JP5392884B2 - Method for producing copper powder - Google Patents
Method for producing copper powder Download PDFInfo
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- JP5392884B2 JP5392884B2 JP2007246083A JP2007246083A JP5392884B2 JP 5392884 B2 JP5392884 B2 JP 5392884B2 JP 2007246083 A JP2007246083 A JP 2007246083A JP 2007246083 A JP2007246083 A JP 2007246083A JP 5392884 B2 JP5392884 B2 JP 5392884B2
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- JP
- Japan
- Prior art keywords
- copper
- copper powder
- slurry
- cuprous oxide
- hydrazine
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 194
- 238000004519 manufacturing process Methods 0.000 title claims description 52
- 239000002002 slurry Substances 0.000 claims description 85
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 79
- -1 copper salt compound Chemical class 0.000 claims description 63
- 239000010949 copper Substances 0.000 claims description 61
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 60
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 60
- 229940112669 cuprous oxide Drugs 0.000 claims description 60
- 229910052802 copper Inorganic materials 0.000 claims description 50
- 238000006722 reduction reaction Methods 0.000 claims description 50
- 239000003638 chemical reducing agent Substances 0.000 claims description 49
- 229910052698 phosphorus Inorganic materials 0.000 claims description 40
- 239000011574 phosphorus Substances 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 33
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 150000001879 copper Chemical class 0.000 claims description 17
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 12
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 11
- 239000012066 reaction slurry Substances 0.000 claims description 11
- 239000012670 alkaline solution Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 230000002829 reductive effect Effects 0.000 claims description 7
- 239000012266 salt solution Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 description 85
- 238000009826 distribution Methods 0.000 description 42
- 230000009467 reduction Effects 0.000 description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 24
- 229910052799 carbon Inorganic materials 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 22
- 239000000243 solution Substances 0.000 description 17
- 239000012535 impurity Substances 0.000 description 15
- 239000007788 liquid Substances 0.000 description 15
- 239000004020 conductor Substances 0.000 description 13
- 238000005406 washing Methods 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 238000004220 aggregation Methods 0.000 description 7
- 230000002776 aggregation Effects 0.000 description 7
- 238000010304 firing Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910000365 copper sulfate Inorganic materials 0.000 description 6
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 230000001186 cumulative effect Effects 0.000 description 5
- 238000004381 surface treatment Methods 0.000 description 5
- GJYJYFHBOBUTBY-UHFFFAOYSA-N alpha-camphorene Chemical compound CC(C)=CCCC(=C)C1CCC(CCC=C(C)C)=CC1 GJYJYFHBOBUTBY-UHFFFAOYSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000003002 pH adjusting agent Substances 0.000 description 4
- 239000012756 surface treatment agent Substances 0.000 description 4
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 238000000889 atomisation Methods 0.000 description 3
- QKSIFUGZHOUETI-UHFFFAOYSA-N copper;azane Chemical compound N.N.N.N.[Cu+2] QKSIFUGZHOUETI-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 239000011164 primary particle Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 238000011946 reduction process Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000011231 conductive filler Substances 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 230000000694 effects Effects 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
- 230000002431 foraging effect Effects 0.000 description 2
- 150000002429 hydrazines Chemical class 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000001603 reducing effect Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 2
- 229940048086 sodium pyrophosphate Drugs 0.000 description 2
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-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
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- FUSNOPLQVRUIIM-UHFFFAOYSA-N 4-amino-2-(4,4-dimethyl-2-oxoimidazolidin-1-yl)-n-[3-(trifluoromethyl)phenyl]pyrimidine-5-carboxamide Chemical compound O=C1NC(C)(C)CN1C(N=C1N)=NC=C1C(=O)NC1=CC=CC(C(F)(F)F)=C1 FUSNOPLQVRUIIM-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 239000012493 hydrazine sulfate Substances 0.000 description 1
- 229910000377 hydrazine sulfate Inorganic materials 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- YWXYYJSYQOXTPL-SLPGGIOYSA-N isosorbide mononitrate Chemical compound [O-][N+](=O)O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 YWXYYJSYQOXTPL-SLPGGIOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001000 micrograph Methods 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
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- ASTWEMOBIXQPPV-UHFFFAOYSA-K trisodium;phosphate;dodecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[Na+].[O-]P([O-])([O-])=O ASTWEMOBIXQPPV-UHFFFAOYSA-K 0.000 description 1
- 238000009692 water atomization Methods 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
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/052—Metallic powder characterised by the size or surface area of the particles characterised by a mixture of particles of different sizes or by the particle size distribution
Description
本発明は、湿式法による銅粉の製造方法に関し、特に、銅塩水溶液を出発液として、二段還元により銅粉を得る製造方法に関する。 The present invention relates to a method for producing copper powder by a wet method, and more particularly to a method for producing copper powder by two-stage reduction using a copper salt aqueous solution as a starting solution.
銅粉は、銅ペーストや銅インクの原料として広く用いられてきた。例えば、銅ペーストは、粒径数μｍの微小な粒子からなる銅粉に樹脂成分を適宜配合してなるものであり、スクリーン印刷法を用いたプリント配線板の回路形成、各種電気的接点部等に応用され、焼成または固化させ導体膜として導電性を発揮するものである。 Copper powder has been widely used as a raw material for copper paste and copper ink. For example, a copper paste is formed by appropriately mixing a resin component with copper powder composed of fine particles having a particle diameter of several μm, forming a circuit on a printed wiring board using a screen printing method, various electrical contact portions, etc. Applied and is fired or solidified to exhibit conductivity as a conductor film.
プリント配線板等の小型化を受けて、当該銅ペーストにより形成された回路の導電性、信頼性等の点で、銅粉の更なる改良が市場において求められている。例えば、微細配線では、電気的特性に関する微少な変動が製品に影響を及ぼす場合があるので、導電性フィラーについても電気的安定性が高精度なレベルで求められている。また、微細配線のファインライン化のために、微粒な導電性フィラーが求められている。しかし、銅粉は微粒になる程表面エネルギーが高くなり、凝集しやすいので、粒度分布幅が広くなり、微粒均一な銅粉を得るのは難しい。そこで、微粒均一な銅粉が求められている。 In response to the miniaturization of printed wiring boards and the like, further improvements in copper powder are required in the market in terms of the conductivity and reliability of circuits formed from the copper paste. For example, in a fine wiring, since a slight variation regarding electrical characteristics may affect a product, electrical stability is also required for a conductive filler with a high accuracy level. In addition, a fine conductive filler is required to make fine wiring finer. However, the finer the copper powder, the higher the surface energy and the easier it is to agglomerate. Therefore, it is difficult to obtain a uniform copper powder with a wide particle size distribution range. Therefore, there is a demand for copper powder that is uniform in size.
また、導体形成の際、銅粉粒子に含まれる炭素成分により、高温焼成時に炭酸ガスが発生し、導体が不均一となり安定した導体形成の妨げとなる点が課題となっている。具体的には、銅粉粒子内部に炭素を多く含有する銅粉を銅ペーストの材料に用いると、高温焼成時に、形成された焼結膜の内部において炭酸ガスが発生する。この炭酸ガスにより、焼結膜の表面にクラックが発生したり、導体の内部欠陥が発生しやすくなる。このように、炭素、その他の不純物を含む銅粉は、抵抗値等の電気的特性に品質変動が生じる。このため、不純物が極力少ない純度の高い銅粉が求められていた。 Moreover, the carbon component contained in the copper powder particles during the formation of the conductor generates carbon dioxide gas at the time of high-temperature firing, causing the conductor to be non-uniform and hindering stable conductor formation. Specifically, when copper powder containing a large amount of carbon in the copper powder particles is used as the material for the copper paste, carbon dioxide gas is generated inside the formed sintered film during high-temperature firing. This carbon dioxide gas tends to cause cracks on the surface of the sintered film and internal defects of the conductor. Thus, the quality of the copper powder containing carbon and other impurities varies in electrical characteristics such as resistance value. For this reason, the copper powder with high purity with few impurities was calculated | required.
銅粉の製造方法の例として特許文献１には、湿式還元法を用いて、良好な粒径に制御されたフレーク銅粉が開示されている。また、特許文献２には、リン含有量が０．０１〜０．１０質量％であり、且つ、酸素含有量が０．３０質量％以下である銅粉末を用いる外部電極用銅ペースト組成物が開示されている。この特許文献２には、外部電極用銅ペースト組成物に用いられる球状の銅粉末として平均粒径を１〜４μｍとしており、外部電極用銅ペースト組成物に適度な粘性及び塗布性を得るために、有機ビヒクルを使用している。なお、この特許文献２に開示の銅粉末の製造方法は、湿式還元法、乾式法等、特に限定しておらず、水アトマイズ法により得られるものが好適であることが記載されている。 As an example of a method for producing copper powder, Patent Document 1 discloses a flake copper powder that is controlled to have a good particle size using a wet reduction method. Patent Document 2 discloses a copper paste composition for an external electrode using a copper powder having a phosphorus content of 0.01 to 0.10% by mass and an oxygen content of 0.30% by mass or less. It is disclosed. In Patent Document 2, an average particle diameter of 1 to 4 μm is used as a spherical copper powder used in a copper paste composition for external electrodes, and in order to obtain an appropriate viscosity and coatability for the copper paste composition for external electrodes. , Using organic vehicles. In addition, the manufacturing method of the copper powder disclosed by this patent document 2 is not specifically limited, such as a wet reduction method and a dry method, It describes that what is obtained by the water atomization method is suitable.
微粒均一且つ低不純物な銅粉へのニーズに対し、アトマイズ法により製造された微粒銅粉の場合、炭素量が低く、分散性の点でも優れた銅粉を製造することができるが、粗粒を含み、微細配線などには不向きであるとともに他の不純物を含む傾向がある。そして、粗粒を解消するために分級を強化すれば製造長期化や収率の低下により、製造コストが高くなるといった問題があった。 In the case of fine copper powder produced by the atomization method for the need for fine, uniform and low-impurity copper powder, it is possible to produce copper powder with low carbon content and excellent dispersibility. It is not suitable for fine wiring and tends to contain other impurities. And if classification was strengthened in order to eliminate coarse grains, there was a problem that the production cost was increased due to the prolonged production and the decrease in yield.
