理に付して、前記球状銅粒子を扁平銅粒子に変形させる工程と、を有する銅粉の製造方法であって、
前記扁平化処理を、前記スラリー中の水分量を0.3質量%以下に維持しながら、不活性雰囲気で行う、銅粉の製造方法を提供するものである。
本発明は、扁平な銅粒子を主として含む銅粉に関するものである。銅粉及び銅粒子は、銅及び不可避不純物からなる。本発明の銅粉は、銅粉の緻密性が高く、また流動性が高い点に特徴の一つを有する。銅粉の緻密性及び流動性が高いことは、本発明の銅粉を用いて調製されたペーストの塗膜における粒子の緻密性が高く、また塗膜の連続性が高いこと、すなわち途切れることなく塗膜を形成し得ることを意味する。
なお、銅粉の種類に応じ、100回タップ密度は、400回タップ密度と同じ値であるか、又はそれよりも小さい値をとる。
同様の観点から、銅粒子の厚み平均値は、0.20μm以上2.00μm以下であることが好ましく、0.30μm以上1.80μm以下であることがより好ましく、0.40μm以上1.70μm以下であることが更に好ましい。銅粒子の厚み平均値の測定は、銅粉と溶剤と樹脂を混合し樹脂組成物とし、その塗膜を形成後に該塗膜を乾燥させ、得られた乾燥塗膜の断面に観察される銅粒子の厚みを測定することで求めることができる。測定は300個以上の銅粒子を対象とする。断面の観察は、走査型電子顕微鏡を用い倍率2000倍で行う。
本明細書において扁平とは、粒子の主面を形成している一対の板面と、これらの板面と交差する側面とを有する形状を指す。板面及び側面はそれぞれ独立して、平面、曲面又は凹凸面であり得る。板面は平面であることが好ましい。
なお、本発明において「扁平な銅粒子を主として含む」とは、上述した側面アスペクト比が上述の範囲を満たす銅粒子の含有割合が例えば個数基準で70%以上であることをいう。
本発明の銅粉中に球状粒子が含まれている場合、球状粒子の割合は、個数基準で30%以下であることが好ましく、28%以下であることがより好ましく、25%以下であることが更に好ましい。
本発明において平面アスペクト比は次の方法で決定される。銅粉について走査型電子顕微鏡(以下「SEM」とも言う。)観察を行い、観察視野中の300個以上の任意の粒子について板面における長径Dと、該長径Dの垂直二等分線が粒子を横切る長さ、すなわち短径dとの比であるD/dで表される。SEMの拡大倍率は、銅粒子の粒径に応じて適切な値を選択する。一般に、視野中に300個以上600以下の粒子が観察されるような倍率を選択する。
・管球:CuKα線
・管電圧:40kV
・管電流:50mA
・測定回折角:2θ=20~100°
・測定ステップ幅:0.01°
・収集時間:3sec/ステップ
・受光スリット幅:0.3mm
・発散縦制限スリット幅:10mm
・検出器:高速1次元X線検出器 D/teX Ultra250
測定対象の銅粉を測定ホルダに敷き詰め、銅粉層の厚さが0.5mmで且つ平滑になるように、ガラスプレートを用いて平滑化した。
・解析ソフトウェア:Rigaku製PDXL2
・平滑処理:ガウス関数、平滑化パラメータ=10
・バックグラウンド除去:フィッティング方式
・Kα2除去:強度比0.497
・ピークサーチ:二次微分法
・プロファイルフィッティング:FP法
・結晶子サイズ分布タイプ:ローレンツモデル
・シェラー定数:0.9400
銅粉中の酸素元素含有量は、例えば後述する銅粉の製造方法における扁平化処理に供するスラリー中の水分量を3000ppm以下とし、扁平化処理を不活性ガス雰囲気中で行うことにより達成することができる。
銅粉の炭素元素含有量を低減させるためには、例えば本発明の銅粉の原料となる原料粉として炭素含有量の少ないものを用いればよい。そのような原料粉としては、例えばガスアトマイズ法や水アトマイズ法等のアトマイズ法で製造された銅粉や、プラズマ法で製造された銅粉が挙げられる。
