CN102811830A - Fine silver-plated copper powder and method for producing same - Google Patents
Fine silver-plated copper powder and method for producing same Download PDFInfo
- Publication number
- CN102811830A CN102811830A CN2011800168261A CN201180016826A CN102811830A CN 102811830 A CN102811830 A CN 102811830A CN 2011800168261 A CN2011800168261 A CN 2011800168261A CN 201180016826 A CN201180016826 A CN 201180016826A CN 102811830 A CN102811830 A CN 102811830A
- Authority
- CN
- China
- Prior art keywords
- silver
- fine powder
- copper fine
- plated
- copper
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 213
- 238000004519 manufacturing process Methods 0.000 title 1
- 239000002245 particle Substances 0.000 claims abstract description 43
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052709 silver Inorganic materials 0.000 claims abstract description 29
- 239000004332 silver Substances 0.000 claims abstract description 29
- 238000007747 plating Methods 0.000 claims abstract description 10
- 239000010949 copper Substances 0.000 claims description 211
- 229910052802 copper Inorganic materials 0.000 claims description 208
- 239000000843 powder Substances 0.000 claims description 156
- 239000002002 slurry Substances 0.000 claims description 62
- 239000003595 mist Substances 0.000 claims description 47
- 238000000034 method Methods 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 34
- 238000002360 preparation method Methods 0.000 claims description 22
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 20
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 19
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 18
- 229940112669 cuprous oxide Drugs 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000003638 chemical reducing agent Substances 0.000 claims description 15
- 230000005855 radiation Effects 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 10
- 239000012670 alkaline solution Substances 0.000 claims description 9
- 238000006073 displacement reaction Methods 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 5
- 238000007772 electroless plating Methods 0.000 claims description 5
- 238000005868 electrolysis reaction Methods 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 150000004676 glycans Chemical class 0.000 claims description 4
- 239000000025 natural resin Substances 0.000 claims description 4
- 230000010355 oscillation Effects 0.000 claims description 4
- 229920001282 polysaccharide Polymers 0.000 claims description 4
- 239000005017 polysaccharide Substances 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 239000012736 aqueous medium Substances 0.000 claims description 3
- 230000001186 cumulative effect Effects 0.000 abstract 1
- 238000005259 measurement Methods 0.000 abstract 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 22
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000000463 material Substances 0.000 description 10
- 238000005406 washing Methods 0.000 description 9
- 239000011260 aqueous acid Substances 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 150000001879 copper Chemical class 0.000 description 5
- 230000018044 dehydration Effects 0.000 description 5
- 238000006297 dehydration reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005554 pickling Methods 0.000 description 5
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 description 5
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 235000010489 acacia gum Nutrition 0.000 description 3
- 239000001785 acacia senegal l. willd gum Substances 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 238000001935 peptisation Methods 0.000 description 3
- 229940074439 potassium sodium tartrate Drugs 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 208000019901 Anxiety disease Diseases 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000036506 anxiety Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- KPVWDKBJLIDKEP-UHFFFAOYSA-L dihydroxy(dioxo)chromium;sulfuric acid Chemical compound OS(O)(=O)=O.O[Cr](O)(=O)=O KPVWDKBJLIDKEP-UHFFFAOYSA-L 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- 235000011852 gelatine desserts Nutrition 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- XNRABACJWNCNEQ-UHFFFAOYSA-N silver;azane;nitrate Chemical compound N.[Ag+].[O-][N+]([O-])=O XNRABACJWNCNEQ-UHFFFAOYSA-N 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000019795 sodium metasilicate Nutrition 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 238000010129 solution processing Methods 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- FZUJWWOKDIGOKH-UHFFFAOYSA-N sulfuric acid hydrochloride Chemical compound Cl.OS(O)(=O)=O FZUJWWOKDIGOKH-UHFFFAOYSA-N 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 241000784732 Lycaena phlaeas Species 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229960005137 succinic acid Drugs 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 230000001052 transient effect Effects 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
- B22F1/17—Metallic particles coated with metal
-
- 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
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
-
- 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
- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Dispersion Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Powder Metallurgy (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Conductive Materials (AREA)
- Non-Insulated Conductors (AREA)
Abstract
Disclosed is a fine silver-plated copper powder, wherein an ultra thin silver plating layer is formed on the surface of each ultra fine copper powder particle. Specifically disclosed is a fine silver-plated copper powder, which is composed of fine copper powder particles each provided with a silver plating film on the surface, and which is characterized in that: the weight of silver is 1-25% by mass; the particle diameter (D50) at the cumulative weight of 50% as determined by laser diffraction/scattering particle size distribution measurement is 1 [mu]m or less; and the thickness of the silver plating film is from 0.1 nm to 0.2 [mu]m.