一方、従来の湿式還元法による銅粉は、一次粒子自体は微粒で均一になる傾向があるものの、反応性の観点から有機系の還元剤を用いることが多かった（例えば、特許文献３）。この結果、銅粉における有機剤吸着量が多くなるため、炭素の含有量が多くなる傾向がある。 On the other hand, the copper powder obtained by the conventional wet reduction method has a tendency that the primary particles themselves are fine and uniform, but an organic reducing agent is often used from the viewpoint of reactivity (for example, Patent Document 3). As a result, since the organic agent adsorption amount in the copper powder increases, the carbon content tends to increase.
また、無機還元剤を用いた湿式還元法の場合（例えば、特許文献４）、炭素含有量についての上記課題は解消されるものの、凝集が生じやすく、得られる銅粉の粒度は分布が広くブロードなものであった。 Further, in the case of a wet reduction method using an inorganic reducing agent (for example, Patent Document 4), although the above-mentioned problem with respect to the carbon content is solved, aggregation is likely to occur, and the resulting copper powder has a broad distribution and a broad particle size. It was something.
本発明は上記課題を受けて、粒度分布幅が極めて狭く、且つ不純物の含有量が少なく、導電率を高め、均質で高品質な銅粉と、このような銅粉を安定的且つ効率良く得られる銅粉の製造方法を提供することを目的とする。 In response to the above-mentioned problems, the present invention has a very narrow particle size distribution width, a small impurity content, an increased electrical conductivity, and a homogeneous and high-quality copper powder, and such a copper powder can be obtained stably and efficiently. It aims at providing the manufacturing method of the copper powder manufactured.
そこで、本発明者等は、鋭意研究を行った結果、湿式還元法を用いた以下の銅粉の製造方法を採用することで上記課題を達成する銅粉を得るに到った。 Therefore, as a result of intensive studies, the present inventors have come to obtain a copper powder that achieves the above problems by adopting the following method for producing a copper powder using a wet reduction method.
銅粉の製造方法：本発明に係る銅粉の製造方法は、銅塩水溶液にアルカリ溶液を添加して得られた銅塩化合物スラリーに、ヒドラジン系還元剤を添加して亜酸化銅スラリーとし、当該亜酸化銅スラリーを水洗し、再スラリー化した洗浄亜酸化銅スラリーに再びヒドラジン系還元剤を添加する銅粉の製造方法において、最終還元反応が終了するまでに、リンと銅のモル比がＰ／Ｃｕ＝０．０００１〜０．００３となるように、リン化合物を反応スラリーに添加することを特徴とする。 Copper powder manufacturing method: The copper powder manufacturing method according to the present invention is a copper salt compound slurry obtained by adding an alkaline solution to a copper salt aqueous solution, to add a hydrazine-based reducing agent to make a cuprous oxide slurry, In the copper powder manufacturing method in which the cuprous oxide slurry is washed with water and the hydrazine-based reducing agent is added again to the reslurried washed cuprous oxide slurry, the molar ratio of phosphorus and copper is increased until the final reduction reaction is completed. A phosphorus compound is added to the reaction slurry so that P / Cu = 0.0001 to 0.003.
更に、本発明に係る銅粉の製造方法は、前記銅塩化合物スラリーの銅濃度を１ｍｏｌ／Ｌ〜３ｍｏｌ／Ｌとすることが好ましい。 Furthermore, in the method for producing copper powder according to the present invention, the copper concentration of the copper salt compound slurry is preferably 1 mol / L to 3 mol / L.
本発明に係る銅粉の製造方法は、前記アルカリ溶液がアンモニア水溶液であることが好ましい。 In the method for producing copper powder according to the present invention, the alkaline solution is preferably an aqueous ammonia solution.
本発明に係る銅粉の製造方法は、前記銅塩化合物スラリーに、ヒドラジン系還元剤を添加し、還元反応を行う際のｐＨを３．５〜６．０に調整することが好ましい。 It is preferable that the manufacturing method of the copper powder which concerns on this invention adjusts pH at the time of adding a hydrazine type reducing agent to the said copper salt compound slurry, and performing a reductive reaction to 3.5-6.0.
本発明に係る銅粉の製造方法は、前記銅塩化合物スラリーに、ヒドラジン系還元剤を添加し、還元反応を行う際のｐＨ調整をアンモニア水溶液で行うことが好ましい。 In the method for producing copper powder according to the present invention, it is preferable to add a hydrazine-based reducing agent to the copper salt compound slurry and perform pH adjustment with an aqueous ammonia solution when performing the reduction reaction.
本発明に係る銅粉の製造方法は、前記洗浄亜酸化銅スラリーに再びヒドラジン系還元剤添加前のスラリーのｐＨを４．１〜６．０に調整することが好ましい。 In the method for producing copper powder according to the present invention, it is preferable to adjust the pH of the slurry before addition of the hydrazine-based reducing agent to the washed cuprous oxide slurry again to 4.1 to 6.0.
本発明に係る銅粉の製造方法は、不純物の含有を極力排除しながら、粒度分布幅が極めて狭い銅粉を製造することができる。 The method for producing copper powder according to the present invention can produce copper powder having a very narrow particle size distribution width while eliminating impurities as much as possible .
以下、本発明に係る銅粉の製造方法の最良の実施の形態に関して説明する。 Hereinafter, the best embodiment of the method for producing copper powder according to the present invention will be described.
銅粉の製造方法：まず、本発明に係る銅粉の製造方法の前提となる工程の概略を説明する。最初に、銅塩水溶液にアルカリ溶液を添加して銅塩化合物スラリーにする。この銅塩化合物スラリーにヒドラジン系還元剤を添加して亜酸化銅スラリーとする（第１還元処理）。次に、亜酸化銅スラリーを水洗し再スラリー化して洗浄亜酸化銅スラリーとし、この洗浄亜酸化銅スラリーに再びヒドラジン系還元剤を添加する工程（第２還元処理）を経て銅粉を還元析出させて銅粉を得るのである。 Method for producing copper powder: First, an outline of the process as a premise of the method for producing copper powder according to the present invention will be described. First, an alkali solution is added to a copper salt aqueous solution to form a copper salt compound slurry. A hydrazine-based reducing agent is added to the copper salt compound slurry to form a cuprous oxide slurry (first reduction treatment). Next, the cuprous oxide slurry is washed with water and reslurried to obtain a washed cuprous oxide slurry, and the copper powder is reduced and precipitated through a step of adding a hydrazine-based reducing agent to the washed cuprous oxide slurry again (second reduction treatment). To obtain copper powder.
そして、本発明に係る銅粉の製造方法では、上記工程において、最終還元反応終了時までに、モル比でＰ／Ｃｕ＝０．０００１〜０．００３となる量のリン化合物を反応スラリーに添加することを特徴とする。即ち、上記方法において、銅に対して極めて微量のリン成分を添加することより析出粒子の成長過程での凝集を抑えて、粒度分布幅が極めて狭く且つ低不純物である高品質な銅粉を製造することができるのである。以下、銅粉の製造方法を詳述する。 And in the manufacturing method of the copper powder which concerns on this invention, in the said process, the phosphorus compound of the quantity used as P / Cu = 0.0001-0.003 by molar ratio is added to reaction slurry by the time of completion | finish of final reduction reaction. It is characterized by doing. That is, in the above method, by adding a very small amount of phosphorus component to copper, the aggregation in the growth process of the precipitated particles is suppressed, and high-quality copper powder having a very narrow particle size distribution width and low impurities is produced. It can be done. Hereinafter, the manufacturing method of copper powder is explained in full detail.
まず、銅塩水溶液にアルカリ溶液を添加することにより、銅塩と反応させて銅塩化合物が生成し、これを銅塩化合物スラリーとする。例えば、銅塩水溶液にアルカリ溶液を３０分掛けて徐々に添加し、その後３０分静置して熟成させることにより、銅塩と反応させて、二価の銅化合物を得る。 First, an alkaline solution is added to an aqueous copper salt solution to react with the copper salt to produce a copper salt compound, which is used as a copper salt compound slurry. For example, an alkaline solution is gradually added to an aqueous copper salt solution over 30 minutes, and then allowed to stand for 30 minutes for aging to react with the copper salt to obtain a divalent copper compound.
ここで、銅塩水溶液は、水に水溶性銅塩を加え、部分溶解させたものである。水溶性銅塩は、硫酸銅、硝酸銅、酢酸銅、塩化銅等が考えられ、中でも硫酸銅、硝酸銅が好ましい。また、アルカリ溶液としては、アンモニア水溶液、水酸化カリウム、水酸化ナトリウム等が挙げられる。特に、アンモニア水溶液を用いると、不純物を排除し、純度の高い銅粉が得られる点で好ましい。 Here, the copper salt aqueous solution is obtained by adding a water-soluble copper salt to water and partially dissolving it. Examples of the water-soluble copper salt include copper sulfate, copper nitrate, copper acetate, copper chloride and the like, and among them, copper sulfate and copper nitrate are preferable. Examples of the alkaline solution include an aqueous ammonia solution, potassium hydroxide, and sodium hydroxide. In particular, it is preferable to use an aqueous ammonia solution in terms of eliminating impurities and obtaining high-purity copper powder.
銅塩化合物スラリーの銅濃度は、１ｍｏｌ／Ｌ〜３ｍｏｌ／Ｌとすることが好ましい。銅塩化合物スラリーの銅濃度が１ｍｏｌ／Ｌ未満であると、従来と比べ生産の効率化を図るという効果が得られない。一方、銅塩化合物スラリーの銅濃度が３ｍｏｌ／Ｌを上回ると、凝集が生じやすくなり、粒度分布の制御が難しく製造安定性が望めない。そして、より好ましい銅塩化合物スラリーの銅濃度は、１．５ｍｏｌ／Ｌ〜２．５ｍｏｌ／Ｌである。 The copper concentration of the copper salt compound slurry is preferably 1 mol / L to 3 mol / L. If the copper concentration of the copper salt compound slurry is less than 1 mol / L, the effect of increasing the production efficiency compared to the conventional case cannot be obtained. On the other hand, when the copper concentration of the copper salt compound slurry exceeds 3 mol / L, aggregation tends to occur, and it is difficult to control the particle size distribution and production stability cannot be expected. And the copper concentration of a more preferable copper salt compound slurry is 1.5 mol / L-2.5 mol / L.