最初に、球状銅粒子の集合体からなる原料銅粉を準備する。この原料銅粉としては広い粒度分布を有するものを用いることが、緻密性及び流動性が高い銅粉を容易に得られる観点から好ましい。この観点から、原料銅粉は、(D90-D10)/D50の値が1.00以上であるもの、特に1.05以上、とりわけ1.10以上であるものを用いることが有利である。このような原料銅粉は、例えばガスアトマイズ法及び水アトマイズ法等のアトマイズ法やプラズマ法によって容易に形成することができる。尤も、これらの方法に限定されるものではなく、銅塩水溶液とアルカリ剤を反応させて水酸化銅を析出させ、この水酸化銅を亜酸化銅に液中で一次還元し、得られた亜酸化銅を金属銅に液中で二次還元する湿式還元法等を用いることもできる。(D90-D10)/D50の値の上限値は2.00程度であることが好ましい。
D10、D50及びD90はそれぞれ、レーザ回折散乱式粒度分布測定法による累積体積10容量%、50容量%及び90容量%における体積累積粒径のことである。
<1>JIS Z2512:2012に準じて400回タップしたときのタップ密度が4.2g/cm3以上5.5g/cm3以下であり、
JIS Z2512:2012に準じて100回タップしたときのタップ密度が4.1g/cm3以上5.5g/cm3以下であり、
粒子の厚みの標準偏差SD(μm)/平均粒径D50(μm)の値が0.08以上0.26以下である、銅粉。
<2>粒子の長径/粒子の短径の値であるアスペクト比の平均値が1.25以上3.00以下である、<1>に記載の銅粉。
<3>前記アスペクト比が1.25以上である粒子を、個数基準で30%以上含む、<2>に記載の銅粉。
<4>酸素元素の含有量が0.5質量%以下である、<1>ないし<3>のいずれか一に記載の銅粉。
<5>平均粒径D50が2.0μm以上5.0μm以下である、<1>ないし<4>のいずれか一に記載の銅粉。
<6>銅の結晶子サイズが50nm以上80nm以下である、<1>ないし<5>のいずれか一に記載の銅粉。
<7>炭素元素の含有量が0.40質量%以下である、<1>ないし<6>のいずれか一に記載の銅粉。
<8>(D90-D10)/D50の値が1.00以上であり、球状銅粒子の集合体からなる原料銅粉を準備する工程と、
前記原料銅粉と有機溶媒とを混合してスラリーを調製する工程と、
前記スラリーをメディアミル装置による扁平化処理に付して、前記球状銅粒子を扁平銅粒子に変形させる工程と、を有する銅粉の製造方法であって、
前記扁平化処理を、前記スラリー中の水分量を0.30質量%以下に維持しながら、不活性雰囲気で行う、銅粉の製造方法。
<9>アトマイズ法で前記原料銅粉を製造する、<8>に記載の製造方法。
<10>粒度分布のSD値が1.00以上である前記原料銅粉を準備する、<8>又は<9>に記載の製造方法。
<11>前記扁平化処理を滑剤の不存在下に行う、<8>ないし<10>のいずれか一に記載の銅粉の製造方法。
原料銅粉として三井金属鉱業(株)製のアトマイズ法銅粉であるMA-C03Kを用いた。この原料粉の平均粒径D50は3.08μmであり、炭素の含有割合は100ppmであった。また、(D90-D10)/D50の値は1.13であり、粒度分布のSD値は1.27であった。
メタノール100kgと原料銅粉100kgを混合してスラリーとなし、このスラリーを、媒体分散ミルであるアシザワファインテック(株)社製スターミル(登録商標)型式LMZ10に供給した。ミルには、直径0.1mmのジルコニアビーズを充填した。
ミルを周速12m/secの条件で300分間運転して、原料銅粉を塑性変形による扁平化処理した。処理後のスラリーにオレイン酸0.1kgを添加し、30分撹拌することで表面処理を施した。このようにして得られた銅スラリーを固液分離し、得られた銅粉を乾燥させ回収した。
ビーズミル処理時における、スラリー中の水分量は3000ppm以下に維持し、ミル内は窒素雰囲気とした。また、ビーズミル処理時には、スラリー中に滑剤を存在させなかった。スラリーは循環槽とミルとの間を循環させた。
本実施例で得られた銅粉のSEM像を図1に示す。
実施例1において、原料銅粉の平均粒径D50が3.30μm、(D90-D10)/D50の値が1.22、粒度分布のSD値が1.47のものを使用した。それ以外は実施例1と同様にして銅粉を得た。