Description
Technical field
The present invention relates to silver-plated copper micro mist and preparation method thereof, particularly relate to and conduction such as use to stick with paste useful silver-plated copper micro mist and preparation method thereof through hole, guide hole (via hole), MLCC internal electrode and outer electrode.
Background technology
The surface-coated silver-plated copper micro mist that silver layer arranged can be processed into conduction to be stuck with paste, and is applied to adopt the circuit of the printing distributing board of silk screen print method to form, various electric contact portion etc., as the material of guaranteeing conductivity.Its reason is that when not compared by the common copper fine powder of silver-coated layer with the surface, the electric conductivity of silver-plated copper micro mist is more excellent than copper fine powder.In addition, its reason is that if be merely then expensive of silver powder, but if silver-plated on copper, then electroconductive powder integral body can become cheap, can significantly reduce preparation cost.Therefore, be coated with the conduction that the excellent more silver-plated copper micro mist of conductive characteristic processes and stick with paste the big advantage that can obtain to prepare with low cost low resistance conductor.
At present, be this advantage of performance silver-plated copper micro mist, and given various characteristics the silver-plated copper micro mist.
In WO2008/059789 number (patent documentation 1); Import surface treatment procedure and utilize no electrolysis displacement plating and reduced form to electroplate through front and back at the surperficial silver layer that forms of copper fine powder at silver plating reaction; The reappearance that can obtain silver-plated when preparation is excellent, has the silver-plated copper micro mist with the tap density of raw copper micro mist equal extent.Particularly, having put down in writing average grain diameter is 1 ~ 30 μ m, and tap density is 2.4g/cm
3More than, specific area is 0.9m
2Silver-plated copper micro mist below the/g.
In patent documentation 1; As this silver-plated copper micropowder preparing process; Record following silver-plated copper micropowder preparing process: copper fine powder is removed copper fine powder surperficial organic matter, washing in alkaline solution, then the oxide to the copper fine powder surface carries out pickling, washing in acid solution, in the acid solution that is dispersed with this copper fine powder, adds reducing agent then; Adjustment pH; Preparation copper fine powder slurry through in this copper fine powder slurry, adding silver ion solution continuously, utilizes no electrolysis displacement plating and reduced form electroless plating to form silver layer on the copper fine powder surface.
On the other hand; In WO2009/001710 (patent documentation 2), record the preparation method of the copper fine powder that utilizes disproportionated reaction: in order rapidly, efficiently and stably to prepare fine copper fine powder; In the aqueous medium of the additive that contains natural resin, polysaccharide or derivatives thereof, add cuprous oxide and prepare slurry; 15 minutes with introversive this slurry in disposable interpolation 5 ~ 50% aqueous acids, carry out disproportionated reaction.
The prior art document
Patent documentation
Patent documentation 1:WO2008/059789 number
Patent documentation 2:WO2009/001710 number.
Summary of the invention
Invent problem to be solved
Though the silver-plated copper micropowder preparing process of record is effective really in the patent documentation 1, if the further miniaturization of silver-plated copper micro mist is then favourable aspect thin space (fine pitch) change.The inventor envisioned if after the method for record obtains fine copper fine powder in patent documentation 2 originally; Use the method for record in the patent documentation 1; Then can solve this problem; But learn that can become is prone to aggegation takes place, and is difficult to obtain fine silver-plated copper micro mist along with the particle diameter of implementing the copper fine powder before silver-plated is decreased to less than 1 μ m.
Therefore, one of problem of the present invention ultramicrofine copper fine powder surface of being to be provided at average grain diameter less than 1 μ m is formed with the silver-plated copper micro mist of silver coating as thin as a wafer.In addition, another problem of the present invention is to provide in order to prepare the method for this type of silver-plated copper micro mist.