アルカリ溶液は、中和生成物としての銅塩化合物を得られる量であれば良く、後の工程におけるｐＨとの関係を考慮する。例えば、アルカリ溶液としてアンモニア水溶液を用いる場合、その添加量は、銅１ｍｏｌに対してアンモニア成分が１．０ｍｏｌ〜３．８ｍｏｌとなるように用いる。アンモニア成分がこの範囲を外れると、後の還元工程における適正なｐＨ範囲へのコントロールが困難となる。 The alkaline solution should just be the quantity which can obtain the copper salt compound as a neutralization product, and considers the relationship with pH in a subsequent process. For example, when an aqueous ammonia solution is used as the alkaline solution, the added amount is such that the ammonia component is 1.0 mol to 3.8 mol with respect to 1 mol of copper. When the ammonia component is out of this range, it becomes difficult to control the pH to an appropriate pH range in the subsequent reduction step.
本発明に係る銅粉の製造方法は、銅塩化合物スラリーの銅濃度を比較的高濃度となるように液量を調整するのが好ましい。従来の湿式還元法では、還元前の銅塩化合物スラリーの銅濃度を高くすると、析出粒子の凝集が生じやすく、粒度分布幅が狭い銅粉を効率良く製造することが出来なかった。しかし、本発明に係る銅粉の製造方法では、ｐＨ変動範囲の調整、使用物質の混合条件等を種々調整することで、還元反応前の銅塩化合物スラリーの銅濃度を上記範囲としても、粒度分布幅が極めて狭い銅粉を得ることができる。 In the method for producing copper powder according to the present invention, the amount of the liquid is preferably adjusted so that the copper concentration of the copper salt compound slurry is relatively high. In the conventional wet reduction method, if the copper concentration of the copper salt compound slurry before reduction is increased, the precipitated particles are likely to aggregate and copper powder having a narrow particle size distribution width cannot be efficiently produced. However, in the method for producing copper powder according to the present invention, it is possible to adjust the pH fluctuation range, the mixing conditions of the substances used, and the like, so that the copper concentration of the copper salt compound slurry before the reduction reaction is within the above range. Copper powder with a very narrow distribution width can be obtained.
次に、前記銅塩化合物スラリーにヒドラジン系還元剤を添加して亜酸化銅スラリーとする（第１還元）。本発明に係る銅粉の製造方法では、銅塩化合物を亜酸化銅に還元する程度にヒドラジン系還元剤の添加量を調整して亜酸化銅スラリーとする。即ち、第１還元処理により、亜酸化銅スラリーを調製し、後の第２還元処理時の反応を安定化させ、還元析出させる粒子の均一化を図るのである。 Next, a hydrazine-based reducing agent is added to the copper salt compound slurry to form a cuprous oxide slurry (first reduction). In the method for producing copper powder according to the present invention, the amount of the hydrazine-based reducing agent is adjusted so as to reduce the copper salt compound to cuprous oxide to obtain a cuprous oxide slurry. That is, a cuprous oxide slurry is prepared by the first reduction treatment, the reaction during the subsequent second reduction treatment is stabilized, and the particles to be reduced and precipitated are made uniform.
この第１還元処理時にヒドラジン系還元剤を用いると、亜酸化銅粒子の表面に対して還元剤成分が残留する可能性が低く、汚染物質となりにくい。 When a hydrazine-based reducing agent is used during the first reduction treatment, the possibility that the reducing agent component remains on the surface of the cuprous oxide particles is low, and it is difficult to become a contaminant.
ヒドラジン系還元剤としては、抱水ヒドラジン、硫酸ヒドラジン、無水ヒドラジン等種々のものが考えられるが、抱水ヒドラジンが最も好ましい。これらのヒドラジン系還元剤は、単独または混合して用いることが可能である。そして、ヒドラジン系還元剤は、反応系の溶液に迅速に拡散し、均一な反応を得るために、溶液の状態で反応に用いることが好ましい。 As the hydrazine-based reducing agent, various substances such as hydrazine hydrate, hydrazine sulfate, and anhydrous hydrazine can be considered, and hydrazine hydrate is most preferable. These hydrazine-based reducing agents can be used alone or in combination. The hydrazine-based reducing agent is preferably used in the reaction in the form of a solution in order to quickly diffuse into the reaction system solution and obtain a uniform reaction.
ヒドラジン系還元剤の添加量は、銅塩化合物スラリー中の銅１ｍｏｌに対して０．３ｍｏｌ〜０．５ｍｏｌとするのが好ましい。ヒドラジン系還元剤の添加量が、上記銅１ｍｏｌに対して０．３ｍｏｌ未満の場合には、未反応の銅塩化合物が多く残留するため好ましくない。一方、ヒドラジン系還元剤の添加量が上記銅１ｍｏｌに対して０．５ｍｏｌを超えるように添加すると、亜酸化銅の段階で還元反応を止めることができない。 The amount of the hydrazine-based reducing agent added is preferably 0.3 mol to 0.5 mol with respect to 1 mol of copper in the copper salt compound slurry. When the addition amount of the hydrazine-based reducing agent is less than 0.3 mol with respect to 1 mol of copper, a large amount of unreacted copper salt compound remains, which is not preferable. On the other hand, when the addition amount of the hydrazine-based reducing agent exceeds 0.5 mol with respect to 1 mol of copper, the reduction reaction cannot be stopped at the cuprous oxide stage.
なお、銅塩化合物スラリーにヒドラジン系還元剤を添加し還元反応を行う際のｐＨを３．５〜６．０に調整する。この溶液ｐＨが上記範囲を外れると、得られる亜酸化銅粒子の粒径のバラツキが大きくなり、最終的製品である銅粉粒子の粒度分布幅が広くなる。 In addition, the pH at the time of performing a reductive reaction by adding a hydrazine type reducing agent to a copper salt compound slurry is adjusted to 3.5-6.0. When the solution pH is out of the above range, the variation in the particle size of the obtained cuprous oxide particles becomes large, and the particle size distribution width of the copper powder particles as the final product becomes wide.
この銅塩化合物スラリーから亜酸化銅スラリーにする第１還元処理では、ヒドラジン系還元剤を添加しつつ、ｐＨ調整剤としてアンモニア水溶液を用いて、ｐＨ変動を制御しながら還元処理を行うのが好ましい。このように、ｐＨ調整剤としてアンモニア水溶液を用いるのは、銅塩化合物スラリーの生成時にアルカリ溶液としてアンモニアを用いて中和したことを考慮すると、使用物質を同一にして、異種成分の使用を可能な限り排除して、残留不純物を極力排除するためである。この結果、得られる銅粉の純度コントロールが容易となる。 In the first reduction treatment from the copper salt compound slurry to the cuprous oxide slurry, it is preferable to carry out the reduction treatment while controlling the pH fluctuation using an aqueous ammonia solution as a pH adjuster while adding a hydrazine-based reducing agent. . As described above, the aqueous ammonia solution is used as the pH adjusting agent, considering that neutralization was performed using ammonia as the alkaline solution during the production of the copper salt compound slurry. This is to eliminate as much as possible and to eliminate residual impurities as much as possible. As a result, purity control of the obtained copper powder becomes easy.
上述の第１還元処理においては、銅塩化合物スラリー中の銅１ｍｏｌに対し、添加終了時において、ヒドラジン系還元剤が０．３ｍｏｌ〜０．５ｍｏｌとし、アンモニア水溶液が（アンモニアとして）０．２ｍｏｌ〜０．４ｍｏｌの割合となるように連続添加することが好ましい。こうして添加された反応スラリーのｐＨは、還元剤及びｐＨ調整剤の添加開始時の始点ｐＨと添加終了時の終点ｐＨとの差が３．０以下となるように調整すればよい。 In the first reduction treatment described above, with respect to 1 mol of copper in the copper salt compound slurry, at the end of addition, the hydrazine-based reducing agent is 0.3 mol to 0.5 mol, and the aqueous ammonia solution (as ammonia) is 0.2 mol to It is preferable to add continuously so that it may become a ratio of 0.4 mol. The pH of the reaction slurry thus added may be adjusted so that the difference between the starting point pH at the start of the addition of the reducing agent and the pH adjusting agent and the end point pH at the end of the addition is 3.0 or less.
ここで、亜酸化銅スラリーは亜酸化銅を含有するスラリーを意味し、亜酸化銅以外の構成成分を含む場合もある。後述する洗浄亜酸化銅スラリーについても同様である。 Here, the cuprous oxide slurry means a slurry containing cuprous oxide, and may contain components other than cuprous oxide. The same applies to the washed cuprous oxide slurry described later.
そして、得られた亜酸化銅スラリーのｐＨを３．５〜６．０の範囲にすると、以降の工程において反応スラリーのｐＨ変動を好適な範囲に抑えられる。この結果、得られる銅粉の粒径の均一化を図ることができる。亜酸化銅スラリーをｐＨ６．０よりアルカリ性側とすると、亜酸化銅スラリー中の銅成分が亜酸化銅に止まらずメタルを形成して凝集が生じる。一方、亜酸化銅スラリーをｐＨ３．５より酸性側とすると、亜酸化銅の還元が不十分となり、製造効率が低下する。 And when pH of the obtained cuprous oxide slurry is made into the range of 3.5-6.0, the pH fluctuation | variation of the reaction slurry can be restrained in a suitable range in subsequent processes. As a result, the particle size of the obtained copper powder can be made uniform. When the cuprous oxide slurry is set to an alkaline side from pH 6.0, the copper component in the cuprous oxide slurry does not stop at the cuprous oxide but forms a metal and agglomerates. On the other hand, when the cuprous oxide slurry is set to the acidic side from pH 3.5, the reduction of cuprous oxide becomes insufficient and the production efficiency is lowered.
そして、第１還元処理時の反応スラリー温度は、４０℃〜６０℃の範囲を採用することが好ましい。４０℃未満の温度では、還元反応速度が遅く工業的生産性を満足しない。一方、反応スラリーの温度が６０℃を超えると、還元速度が速くなりすぎて不均一な還元反応が起こるため、得られる銅粉の粉体特性が劣化する。 And it is preferable to employ | adopt the range of 40 to 60 degreeC as the reaction slurry temperature at the time of a 1st reduction process. At temperatures below 40 ° C., the reduction reaction rate is slow and industrial productivity is not satisfied. On the other hand, when the temperature of the reaction slurry exceeds 60 ° C., the reduction rate becomes too fast and a non-uniform reduction reaction occurs, so that the powder characteristics of the obtained copper powder deteriorate.