実施例1において、原料銅粉の平均粒径D50が2.90μm、(D90-D10)/D50の値が1.16、粒度分布のSD値が1.10のものを使用し、ミル運転時間を240分とした。それ以外は実施例1と同様にして銅粉を得た。
実施例1において、原料銅粉の平均粒径D50が2.60μm、(D90-D10)/D50の値が1.44、粒度分布のSD値が1.45のものを使用し、ミル運転時間を660分とし、スラリー中にオレイン酸を250g溶解させて扁平処理を実施した。このようにして得られた銅粉を固液分離し乾燥させ回収した。また、扁平処理後にオレイン酸の添加は行わなかった。それ以外は実施例1と同様にして銅粉を得た。
実施例1において、原料銅粉の平均粒径D50が3.19μm、(D90-D10)/D50の値が1.07、粒度分布のSD値が1.10のものを使用し、ミル運転時間を300分として扁平処理を実施した。処理後のスラリーにオレイルアミンを0.1kg溶解させて表面処理を実施した。このようにして得られた銅粉を固液分離し乾燥させ回収した。それ以外は実施例1と同様にして銅粉を得た。
実施例4において、スラリー中の雰囲気を大気雰囲気にして、水分量を3000ppm以下に維持しない状態とし、ミル運転時間を300分とした。それ以外は実施例4と同様にして銅粉を得た。
実施例1において、原料銅粉の平均粒径D50が3.10μm、(D90-D10)/D50の値が1.20、粒度分布のSD値が1.37のものを使用し、スラリー中の雰囲気を大気雰囲気にして、水分量を3000ppm以下に維持しない状態とした。それ以外は実施例1と同様にして銅粉を得た。本比較例で得られた銅粉のSEM像を図2に示す。水分量を制御していないため、酸化に由来する表面凹凸を確認することができる。
実施例及び比較例で得られた銅粉について、400回タップ密度及び100回タップ密度を上述の方法で測定した。また、厚みの標準偏差SD/D50、平面アスペクト比、側面アスペクト比、結晶子サイズ、酸素元素の含有量、及び炭素元素の含有量を上述の方法で測定した。更に、塗膜緻密性及び塗膜連続性を以下の方法で評価した。これらの結果を表1に示す。なお、表には示していないが、実施例で得られた銅粉は、側面アスペクト比が2.0以上である銅粒子を個数基準で70%以上含んでいた。
実施例及び比較例で得られた銅粉10gに、エチルセルロース10質量%溶解させたターピネオール2.5gを加え、自公転ミキサーにて、混合を2000rpmで1分間行い、脱泡を2200rpmで30秒間行うことでペーストを得た。このペーストをガラス基板に幅10mm、長さ20mmに塗布した。この基板を窒素雰囲気で120℃度加熱することで乾燥塗膜を得た。この塗膜厚みを計測することで塗膜体積を求めた。また、あらかじめ測定した基板重量から塗膜重量を求め、塗膜重量/塗膜体積から塗膜密度g/cm3を算出した。
実施例及び比較例で得られた銅粉10gに、エチルセルロース10質量%溶解させたターピネオール10gを加え、自公転ミキサーにて、混合を2000rpmで1分間行い、脱泡を2200rpmで30秒間行うことでペーストを得た。このペーストをPETフィルムに厚み約20μmで塗布し、窒素雰囲気で120℃度加熱することで乾燥塗膜を得た。この塗膜を角度90°になるよう折り曲げた。折り曲げ回数は3回とした。折り曲げ後、光学顕微鏡で折り曲げ部分を観察し、基板であるPETフィルムが露出しておらず銅粉の連続性が保たれているものを〇評価とし、銅粉の連続性が無くPETフィルムが露出しているものを×評価とした。
また、図1と図2との対比から明らかなとおり、実施例1で得られた銅粉は、これを構成する銅粒子の表面が平滑であるのに対し、比較例2で得られた銅粉は、これを構成する銅粒子の表面が荒れていることが分かる。表面の荒れは、銅の酸化に起因して生じる亜酸化銅由来の凹凸であることが、本発明者の分析の結果判明した。
Claims (11)
- JIS Z2512:2012に準じて400回タップしたときのタップ密度が4.2g/cm3以上5.5g/cm3以下であり、