Solve the means of problem
The inventor is learning when above-mentioned problem is studied repeatedly for solving, if will process dry copper fine powder through copper fine powder filtration washing or dehydration that disproportionated reaction obtains, then is prone to carry out aggegation.And find then can in electroplate liquid, to keep the dispersion of copper fine powder if after obtaining the pulp-like copper fine powder through disproportionated reaction, directly keep the wet method condition and be transferred to silver-plated operation continuously simultaneously, can aggegation not take place and carry out as thin as a wafer silver-plated.In addition, find that also then only this is also insufficient, need in the ultrasonic wave radiation, carry out silver-plated if the average grain diameter (D50) of copper fine powder is less than 0.4 μ m.
The present invention is based on above opinion and accomplish; Be the silver-plated copper micro mist on the one hand; Said micro mist is for implementing to have silver-plated copper fine powder on the surface; Wherein, utilizing the accumulating weight of laser diffraction and scattering formula particle size distribution to reach 50% particle diameter (D50) is less than 1 μ m, and the thickness of silver-plated film is 0.1nm ~ 0.2 μ m.
With regard to silver-plated copper micro mist involved in the present invention, in one embodiment, it has silver-plated copper fine powder for implementing on the surface, and wherein, the weight of silver is 1 ~ 25% quality.
With regard to silver-plated copper micro mist involved in the present invention, in one embodiment, D50 is 0.05 ~ 0.5 μ m, and the thickness of silver-plated film is 0.2nm ~ 0.05 μ m.
With regard to silver-plated copper micro mist involved in the present invention, in another embodiment, the BET specific area is 3.0 ~ 10.0m
2/ g.
With regard to silver-plated copper micro mist involved in the present invention, in another embodiment again, tap density is greater than apparent density, and apparent density is 1.0 ~ 3.0g/cm
3, tap density is 2.0 ~ 4.0g/cm
3
With regard to silver-plated copper micro mist involved in the present invention, in another embodiment again, implementing copper fine powder before silver-plated, to utilize the accumulating weight of laser diffraction and scattering formula particle size distribution to reach 50% particle diameter (D50) be 0.05 ~ 0.9 μ m.
Another aspect of the invention is the silver-plated copper micropowder preparing process; Said preparation method comprises and implements following operation successively: in the aqueous medium of the additive that contains natural resin, polysaccharide or derivatives thereof, add cuprous oxide and prepare slurry; Added acidic aqueous solution with introversion in the said slurry at 16 minutes; Carry out disproportionated reaction; It is the operation 1 of the copper fine powder slurry of 0.05 ~ 0.9 μ m that thereby the preparation accumulating weight reaches 50% particle diameter (D50); Said copper fine powder slurry is handled the organic operation 2 of removing the copper fine powder surface with alkaline solution; Said copper fine powder is handled the operation 3 of removing the surperficial oxide of copper fine powder with acid solution, prepare the operation 4 that makes said copper fine powder be scattered in the copper fine powder slurry of pH3.5 ~ 4.5 in the reducing agent, through in said copper fine powder slurry, adding silver ion solution continuously; Utilize no electrolysis displacement plating and reduced form electroless plating to carry out the operation 6 of Separation of Solid and Liquid in the operation 5 of copper fine powder surface formation silver layer with to the silver-plated copper micro mist slurry that in operation 5, obtains.
With regard to silver-plated copper micropowder preparing process involved in the present invention; In one embodiment; The preparation accumulating weight reaches 50% particle diameter (D50) and is the copper fine powder slurry of less than 0.4 μ m in operation 1, in operation 5 in the interpolation process of silver ion solution radiate supersonic wave.
With regard to silver-plated copper micropowder preparing process involved in the present invention, in another embodiment, in operation 5,, the interpolation of silver ion solution still continues the ultrasonic wave radiation more than 10 minutes after finishing.
With regard to silver-plated copper micropowder preparing process involved in the present invention, in another embodiment, hyperacoustic frequency of oscillation of institute's radiation is 16 ~ 50kHz.
Of the present invention again on the other hand for conducting electricity paste, said conduction is stuck with paste and is contained silver-plated copper micro mist involved in the present invention.
The effect of invention
According to the present invention, the ultramicrofine copper fine powder surface that can be provided at average grain diameter less than 1 μ m is formed with the silver-plated copper micro mist of silver coating as thin as a wafer.Thus, can satisfy the requirement of thin spaceization, particularly be suitable for the purposes that through hole, guide hole, MLCC internal electrode and outer electrode such as use to stick with paste at conduction.