次に、亜酸化銅スラリーを水洗し、再スラリー化して洗浄亜酸化銅スラリーとする。まず、亜酸化銅スラリーを静置して亜酸化銅粒子を沈殿させる。亜酸化銅粒子の沈殿後、上澄液を除去して水を添加することにより亜酸化銅粒子を洗浄し、再スラリー化して洗浄亜酸化銅スラリーとする。洗浄亜酸化銅スラリーのｐＨが４．１〜６．０であると、以降の工程におけるｐＨ変動を好適な範囲に抑えられ、得られる銅粉の粒径を精度良く揃えることができる。 Next, the cuprous oxide slurry is washed with water and reslurried to obtain a washed cuprous oxide slurry. First, a cuprous oxide slurry is allowed to stand to precipitate cuprous oxide particles. After precipitation of the cuprous oxide particles, the supernatant is removed and water is added to wash the cuprous oxide particles and reslurry to obtain a washed cuprous oxide slurry. When the pH of the washed cuprous oxide slurry is 4.1 to 6.0, the pH fluctuation in the subsequent steps can be suppressed within a suitable range, and the particle size of the obtained copper powder can be accurately aligned.
亜酸化銅粒子の洗浄方法に関しては、特段の限定はなく、公知の洗浄方法を採用することが可能である。しかし、以下に示すリパルプ洗浄を採用して、洗浄レベルを洗浄中の亜酸化銅スラリーのｐＨ値で管理することが好ましい。リパルプ洗浄は、亜酸化銅を沈殿させて上澄みを廃棄し、洗浄水を注ぎ足すという操作を複数回行う。そして、リパルプ洗浄は、洗浄水を注ぎ足した洗浄亜酸化銅スラリーのｐＨが４．１〜６．０の範囲のいずれか一定のｐＨ値になるまで繰り返し洗浄するのが好ましい。洗浄亜酸化銅スラリーのｐＨが４．１より酸性側にあると、還元効率が悪くなる。一方、洗浄亜酸化銅スラリーのｐＨが６．０よりアルカリ性側にあると、その後、銅粉を得るために還元剤を添加する際の反応のバラツキが大きく、分散性が劣る等粉体特性が悪くなる。 There is no particular limitation on the cleaning method for the cuprous oxide particles, and a known cleaning method can be employed. However, it is preferable to employ the following repulp washing and manage the washing level with the pH value of the cuprous oxide slurry being washed. In the repulp washing, the operation of precipitating cuprous oxide, discarding the supernatant, and adding washing water is performed a plurality of times. The repulp washing is preferably carried out repeatedly until the pH of the washed cuprous oxide slurry into which washing water has been added reaches a certain pH value in the range of 4.1 to 6.0. When the pH of the washed cuprous oxide slurry is on the acidic side from 4.1, the reduction efficiency is deteriorated. On the other hand, when the pH of the washed cuprous oxide slurry is more alkaline than 6.0, the powder characteristics such as the dispersion of the reaction when the reducing agent is added to obtain copper powder and the dispersibility are poor. Deteriorate.
そして、より好ましくは、洗浄亜酸化銅スラリーは、ｐＨ４．３〜４．７の範囲のいずれか一定のｐＨになるまで洗浄する。洗浄亜酸化銅スラリーのｐＨをこの範囲とすることにより、工程安定性に最も優れる。 More preferably, the washed cuprous oxide slurry is washed until a certain pH in the range of pH 4.3 to 4.7 is reached. By setting the pH of the washed cuprous oxide slurry within this range, the process stability is most excellent.
こうして調製された洗浄亜酸化銅スラリーにヒドラジン系還元剤を添加して銅粉を還元析出させる（第２還元処理）。そして、析出粒子を濾過、洗浄、乾燥させて銅粉を得る。添加するヒドラジン系還元剤の量は、添加終了時において、洗浄亜酸化銅スラリーに含まれる銅１ｍｏｌに対して０．３ｍｏｌ〜１．５ｍｏｌの割合で添加することが好ましい。そして、銅塩化合物スラリーに添加するヒドラジン系還元剤と、洗浄亜酸化銅スラリーに添加するヒドラジン系還元剤は、トータルで銅１ｍｏｌに対して０．６ｍｏｌ〜２．０ｍｏｌの割合にする。 A hydrazine-based reducing agent is added to the washed cuprous oxide slurry thus prepared to reduce and precipitate copper powder (second reduction treatment). Then, the precipitated particles are filtered, washed and dried to obtain copper powder. The amount of the hydrazine-based reducing agent to be added is preferably 0.3 to 1.5 mol with respect to 1 mol of copper contained in the washed cuprous oxide slurry at the end of the addition. The hydrazine-based reducing agent added to the copper salt compound slurry and the hydrazine-based reducing agent added to the washed cuprous oxide slurry are in a ratio of 0.6 mol to 2.0 mol with respect to 1 mol of copper in total.
ヒドラジン系還元剤の添加により還元反応を行う直前のスラリーｐＨを４．１〜６．０の範囲に調整するのが好ましい。還元反応時のｐＨが４．１より酸性側であると、粗粒が増えて分散性が悪くなる。一方、還元反応時のｐＨが６．０よりアルカリ性側にあると、還元剤が多くなり微粒な析出粒子数が過剰に多くなる。 It is preferable to adjust the slurry pH immediately before performing the reduction reaction to a range of 4.1 to 6.0 by adding a hydrazine-based reducing agent. If the pH during the reduction reaction is more acidic than 4.1, coarse particles increase and dispersibility deteriorates. On the other hand, if the pH during the reduction reaction is more alkaline than 6.0, the reducing agent is increased and the number of fine precipitated particles is excessively increased.
なお、銅塩化合物スラリーにヒドラジン系還元剤を添加する（第１還元処理）と同様に、ヒドラジン系還元剤を添加する（第２還元処理）前の洗浄亜酸化銅スラリーの銅濃度を、１ｍｏｌ／Ｌ〜３ｍｏｌ／Ｌとなるように液量調整すると、粒度分布幅が狭い銅粉を得ることができる。なお、より好ましい銅濃度は、１．５ｍｏｌ／Ｌ〜２．５ｍｏｌ／Ｌである。 In addition, similarly to adding a hydrazine-based reducing agent to the copper salt compound slurry (first reduction treatment), the copper concentration of the washed cuprous oxide slurry before adding the hydrazine-based reducing agent (second reduction treatment) is 1 mol. When the liquid volume is adjusted to be / L to 3 mol / L, copper powder having a narrow particle size distribution width can be obtained. A more preferable copper concentration is 1.5 mol / L to 2.5 mol / L.
添加するヒドラジン系還元剤の温度は４０℃〜６０℃の範囲の一定温度レベルに保つことが好ましい。ヒドラジン系還元剤の温度が４０℃より低いと、還元反応が鈍くなり、工業上望ましい生産性を満たさない。一方、ヒドラジン系還元剤の温度が６０℃より高いと、還元反応が早くなりすぎて粒径が不揃いとなりやすい。 The temperature of the hydrazine-based reducing agent to be added is preferably maintained at a constant temperature level in the range of 40 ° C to 60 ° C. When the temperature of the hydrazine-based reducing agent is lower than 40 ° C., the reduction reaction becomes dull and the industrially desirable productivity is not satisfied. On the other hand, when the temperature of the hydrazine-based reducing agent is higher than 60 ° C., the reduction reaction becomes too fast, and the particle size tends to be uneven.
第１還元処理と第２還元処理で用いる還元剤は、同種のヒドラジン系還元剤を用いるので、還元剤としてのヒドラジン類の還元能が粉体特性の良好な銅粉を得るのに適している。加えて、銅粉の還元に用いる異種成分を可能な限り少なくし、銅粉の粒子表面への不純物質の混入を抑制することができる。 The reducing agent used in the first reduction treatment and the second reduction treatment uses the same type of hydrazine-based reducing agent, so that it is suitable for obtaining copper powder with good reducing properties of the hydrazines as the reducing agent. . In addition, it is possible to reduce the number of different components used for the reduction of the copper powder as much as possible, and to suppress contamination of impurities on the surface of the copper powder particles.
なお、第２還元処理が終了した段階の反応スラリーの状態のまま、流体ミル法（ファインロールミル等）、層流混合法（Ｔ．Ｋ．フィルミックス等）を用いて、高速で遠心流動するスラリー内で、粒子同士を衝突させて解砕し、一次粒子に近付け、同時に粒子表面の平滑化を行う解粒処理を施し、粒子分散性を更に向上させることも好ましい。 In addition, the slurry which carries out the centrifugal flow at high speed using the fluid mill method (fine roll mill etc.) and the laminar flow mixing method (TK fill mix etc.) with the state of the reaction slurry in the stage which the 2nd reduction process was complete | finished. Among them, it is also preferable to further improve the particle dispersibility by pulverizing particles by colliding them, bringing them closer to the primary particles, and simultaneously performing a pulverization treatment for smoothing the particle surface.
リン化合物の添加：本発明に係る銅粉の製造方法は、上述の製造方法において、最終還元反応が終了するまでに、リンと銅のモル比がＰ／Ｃｕ＝０．０００１〜０．００３となるように、リン化合物を反応スラリーに添加することが特徴である。リン化合物を添加することにより、リン化合物が立体障害として作用し、析出粒子の凝集成長を防ぎ、単分散化を図ることができる。その結果、得られた銅粉の粒度分布は飛躍的に狭くすることができる。 Addition of phosphorus compound: The method for producing copper powder according to the present invention is such that the molar ratio of phosphorus and copper is P / Cu = 0.0001 to 0.003 before the final reduction reaction is completed in the above production method. Thus, the phosphorus compound is added to the reaction slurry. By adding the phosphorus compound, the phosphorus compound acts as a steric hindrance, preventing the aggregated growth of the precipitated particles and achieving monodispersion. As a result, the particle size distribution of the obtained copper powder can be dramatically narrowed.