JIS Z2512:2012に準じて100回タップしたときのタップ密度が4.1g/cm3以上5.5g/cm3以下であり、
粒子の厚みの標準偏差SD(μm)/平均粒径D50(μm)の値が0.08以上0.26以下である、銅粉。 - 粒子の長径/粒子の短径の値であるアスペクト比の平均値が1.25以上3.00以下である、請求項1に記載の銅粉。
- 前記アスペクト比が1.25以上である粒子を、個数基準で30%以上含む、請求項2に記載の銅粉。
- 酸素元素の含有量が0.5質量%以下である、請求項1に記載の銅粉。
- 平均粒径D50が2.0μm以上5.0μm以下である、請求項1に記載の銅粉。
- 銅の結晶子サイズが50nm以上80nm以下である、請求項1に記載の銅粉。
- 炭素元素の含有量が0.40質量%以下である、請求項1に記載の銅粉。
- (D90-D10)/D50の値が1.00以上であり、球状銅粒子の集合体からなる原料銅粉を準備する工程と、
前記原料銅粉と有機溶媒とを混合してスラリーを調製する工程と、
前記スラリーをメディアミル装置による扁平化処理に付して、前記球状銅粒子を扁平銅粒子に変形させる工程と、を有する銅粉の製造方法であって、
前記扁平化処理を、前記スラリー中の水分量を0.30質量%以下に維持しながら、不活性雰囲気で行う、銅粉の製造方法。 - アトマイズ法で前記原料銅粉を製造する、請求項8に記載の製造方法。
- 粒度分布のSD値が1.00以上である前記原料銅粉を準備する、請求項8又は9に記載の製造方法。
- 前記扁平化処理を滑剤の不存在下に行う、請求項8に記載の銅粉の製造方法。
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JP2005200734A (ja) * | 2004-01-19 | 2005-07-28 | Dowa Mining Co Ltd | フレーク状銅粉およびその製造法 |
WO2007111231A1 (ja) * | 2006-03-24 | 2007-10-04 | Mitsui Mining & Smelting Co., Ltd. | 銅粉の製造方法及びその製造方法で得られた銅粉 |
JP2014222619A (ja) * | 2013-05-14 | 2014-11-27 | Dowaエレクトロニクス株式会社 | 導電膜 |
WO2015015865A1 (ja) * | 2013-07-31 | 2015-02-05 | 株式会社村田製作所 | 導電性ペースト、セラミック電子部品およびセラミック電子部品の製造方法 |
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JPH03247702A (ja) * | 1990-02-23 | 1991-11-05 | Asahi Chem Ind Co Ltd | 銀含有合金粉末ならびに該粉末を用いた導電性ペースト |
JP2005200734A (ja) * | 2004-01-19 | 2005-07-28 | Dowa Mining Co Ltd | フレーク状銅粉およびその製造法 |
WO2007111231A1 (ja) * | 2006-03-24 | 2007-10-04 | Mitsui Mining & Smelting Co., Ltd. | 銅粉の製造方法及びその製造方法で得られた銅粉 |
JP2014222619A (ja) * | 2013-05-14 | 2014-11-27 | Dowaエレクトロニクス株式会社 | 導電膜 |
WO2015015865A1 (ja) * | 2013-07-31 | 2015-02-05 | 株式会社村田製作所 | 導電性ペースト、セラミック電子部品およびセラミック電子部品の製造方法 |
WO2018123809A1 (ja) * | 2016-12-28 | 2018-07-05 | Dowaエレクトロニクス株式会社 | 銅粉およびその製造方法 |
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