The specific embodiment
< operation 1: the preparation of spherical copper fine powder >
As the raw material of silver-plated copper micro mist involved in the present invention, can use accumulating weight to reach 50% particle diameter and (also claim " average grain diameter " or " D50 " here.) be the copper fine powder of 0.05 ~ 0.9 μ m, wherein when with fine when turning to purpose, can use D50 is the spherical copper fine powder of 0.05 ~ 0.3 μ m.This is in order when sticking with paste the purposes use as conduction, to improve packed density as far as possible.
Copper fine powder can use spherical copper fine powder.Here, the ratio average out to of the minor axis of spherical each copper particle of finger and major diameter is below 150%, and particularly average out to is below 120%.Therefore, the ratio of minor axis and major diameter on average surpasses 150% particle and has flat shape, is not referred to as spherical.The ratio of minor axis and major diameter on average particularly be: directly measure the minor axis and the major diameter of the copper particle image that obtains by the SEM photo, get the above mean value of 20 particles and get.The minimum diameter of a circle that can surround each particle is as major diameter, with maximum diameter of a circle that particle surrounded as minor axis.
The spherical copper fine powder itself of average grain diameter with this scope is known, for example can be according to the method preparation of record in WO2009/001710 number (patent documentation 2), following simple declaration.
Spherical copper fine powder can prepare through the disproportionated reaction of cuprous oxide with acid.Particularly, according to following method preparation: prepare in water, to be dispersed with the slurry that cuprous oxide forms, obtain spherical copper fine powder slurry, carry out Separation of Solid and Liquid through it is added aqueous acid.
Can the particle diameter of the spherical copper fine powder of acquisition be reduced through in the slurry of cuprous oxide, adding natural resin, polysaccharide or derivatives thereof.Its reason is that these additives have the effect that suppresses the particle growth as protecting colloid, and performance reduces the effect of the contact frequency between the particle.Additive can use natural rubber class or gelatin class.Particularly, rosin, gelatin, glue, carboxymethyl cellulose (CMC), starch, dextrin, Arabic gum, casein etc. are effective.
In addition, can particle diameter be reduced through the interpolation time that shortening makes an addition to the aqueous acid in the cuprous oxide slurry.For example can 20 minutes with interior so that 15 minutes with interior so that 3 minutes with interior so that 1 minute with interior disposable interpolation.
The slurry of the spherical copper fine powder that obtains through wet method (disproportionated reaction) is preferred moist and directly in silver-plated operation, use.Its reason is, can omit the operation of temporary transient filtration or dry spherical copper fine powder, and can be not copper fine powder is not exposed in the air and is connected with operation 2, thereby can prevent the carrying out of oxidation.In addition, its reason is, and is silver-plated through under the wet method condition, carrying out continuously, is prone to guarantee the dispersiveness of copper fine powder, can suppress aggegation.
< operation 2: the alkali treatment of copper fine powder >
After operation 1, copper fine powder is removed the organic matter on copper fine powder surface with the alkaline solution processing.Can remove the antirust tunicle or the impurity component on copper fine powder surface thus, can more effective pickling processes of carrying out subsequent processing.As alkaline solution, if can remove the organic alkaline solution that is attached to the copper fine powder surface really, then there is not particular restriction, for example can enumerate out the aqueous solution of NaOH, potassium hydroxide, sodium carbonate, sodium metasilicate, sodium phosphate.Wherein, stronger when alkaline when needing because of hydrolysis etc., preferably use potassium hydroxide aqueous solution.For example, with respect to the copper powder of 100g, the concentration that can use 50 ~ 500ml is the aqueous slkali of 0.1 ~ 5.0% quality.
As the concrete grammar of alkali treatment, if can fully carry out the method that contacts of copper fine powder and alkaline solution, then there is not particular restriction, for example make copper fine powder be scattered in the simple and reliable method that certain hour (for example 10 ~ 20 minutes) is stirred in back in the alkaline solution.Fluid temperature can be room temperature.Preventing aspect the copper fine powder oxidation, preferably will not prepare that the copper fine powder slurry is processed dry powder and directly in operation 2, use through damp process.