リン化合物は、反応スラリー中のリンと銅のモル比がＰ／Ｃｕ＝０．０００１〜０．００３と、極めて微量を添加する。不純物含有量を抑えて、高純度の銅粉を得るためには、製造工程における添加物質の量や種類を極力抑える必要がある。しかし、微粒化を図ると、凝集しやすくなるので、微粒且つ粒度分布幅の極めて狭い銅粉を得るためには、リン化合物の添加が有効である。本発明者等は、リン化合物の添加量を最小限とすべく検討した結果、上記割合でリン化合物を添加すると、最も効果的であることに想到したのである。 The phosphorus compound is added in a very small amount such that the molar ratio of phosphorus and copper in the reaction slurry is P / Cu = 0.0001 to 0.003. In order to suppress the impurity content and obtain high-purity copper powder, it is necessary to suppress the amount and type of additive substances in the manufacturing process as much as possible. However, since atomization tends to agglomerate, the addition of a phosphorus compound is effective to obtain finely divided copper powder having a very narrow particle size distribution width. The inventors of the present invention have studied to minimize the addition amount of the phosphorus compound, and as a result, have found that it is most effective to add the phosphorus compound at the above ratio.
ここで、図１に、リン化合物の添加割合と、粒度分布幅との相関を示す。図１のグラフでは、横軸にリン化合物の添加割合を示すＰ／Ｃｕをとり、縦軸には銅粉の粒度分布幅の広さを示す値として、体積累積平均粒径Ｄ５０及びレーザー回折散乱式粒度分布測定法により測定した粒度分布の標準偏差ＳＤを用いて表されるＳＤ／Ｄ５０の値をとった。 Here, FIG. 1 shows the correlation between the addition ratio of the phosphorus compound and the particle size distribution width. In the graph of FIG. 1, P / Cu indicating the addition ratio of the phosphorus compound is taken on the horizontal axis, and the volume cumulative average particle diameter D 50 and laser diffraction are taken on the vertical axis as values showing the width of the particle size distribution width of the copper powder. using the standard deviation SD of the particle size distribution measured by scattering particle size distribution measuring method took the value of SD / D 50 represented.
ここでいう標準偏差ＳＤとは、レーザー回折散乱式粒度分布測定法を用いて得られる全粒径データのバラツキを表す指標であり、この値が大きな程、バラツキが大きなものとなる。そして、標準偏差ＳＤと、体積累積平均粒径Ｄ５０との比であるＳＤ／Ｄ５０により粒度分布幅の程度を示す。この値が大きい程、粒度分布幅が広いと言える。 The standard deviation SD here is an index representing the variation of the total particle size data obtained using the laser diffraction / scattering particle size distribution measuring method, and the larger this value, the larger the variation. The degree of the particle size distribution width is indicated by SD / D 50 which is a ratio of the standard deviation SD and the volume cumulative average particle diameter D 50 . It can be said that the larger this value, the wider the particle size distribution width.
図１を見ると、リンを添加しない場合（Ｐ／Ｃｕ＝０）からＰ／Ｃｕ＝０．０００１より少ないリン添加量の場合は、ＳＤ／Ｄ５０の値が０．５５を上回る値となり、リンを添加することによる単分散化の効果が十分に得られない。これに対し、リン添加割合が、Ｐ／Ｃｕ＝０．０００１以上にすると、ＳＤ／Ｄ５０の値が顕著に低下する。そして、本発明の上限であるＰ／Ｃｕ＝０．００３を上回る量のリンを添加しても、ＳＤ／Ｄ５０の値に変化が見られない。そもそも、本発明は、不純物含有量を抑えた高純度の銅粉を得ることを目的としているので、リンの添加量は最小限に抑えたい。したがって、リンの添加量の上限をＰ／Ｃｕ＝０．００３とする。 Referring to FIG. 1, when phosphorus is not added (P / Cu = 0) to phosphorus addition amount less than P / Cu = 0.0001, the SD / D 50 value exceeds 0.55. The effect of monodispersing by adding phosphorus cannot be sufficiently obtained. On the other hand, when the phosphorus addition ratio is P / Cu = 0.0001 or more, the value of SD / D 50 is significantly reduced. Even with the addition of phosphorus in an amount in excess of P / Cu = 0.003 which is the upper limit of the present invention, not change was observed in the value of SD / D 50. In the first place, the purpose of the present invention is to obtain high-purity copper powder with a reduced impurity content, so it is desirable to minimize the amount of phosphorus added. Therefore, the upper limit of the addition amount of phosphorus is set to P / Cu = 0.003.
リン化合物の添加時期は、洗浄亜酸化銅スラリーにヒドラジン系還元剤を添加し、その還元反応が終了するまでのいずれかの段階でリン化合物を上記割合で添加すれば良い。特に、洗浄亜酸化銅スラリーを調製した後に添加すると、洗浄後になるので、リン化合物の添加量を少量に抑えることができるので、不純物含有量を抑える点で好ましい。 The phosphorus compound may be added at the above ratio at any stage until the hydrazine-based reducing agent is added to the washed cuprous oxide slurry and the reduction reaction is completed. In particular, when the cleaning cuprous oxide slurry is prepared and then added, it is after the cleaning, so that the amount of the phosphorus compound added can be suppressed to a small amount, which is preferable in terms of suppressing the impurity content.
リン化合物としては、反応スラリーにおいてリン成分を効率良く分散させるためには水溶性リン化合物が好ましい。水溶性リン化合物としては、リン酸ナトリウム、リン酸、次亜リン酸アンモニウムのいずれかを用いることが好ましい。特に、次亜リン酸アンモニウムを用いると、微粒且つ均一な粒径の粒子の析出に好適である。 As the phosphorus compound, a water-soluble phosphorus compound is preferable in order to efficiently disperse the phosphorus component in the reaction slurry. As the water-soluble phosphorus compound, it is preferable to use any one of sodium phosphate, phosphoric acid, and ammonium hypophosphite. In particular, when ammonium hypophosphite is used, it is suitable for precipitation of fine particles having a uniform particle size.
以上のようにして得た銅粉は、濾過、洗浄、乾燥等の一般的工程を経て、銅粉として製品化される。そして、この銅粉は、耐酸化性を向上させるため、有機表面処理を施すことが好ましい。表面処理剤としては、必要に応じて脂肪酸又はアミン類のいずれかを含むのが好ましく、具体的には、オレイン酸、ステアリン酸等の脂肪酸やオクタデシルアミン、オレイルアミン等のアミン類が好ましい。また、乾燥した銅粉の状態でも、必要に応じて分級装置、ハイブリタイザー、ターボクラシファイア等の粒子同士の衝突処理が可能な装置を用いて解粒処理を行い、粒子分散性を向上させることも可能である。 The copper powder obtained as described above is commercialized as copper powder through general steps such as filtration, washing, and drying. The copper powder is preferably subjected to an organic surface treatment in order to improve oxidation resistance. The surface treatment agent preferably contains either a fatty acid or an amine as required. Specifically, fatty acids such as oleic acid and stearic acid, and amines such as octadecylamine and oleylamine are preferred. In addition, even in the state of dried copper powder, it is possible to improve the particle dispersibility by performing a pulverization process using an apparatus capable of collision processing between particles such as a classifier, a hybridizer, and a turbo classifier as necessary. Is possible.
本発明の製造方法により得られる銅粉：本発明に係る銅粉の製造方法によれば、レーザー回折散乱式粒度分布測定法による体積累積平均粒径Ｄ５０が０．１μｍ〜５．０μｍであり、粒度分布幅の広さを示す前記ＳＤ／Ｄ５０の値が０．２〜０．５という粒度分布幅が狭い状態で製造可能となる。 Copper powder obtained by the production method of the present invention: According to the production method of the copper powder according to the present invention, the volume accumulated average particle diameter D 50 by laser diffraction scattering particle size distribution measuring method be 0.1μm~5.0μm The SD / D 50 value indicating the width of the particle size distribution width can be produced in a state where the particle size distribution width is 0.2 to 0.5 .
本発明に係る銅粉の製造方法により得られる銅粉は、Ｄ５０が０．１μｍ未満となると、微粒化に伴う凝集が生じる。その一方で、凝集を抑えるためにリン化合物の添加量を増やすと、微細配線の形成回路の導電不良を起こさないレベルの低不純物量にするという本発明の目的が達成できない。一方、Ｄ５０が５．０μｍを上回るレベルとなると、微細配線の形成には適さない。なお、より好ましい平均粒径Ｄ５０は０．５〜３．５μｍである。 Copper powder obtained by the production method of the copper powder according to the present invention, when D 50 is less than 0.1 [mu] m, aggregation associated with atomization occurs. On the other hand, when the addition amount of the phosphorus compound is increased in order to suppress aggregation, the object of the present invention, that is, a low impurity amount at a level that does not cause poor conductivity in the formation circuit of the fine wiring, cannot be achieved. On the other hand, if the level of D 50 is greater than 5.0 .mu.m, not suitable for the formation of fine wiring. A more preferred average particle size D 50 is 0.5～3.5Myuemu.
そして、一般に、微粒粉は凝集しやすいが、本発明に係る銅粉の製造方法により得られる銅粉は、Ｄ５０が０．１μｍ〜５．０μｍという微粒な範囲の粒径でありながら、ＳＤ／Ｄ５０＝０．２〜０．５という粒度分布幅が極めて狭いシャープな銅粉である。上述の通り、ＳＤ／Ｄ５０は、銅粉の粒度分布幅の程度を示す。そして、ＳＤ／Ｄ５０の値が０．２〜０．５という範囲であると、凝集が少なく、０．５を上回ると、粒子のバラツキが多く、微細配線の形成に適さない。 And, in general, fine powder tends to aggregate, but copper powder obtained by the production method of the copper powder according to the present invention, D 50 is yet particle size of fine range of 0.1Myuemu～5.0Myuemu, SD / D 50 = A sharp copper powder having a very narrow particle size distribution width of 0.2 to 0.5. As described above, SD / D 50 indicates the degree of the particle size distribution width of the copper powder. And when the value of SD / D 50 is in the range of 0.2 to 0.5, there is little aggregation, and when it exceeds 0.5, there are many particle variations and it is not suitable for forming fine wiring.
また、本発明に係る銅粉の製造方法により得られる銅粉は、大気雰囲気中、４００℃で３０分熱処理した後の炭素含有量が０．０１質量％未満であり、炭素含有量が極めて低い。ここで、本発明に係る銅粉の製造方法により得られる銅粉は酸化防止のための有機表面処理を施しているが、この表面処理剤は、２００℃〜３００℃付近で銅粉の表面から消失する。したがって、４００℃で３０分焼成後の銅粉は、表面処理剤が除去された状態であり、この状態で測定した銅粉の炭素含有量は、焼成により導体膜が形成される温度下の銅粉の炭素含有量を推定できるのである。なお、本明細書における銅粉の炭素含有量は、炭素分析装置（堀場製作所社製 ＥＭＩＡ−３２０Ｖ）を用いて測定した。 Moreover, the copper powder obtained by the copper powder manufacturing method according to the present invention has a carbon content of less than 0.01% by mass after being heat-treated at 400 ° C. for 30 minutes in the air atmosphere, and the carbon content is extremely low. . Here, the copper powder obtained by the method for producing copper powder according to the present invention has been subjected to an organic surface treatment for oxidation prevention, but this surface treatment agent is from the surface of the copper powder at around 200 ° C to 300 ° C. Disappear. Therefore, the copper powder after firing at 400 ° C. for 30 minutes is in a state where the surface treatment agent has been removed, and the carbon content of the copper powder measured in this state is the copper under the temperature at which the conductor film is formed by firing. The carbon content of the powder can be estimated. In addition, the carbon content of the copper powder in this specification was measured using the carbon analyzer (EMIA-320V by Horiba Ltd.).
本発明に係る銅粉の製造方法により得られる銅粉を銅ペースト等に用いた場合、銅ペーストの焼成時に、導体表面の焼結開始温度以前に表面処理剤は消失し、その後、銅体表面に焼結膜が形成された後は、導体内部に炭酸ガスが発生しないので、導体表面のクラックの発生を防止し、高品質な導体を形成することができる。 When the copper powder obtained by the method for producing copper powder according to the present invention is used for a copper paste or the like, the surface treatment agent disappears before the sintering start temperature of the conductor surface when firing the copper paste, and then the surface of the copper body After the sintered film is formed, carbon dioxide gas is not generated inside the conductor, so that generation of cracks on the conductor surface can be prevented and a high-quality conductor can be formed.
以下、実施例及び比較例を示して本件発明を具体的に説明する。本発明は以下の実施例に制限されるものではない。なお、以下の実施例及び比較例２における銅粉の製造条件が対比しやすいように、製造条件の概略を表１に掲載する。 Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. The present invention is not limited to the following examples. In addition, the outline of manufacturing conditions is listed in Table 1 so that the manufacturing conditions of the copper powder in the following Examples and Comparative Examples 2 can be easily compared.
まず、純水６．５Ｌに硫酸銅６０００ｇを投入して撹拌し、その後、液温を５０℃に保持しつつ、硫酸銅水溶液（銅塩水溶液）の液量が９Ｌとなるように、更に水を添加して、濃度を調整した。当該硫酸銅水溶液に、アンモニア水溶液（濃度２５ｗｔ％）２５３７ｍｌを３０分で添加して中和し、銅塩化合物スラリーを得た。そして、銅塩化合物スラリーを３０分静置して熟成させた。ここまでは銅塩化合物スラリーの液温を５０℃に保持したが、熟成後は液温を４５℃に調整した。 First, 6000 g of copper sulfate was added to 6.5 L of pure water and stirred, and then water was further added so that the liquid volume of the copper sulfate aqueous solution (copper salt aqueous solution) was 9 L while maintaining the liquid temperature at 50 ° C. Was added to adjust the concentration. To this copper sulfate aqueous solution, 2537 ml of an aqueous ammonia solution (concentration 25 wt%) was added in 30 minutes for neutralization to obtain a copper salt compound slurry. The copper salt compound slurry was allowed to stand for 30 minutes for aging. Up to this point, the liquid temperature of the copper salt compound slurry was maintained at 50 ° C., but after aging, the liquid temperature was adjusted to 45 ° C.
次に、銅塩化合物スラリーの銅濃度が２．０ｍｏｌ／Ｌとなるように水を添加して液量を調整した。この銅塩化合物スラリーをｐＨ６．３、液温５０℃の条件に保ち、ここに、ヒドラジン１水和物（ヒドラジン系還元剤）４５０ｇとｐＨ調整剤としてのアンモニア水溶液（濃度２５ｗｔ％）５９１ｍｌとを３０分間かけて連続添加し、亜酸化銅スラリーとした（第１還元処理）。そして、還元反応を完全に行うため、更に３０分間撹拌を続けた。 Next, the amount of liquid was adjusted by adding water so that the copper concentration of the copper salt compound slurry was 2.0 mol / L. This copper salt compound slurry was maintained at a pH of 6.3 and a liquid temperature of 50 ° C., and 450 g of hydrazine monohydrate (hydrazine reducing agent) and 591 ml of an aqueous ammonia solution (concentration 25 wt%) as a pH adjuster were added. It added continuously over 30 minutes and was set as the cuprous oxide slurry (1st reduction process). Then, in order to complete the reduction reaction, stirring was continued for another 30 minutes.
その後、リパルプ洗浄のため、亜酸化銅スラリーに純水を加えて１８Ｌに液量調整した後、静置して亜酸化銅粒子を沈殿させ、静置後の上澄液を１４Ｌ抜く操作を、ｐＨが４．７になるまで繰り返した。そして、温めた純水８Ｌを加えて全液量を１２Ｌにし、液温を４５℃に維持して、銅濃度を２．０ｍｏｌ／Ｌに調整し、これを洗浄亜酸化銅スラリーとした。 Then, for repulp washing, after adding pure water to the cuprous oxide slurry and adjusting the liquid volume to 18 L, the operation is performed by allowing to stand and precipitating cuprous oxide particles, and removing 14 L of the supernatant after standing, Repeated until pH was 4.7. Then, 8 L of warm pure water was added to make the total liquid volume 12 L, the liquid temperature was maintained at 45 ° C., the copper concentration was adjusted to 2.0 mol / L, and this was used as a washed cuprous oxide slurry.
銅濃度調整後の洗浄亜酸化銅スラリーに、次亜リン酸アンモニウム３．０２ｇを添加し、５分間撹拌した（リン化合物添加工程）。 To the washed cuprous oxide slurry after adjusting the copper concentration, 3.02 g of ammonium hypophosphite was added and stirred for 5 minutes (phosphorus compound addition step).
再び、洗浄亜酸化銅スラリーの銅濃度が２．０ｍｏｌ／Ｌとなるように水を添加して液量を調整した。この洗浄亜酸化銅スラリーに、ヒドラジン１水和物（ヒドラジン系還元剤）１２００ｇを３０分間で添加した。次に、更に１５分間撹拌を行い、還元反応を完全に行わせ銅粉を還元析出させた（第２還元処理）。 Again, the amount of liquid was adjusted by adding water so that the copper concentration of the washed cuprous oxide slurry was 2.0 mol / L. To this washed cuprous oxide slurry, 1200 g of hydrazine monohydrate (hydrazine reducing agent) was added over 30 minutes. Next, the mixture was further stirred for 15 minutes to complete the reduction reaction, thereby reducing and precipitating copper powder (second reduction treatment).
析出した銅粒子を濾過して採取した。そして、洗浄後、当該銅粉に、オクタデシルアミン１．５ｇを溶解させたメタノール溶液５Ｌに入れ有機表面処理を施し、濾別分離後、７０℃、５時間の加熱乾燥を行い、更に解砕処理を施して銅粉を得た。 The precipitated copper particles were collected by filtration. And after washing | cleaning, it puts in the methanol solution 5L which dissolved 1.5 g of octadecylamine in the said copper powder, and performs organic surface treatment, and after separating by filtration, it heat-drys at 70 degreeC for 5 hours, and also crushes. To obtain copper powder.
実施例１で得られた銅粉について、Ｄ１０、Ｄ５０、Ｄ９０、ＢＥＴ比表面積、タップ充填密度、炭素含有量を測定した。また、得られた銅粉のＢＥＴ比表面積に基づいて比表面積径ＤＢＥＴを算出した。また、実施例１で得られた有機表面処理後の銅粉を、大気雰囲気、４００℃で３０分焼成した後の炭素含有量を測定した。この結果を表２に示す。また、粒度体積基準分布図を図２に示し、走査型電子顕微鏡（ＳＥＭ）像を図３に示す。以下、それぞれの測定方法について示す。 For copper powder obtained in Example 1 was measured D 10, D 50, D 90 , BET specific surface area, tap packing density, the carbon content. Moreover, the specific surface area diameter D BET was calculated based on the BET specific surface area of the obtained copper powder. Moreover, the carbon content after baking the copper powder after the organic surface treatment obtained in Example 1 at 400 degreeC in air | atmosphere for 30 minutes was measured. The results are shown in Table 2. Moreover, a particle size volume reference distribution diagram is shown in FIG. 2, and a scanning electron microscope (SEM) image is shown in FIG. Hereinafter, each measurement method will be described.
レーザー回折散乱式粒度分布測定法による体積累積平均粒径Ｄ５０：銅粉０．１ｇをＳＮディスパーサント５４６８の０．１％水溶液（サンノプコ社製）と混合し、超音波ホモジナイザ（日本精機製作所製 ＵＳ−３００Ｔ）で５分間分散させた後、レーザー回折散乱式粒度分布測定装置 Ｍｉｃｒｏ Ｔｒａｃ ＨＲＡ ９３２０−Ｘ１００型（Ｌｅｅｄｓ＋Ｎｏｒｔｈｒｕｐ社製）を用いて、流量速度５０ｃｍ３／ｍｉｎで測定した。体積累積５０％における粒径をＤ５０とし、同様にして、体積累積１０％ならびに９０％の粒径Ｄ１０、Ｄ９０を測定した。 Volume cumulative average particle diameter D 50 by laser diffraction scattering particle size distribution measurement method: 0.1 g of copper powder is mixed with a 0.1% aqueous solution of SN Dispersant 5468 (manufactured by San Nopco), and an ultrasonic homogenizer (manufactured by Nippon Seiki Seisakusho). (US-300T) for 5 minutes, and measurement was performed at a flow rate of 50 cm 3 / min using a laser diffraction / scattering particle size distribution analyzer, Micro Trac HRA 9320-X100 (Leeds + Northrup). The particle size and D 50 in the volume cumulative 50% in the same manner, the particle size was determined D 10, D 90 volume cumulative 10% and 90%.
タップ充填密度（ＴＤ）：パウダースターＰＴ−Ｅ（ホソカワミクロン株式会社製）を用いて測定した。 Tap filling density (TD): Measured using Powder Star PT-E (manufactured by Hosokawa Micron Corporation).
比表面積：試料２．００ｇを７５℃で１０分間の脱気処理を行った後、モノソーブ（カンタクロム社製）を用いてＢＥＴ１点法で測定した。そして、比表面積径ＤＢＥＴは、得られた銅粉を真球と仮定し、ＢＥＴ１点法で測定した比表面積ＳＳＡと、銅の真比重８．９２とを用いた式ＤＢＥＴ＝６／（８．９２×ＳＳＡ）を用いて算出した。 Specific surface area: A sample of 2.00 g was degassed at 75 ° C. for 10 minutes, and then measured by a BET one-point method using a monosorb (manufactured by Cantachrome). The specific surface area diameter D BET is obtained by using the formula D BET = 6 / () using the specific surface area SSA measured by the BET one -point method and the true specific gravity of copper 8.92, assuming that the obtained copper powder is a true sphere. 8.92 × SSA).
炭素含有量：４００℃で３０分保持後の炭素含有量を炭素分析装置（堀場製作所社製 ＥＭＩＡ−３２０Ｖ）を用いて測定した。 Carbon content: The carbon content after being held at 400 ° C. for 30 minutes was measured using a carbon analyzer (EMIA-320V, manufactured by Horiba, Ltd.).
実施例２は、実施例１と比べて、リン化合物の添加時期が異なる例である。 Example 2 is an example in which the addition time of the phosphorus compound is different from that in Example 1.
即ち、洗浄亜酸化銅スラリーに次亜リン酸アンモニウムを添加する代わりに、硫酸銅水溶液の液温を５０℃に保持しつつ、リン化合物としてリン酸三ナトリウム１２水和物１１．０６ｇを添加する以外は実施例１と同様の方法で銅粉を得た。 That is, instead of adding ammonium hypophosphite to the washed cuprous oxide slurry, 11.06 g of trisodium phosphate dodecahydrate is added as a phosphorus compound while maintaining the temperature of the copper sulfate aqueous solution at 50 ° C. Except for the above, copper powder was obtained in the same manner as in Example 1.
実施例２で得られた銅粉について、実施例１と同様のデータを測定、算出した。この結果を表２に示す。また、体積基準粒度分布図を図４に示し、走査型電子顕微鏡（ＳＥＭ）像を図５に示す。 About the copper powder obtained in Example 2, the same data as Example 1 were measured and calculated. The results are shown in Table 2. Further, a volume-based particle size distribution diagram is shown in FIG. 4, and a scanning electron microscope (SEM) image is shown in FIG.
［比較例１］
比較例１は、湿式還元法による銅粉の製造に際し、有機系還元剤を用いる例である。
[Comparative Example 1]
Comparative Example 1 is an example in which an organic reducing agent is used in the production of copper powder by a wet reduction method.
まず、６０℃の純水３Ｌに硫酸銅５水和物４００ｇを添加し、二価の銅イオンを含む銅塩水溶液を準備する。そして、温度６０℃に保持した銅塩水溶液に、純水を加え、銅濃度を２ｍｏｌ／Ｌとした。 First, 400 g of copper sulfate pentahydrate is added to 3 L of pure water at 60 ° C. to prepare a copper salt aqueous solution containing divalent copper ions. And the pure water was added to the copper salt aqueous solution hold | maintained at the temperature of 60 degreeC, and copper concentration was 2 mol / L.
次に、銅塩水溶液の液温を６０℃に保ち、２５％水酸化ナトリウム水溶液４６０ｍｌとを順に添加し、銅塩化合物スラリーを得た。 Next, the liquid temperature of the copper salt aqueous solution was kept at 60 ° C., and 460 ml of a 25% aqueous sodium hydroxide solution was added in order to obtain a copper salt compound slurry.
次に、銅塩化合物スラリーの液温を５０℃に維持して、ヒドラジン１水和物１００ｇを３０分間で添加した。更に６０分間撹拌を行い、還元反応を完全に行わせ銅粉を還元析出させた。 Next, the liquid temperature of the copper salt compound slurry was maintained at 50 ° C., and 100 g of hydrazine monohydrate was added over 30 minutes. The mixture was further stirred for 60 minutes to complete the reduction reaction and reduce the copper powder.
このようにして得た銅粉を濾過して採取した。そして、当該銅粉に、オクタデシルアミン１．５ｇを溶解させたメタノール溶液５Ｌに入れ有機表面処理を施し、３０分間撹拌し、８０℃、５時間の加熱乾燥を行って粉体を得た。得られた銅粉の粉体特性について、実施例１と同様のデータを測定した。この結果、粒度分布はシャープであるものの、４００℃で３０分焼成後の炭素含有量が０．０７ｗｔ％となった。 The copper powder thus obtained was collected by filtration. Then, the copper powder was put into 5 L of a methanol solution in which 1.5 g of octadecylamine was dissolved, subjected to organic surface treatment, stirred for 30 minutes, and heated and dried at 80 ° C. for 5 hours to obtain a powder. About the powder characteristic of the obtained copper powder, the same data as Example 1 were measured. As a result, although the particle size distribution was sharp, the carbon content after firing at 400 ° C. for 30 minutes was 0.07 wt%.
［比較例２］
比較例２は、湿式還元法による銅粉の製造に際し、リン化合物を添加しない例である。即ち、リン化合物を全く添加しない点以外は、実施例１と同様の方法で銅粉を得た。得られた銅粉の粉体特性について、実施例１と同様のデータを測定、算出した。この結果を表２に示す。また、比較例２で得られた銅粉の体積基準粒度分布図を図６に示す。
[Comparative Example 2]
Comparative Example 2 is an example in which no phosphorus compound is added when copper powder is produced by a wet reduction method. That is, copper powder was obtained in the same manner as in Example 1 except that no phosphorus compound was added. About the powder characteristic of the obtained copper powder, the same data as Example 1 were measured and computed. The results are shown in Table 2. Moreover, the volume reference | standard particle size distribution figure of the copper powder obtained by the comparative example 2 is shown in FIG.
［比較例３］
比較例３は、特許文献４に開示の方法を用いて、銅含有溶液の濃度を実施例１の銅塩含有スラリーと同等の濃度とした例である。まず、硫酸銅五水和物３９５ｇと純水０．０５Ｌとを混合し、更に、ピロリン酸ナトリウム４０ｇを添加して銅含有溶液を作製した。次に、この銅含有溶液中に、濃アンモニア水（濃度２８％）５００ｇを加え、混合して銅アンモニア錯イオン溶液を作製した。この銅アンモニア錯イオン溶液中に純水を加えて全液量を０．７９Ｌにし、実施例１と同じ銅濃度とした。この銅アンモニア錯イオン溶液に、還元剤として飽水ヒドラジン２００ｇを３０℃の温度下で添加して混合した後、液温を８０℃まで上昇させて２時間維持することにより反応を十分に行わせた。その後、金属銅として得られた銅粉末を溶液中から回収し、洗浄した。
[Comparative Example 3]
Comparative Example 3 is an example in which the concentration of the copper-containing solution was set to the same concentration as that of the copper salt-containing slurry of Example 1 using the method disclosed in Patent Document 4. First, 395 g of copper sulfate pentahydrate and 0.05 L of pure water were mixed, and 40 g of sodium pyrophosphate was further added to prepare a copper-containing solution. Next, 500 g of concentrated ammonia water (concentration 28%) was added to this copper-containing solution and mixed to prepare a copper ammonia complex ion solution. Pure water was added to the copper ammonia complex ion solution to make the total liquid volume 0.79 L, and the same copper concentration as in Example 1 was obtained. To this copper ammonia complex ion solution, 200 g of saturated hydrazine as a reducing agent was added and mixed at a temperature of 30 ° C., and then the temperature of the solution was raised to 80 ° C. and maintained for 2 hours to sufficiently perform the reaction. It was. Thereafter, the copper powder obtained as metallic copper was recovered from the solution and washed.
なお、上述の通り、比較例３では、リン化合物であるピロリン酸ナトリウムを銅含有溶液作製時に添加し、その後、還元反応を行わせている。得られた銅粉の粉体特性について、実施例１と同様のデータを測定、算出した。この結果を表２に示す。また、比較例３で得られた銅粉の体積基準粒度分布図を図７に示し、走査型電子顕微鏡（ＳＥＭ）像を図８に示す。 In addition, as above-mentioned, in the comparative example 3, sodium pyrophosphate which is a phosphorus compound is added at the time of copper-containing solution preparation, and a reduction reaction is performed after that. About the powder characteristic of the obtained copper powder, the same data as Example 1 were measured and computed. The results are shown in Table 2. Moreover, the volume reference | standard particle size distribution figure of the copper powder obtained by the comparative example 3 is shown in FIG. 7, and a scanning electron microscope (SEM) image is shown in FIG.
以下、実施例で得られた銅粉と比較例で得られた銅粉とを対比する。 Hereinafter, the copper powder obtained in the example and the copper powder obtained in the comparative example will be compared.
まず、実施例について、図２の粒度体積基準分布図を見ると、粒径１μｍを頻度ピークとして、粒度分布幅が狭くシャープな分布を示している。それは、ＳＤ／Ｄ５０、Ｄ９０／Ｄ１０の値が低いことからも明らかである。タップ充填密度（ＴＤ）は低い値を示した。更に、収率は９６％と高い値を示している。大気雰囲気、４００℃で３０分焼成後の炭素含有量については、測定装置で検出可能な下限である０．０１ｗｔ％に達する量とはならなかったので、０．０１ｗｔ％未満とした。 First, regarding the example, the particle size volume reference distribution diagram of FIG. 2 shows a sharp distribution with a narrow particle size distribution width with a particle size of 1 μm as a frequency peak. This is also clear from the low values of SD / D 50 and D 90 / D 10 . The tap packing density (TD) showed a low value. Furthermore, the yield is as high as 96%. The carbon content after firing at 400 ° C. for 30 minutes in the air atmosphere was not less than 0.01 wt% because it did not reach 0.01 wt%, which is the lower limit detectable by the measuring device.
次に、実施例１及び実施例２と比較例１とを対比すると、実施例１及び実施例２の炭素含有量は０．０１ｗｔ％未満であるのに対し、比較例１は０．０７ｗｔ％であり、炭素含有量が多い。有機還元剤を使用した比較例１の銅粉は、本発明に係る銅粉の炭素含有量を大きく上回る値を示し、このような炭素含有量レベルの銅粉は、本発明の課題である微粒且つ、導体の安定した形成と導電性向上を図ることが難しい。 Next, when Example 1 and Example 2 are compared with Comparative Example 1, the carbon content of Example 1 and Example 2 is less than 0.01 wt%, while that of Comparative Example 1 is 0.07 wt%. And has a high carbon content. The copper powder of the comparative example 1 which uses an organic reducing agent shows the value which exceeds the carbon content of the copper powder which concerns on this invention greatly, The copper powder of such a carbon content level is a fine particle which is a subject of this invention In addition, it is difficult to stably form the conductor and improve the conductivity.
次に、実施例２と比較例２とを対比すると、平均粒径ならびに炭素含有量は同等である。しかし、ＳＤ／Ｄ５０、Ｄ９０／Ｄ１０は実施例が著しく低く、ＳＤ／Ｄ５０に至っては、約３割程度の顕著な差が見られ、実施例の粒度分布幅が狭いことが明白である。 Next, when Example 2 and Comparative Example 2 are compared, the average particle diameter and the carbon content are the same. However, SD / D 50 and D 90 / D 10 are remarkably low in the examples, and when SD / D 50 is reached, a remarkable difference of about 30% is seen, and it is clear that the particle size distribution width of the examples is narrow. It is.
比較例３で得られた銅粉は、図７に示す銅粉の走査型電子顕微鏡（ＳＥＭ）像を見ると、凝集が多く発生していることが明らかである。また、図７に示す走査型電子顕微鏡像の画像解析により得られる一次粒子の平均径は２μｍ程度であるものの凝集が激しく、その結果、Ｄ５０＝３４．６８μｍ程度となっている。また、ＳＤ／Ｄ５０は低いものの上記のとおり、凝集粒子の大きさは実施例に比べ、はるかに大きく、微粒銅粉としての粒度分布を呈したものとは言い難い。したがって、粗粒が多く含まれ微細配線の形成には不適である。また、収率も実施例に劣ることは明らかである。即ち、比較例３の方法では、粒度分布がシャープな微粒銅粉を高収率で製造することは難しいことが示された。 When the copper powder obtained in Comparative Example 3 is viewed by a scanning electron microscope (SEM) image of the copper powder shown in FIG. Moreover, although the average diameter of the primary particles obtained by the image analysis of the scanning electron microscope image shown in FIG. 7 is about 2 μm, aggregation is severe, and as a result, D 50 = 34.68 μm. Further, SD / D 50 is as low in the size of the agglomerated particles is compared with the embodiment, much larger, it is hard to say that those exhibiting a particle size distribution of the fine copper powder. Therefore, many coarse grains are contained and it is not suitable for forming fine wiring. It is also clear that the yield is inferior to that of the example. That is, with the method of Comparative Example 3, it was shown that it was difficult to produce a fine copper powder with a sharp particle size distribution in a high yield.
本発明に係る銅粉の製造方法は、粒子の均一化を図り、従来品より不純物が少ない銅粉を製造することができる。そして、得られた銅粉は、スクリーン印刷法による導体形成用の材料として用いると、微細配線の形成不良を防ぎ、且つ電気的安定性に優れた導体形成が可能となる。したがって、本発明に係る銅粉の製造方法により得られる銅粉は、微細配線の形成材料に好適である。 The method for producing copper powder according to the present invention makes it possible to produce uniform copper particles and to produce copper powder with less impurities than conventional products. And when the obtained copper powder is used as a material for forming a conductor by a screen printing method, it is possible to prevent the formation of fine wiring and to form a conductor with excellent electrical stability. Therefore, the copper powder obtained by the copper powder manufacturing method according to the present invention is suitable as a material for forming fine wiring.
Claims (6)
最終還元反応が終了するまでに、リンと銅のモル比がＰ／Ｃｕ＝０．０００１〜０．００３となるように、リン化合物を反応スラリーに添加することを特徴とする銅粉の製造方法。 To a copper salt compound slurry obtained by adding an alkaline solution to an aqueous copper salt solution, a hydrazine-based reducing agent is added to form a cuprous oxide slurry, and the cuprous oxide slurry is washed with water and reslurried to washed cuprous oxide. In the method for producing copper powder in which a hydrazine reducing agent is added again to the slurry,
Before the final reduction reaction is completed, the phosphorus compound is added to the reaction slurry so that the molar ratio of phosphorus and copper is P / Cu = 0.0001 to 0.003. .
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| KR20107004861A KR101510369B1 (en) | 2007-09-21 | 2008-09-22 | Process for producing copper powder and copper powder |
| PCT/JP2008/067078 WO2009038207A1 (en) | 2007-09-21 | 2008-09-22 | Process for producing copper powder and copper powder |
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| JP5476631B2 (en) * | 2010-03-05 | 2014-04-23 | 株式会社村田製作所 | Electronic component and manufacturing method thereof |
| JP5531691B2 (en) * | 2010-03-16 | 2014-06-25 | 株式会社村田製作所 | Conductive paste and method for manufacturing ceramic electronic component |
| JP5759688B2 (en) * | 2010-08-17 | 2015-08-05 | 三井金属鉱業株式会社 | Flat copper particles |
| JP5820202B2 (en) * | 2010-09-30 | 2015-11-24 | Ｄｏｗａエレクトロニクス株式会社 | Copper powder for conductive paste and method for producing the same |
| TWI487581B (en) * | 2010-11-12 | 2015-06-11 | Mitsui Mining & Smelting Co | Low carbon copper particles and methods for producing the same |
| KR101239391B1 (en) * | 2011-01-05 | 2013-03-05 | 한국지질자원연구원 | Method of manufacturing fine cupper powders for electronic materials with easily size control |
| JP5120477B2 (en) * | 2011-04-07 | 2013-01-16 | 日立化成工業株式会社 | Electrode paste composition and solar cell |
| JP5785433B2 (en) * | 2011-04-28 | 2015-09-30 | 三井金属鉱業株式会社 | Low carbon copper particles |
| JP6028727B2 (en) * | 2011-05-18 | 2016-11-16 | 戸田工業株式会社 | Copper powder, copper paste, method for producing conductive coating film and conductive coating film |
| JP6199430B2 (en) * | 2011-09-30 | 2017-09-20 | Ｄｏｗａエレクトロニクス株式会社 | Cuprous oxide powder and method for producing the same |
| EP2923781A4 (en) * | 2012-11-26 | 2016-07-13 | Mitsui Mining & Smelting Co | Copper powder and method for producing same |
| JP5700864B2 (en) * | 2013-05-15 | 2015-04-15 | 石原ケミカル株式会社 | Copper fine particle dispersion, conductive film forming method, and circuit board |
| JP6303022B2 (en) * | 2014-10-03 | 2018-03-28 | 三井金属鉱業株式会社 | Copper powder |
| JP6698367B2 (en) * | 2015-03-31 | 2020-05-27 | 山陽特殊製鋼株式会社 | Metal powder consisting of spherical particles |
| JP6256616B2 (en) * | 2015-04-22 | 2018-01-10 | 日立金属株式会社 | Metal particles and production method thereof, coated metal particles, metal powder |
| CN107921532B (en) * | 2015-09-03 | 2020-05-08 | 同和电子科技有限公司 | Phosphorus-containing copper powder and method for producing same |
| JP2017179428A (en) * | 2016-03-29 | 2017-10-05 | Ｄｏｗａエレクトロニクス株式会社 | Conductive material, forming method of conducive film, circuit board, semiconductor device, and manufacturing method of semiconductor device |
| US9975110B1 (en) | 2016-11-23 | 2018-05-22 | Honda Motor Co., Ltd. | Method for producing metal catalyst nanoparticles |
| CN108526490B (en) * | 2018-05-14 | 2021-05-25 | 六盘水中联工贸实业有限公司 | Method for producing copper metal powder by using copper chloride or cuprous chloride |
| CN112296345B (en) * | 2019-07-23 | 2022-02-18 | 富兰克科技（深圳）股份有限公司 | Preparation method of self-dispersible nano-copper with long organic carbon chain, nano-copper preparation and application thereof |
| CN110773177B (en) * | 2019-09-10 | 2022-05-20 | 安徽德诠新材料科技有限公司 | Preparation method of ternary copper catalyst with high specific surface area |
| JP6704083B1 (en) * | 2019-11-22 | 2020-06-03 | 東邦チタニウム株式会社 | Copper powder and its manufacturing method |
| JP7000621B1 (en) * | 2021-06-17 | 2022-01-19 | 古河ケミカルズ株式会社 | Method for manufacturing copper fine particles |
| CN117651693A (en) * | 2021-09-27 | 2024-03-05 | 宇部材料工业株式会社 | Magnesium oxide powder, vulcanizing agent composition for rubber, rubber composition, and method for producing magnesium oxide powder |
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| JP3570591B2 (en) * | 1996-03-22 | 2004-09-29 | 株式会社村田製作所 | Production method of copper powder |
| CN1060108C (en) * | 1997-01-21 | 2001-01-03 | 北京化工大学 | Method for preparing superfine copper powder |
| JP2911429B2 (en) * | 1997-06-04 | 1999-06-23 | 三井金属鉱業株式会社 | Production method of copper fine powder |
| JP3635451B2 (en) * | 1998-09-11 | 2005-04-06 | 株式会社村田製作所 | Metal powder, method for producing the same, and conductive paste |
| KR100743844B1 (en) * | 1999-12-01 | 2007-08-02 | 도와 마이닝 가부시끼가이샤 | Copper powder and process for producing copper powder |
| JP2002363618A (en) * | 2001-06-11 | 2002-12-18 | Sumitomo Electric Ind Ltd | Copper ultrafine grain and production method therefor |
| JP4868716B2 (en) * | 2004-04-28 | 2012-02-01 | 三井金属鉱業株式会社 | Flake copper powder and conductive paste |
| JP4879473B2 (en) * | 2004-10-25 | 2012-02-22 | 三井金属鉱業株式会社 | Flake copper powder, method for producing flake copper powder, and conductive slurry containing flake copper powder |
| JP4662760B2 (en) * | 2004-12-22 | 2011-03-30 | 三井金属鉱業株式会社 | Ultrafine copper powder, ultrafine copper powder slurry, and method for producing ultrafine copper powder slurry |
| JP4651533B2 (en) * | 2005-12-26 | 2011-03-16 | 三井金属鉱業株式会社 | Method for producing copper particles |
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