< operation 3: the pickling processes of copper fine powder >
After operation 2, this copper fine powder is removed the oxide on copper fine powder surface with the acid solution processing.Thus, can obtain clean copper surface, can carry out silver-plated with homogeneous thickness.As acid solution, if can remove the acid solution of the Cu oxide on copper fine powder surface really, then there is not particular restriction, for example can enumerate out sulfuric acid, hydrochloric acid, phosphoric acid, sulfuric acid-chromic acid, sulfuric acid-hydrochloric acid.Wherein, because sulfuric acid uses when formerly the copper fine powder of operation prepares and can obtain more at an easy rate, so preferred.What need explanation is, kind or the concentration that should be careful selected acid is the copper of dissolved copper micro mist itself excessively not.
The pH that hopes to make this acid solution is 2.0 ~ 5.0 acidic region.If pH surpasses 5.0, then can't fully dissolve the oxide of removing copper fine powder, less than 2.0, then copper powder dissolves as if pH, and the aggegation of copper fine powder itself is also carried out easily.
As the concrete grammar of pickling processes, if can fully carry out the method that contacts of copper fine powder and acid solution, then there is not particular restriction, for example make copper fine powder be scattered in the simple and reliable method that certain hour is stirred in back in the acid solution.Preferably in operation 3, use: after operation 2, aqueous slkali is separated from copper fine powder, then after washing, be scattered in the copper fine powder slurry that forms in the water through suitable decant processing through the decant processing.
Decant is handled and is also claimed gradient method, refers to the slow inclination of container only made the operation of supernatant outflow in the liquid placement that will contain deposition and after making the solid matter sedimentation.Thus, copper fine powder is not contacted with atmosphere and be transferred to subsequent processing (here for shifting to operation 3) by operation 2.
< operation 4: the dispersion of copper fine powder in reducing agent >
After operation 3, preparation makes this copper fine powder be scattered in the copper fine powder slurry of pH3.5 ~ 4.5 in the reducing agent.As the concrete grammar that is used to disperse, can enumerate out the method that the copper fine powder in the reducing agent is stirred certain hour (for example 10 ~ 20 minutes).Fluid temperature can be room temperature.
As spendable reducing agent among the present invention, can use various reducing agents.Preferred reducing agent is a weak reductant.Its reason is, though through utilizing the displacement of adding silver ion to separate out the silver-colored tunicle of formation, as accessory substance generation oxide (CuO, the Cu of this displacement reaction
2O, AgO, Ag
2O), be necessary with they reduction, even but the complex ion of copper can not make its reduction.
Spendable weak reductant has the reproducibility organic compound among the present invention, as such material, for example can use carbohydrate, polybasic carboxylic acid and its esters, aldehydes etc.Particularly can enumerate out glucose (glucose), malonic acid, butanedioic acid, glycolic, lactic acid, malic acid, tartaric acid, oxalic acid, potassium sodium tartrate (Rochelle salt), formalin etc.
In reducing agent, preferred potassium sodium tartrate (Rochelle salt).Owing to have gentle reduction, be used as reducing agent often at the electroless plating that carries out silver.
For example, with respect to the copper powder of 100g, the concentration that can use 100 ~ 1000ml is the reducing agent aqueous solution of 0.1 ~ 5.0% quality.
Here pH is adjusted to 3.5 ~ 4.5 reason for identical with the effect of pickling processes.Preferred pH is 3.7 ~ 4.3.PH regulates and can suitably carry out through acid or alkali, as acid, if can remove the acid solution of the Cu oxide on copper fine powder surface really, does not then have particular restriction, for example can enumerate out sulfuric acid, hydrochloric acid, phosphoric acid, sulfuric acid-chromic acid, sulfuric acid-hydrochloric acid.Wherein, owing to formerly use and the reason that can obtain more at an easy rate, preferably sulfuric acid in the copper fine powder of operation.As alkali, if can be attached to the organic alkaline solution on copper fine powder surface really, then there is not particular restriction, for example can enumerate out the aqueous solution of NaOH, potassium hydroxide, sodium carbonate, sodium metasilicate, sodium phosphate.Wherein, stronger when alkaline when needing because of hydrolysis etc., preferred potassium hydroxide.
When making copper fine powder be scattered in the reducing agent; After operation 3, acid solution is separated from copper fine powder through the decant processing, then suitably utilize decant to handle and wash; Be scattered in the copper fine powder slurry that forms in the water then and be used for operation 4 and can avoid equally and the contacting of atmosphere, so preferred.
< operation 5: the formation of silver layer >
For the copper fine powder slurry that in operation 4, obtains,, utilize no electrolysis displacement plating and reduced form electroless plating to form silver layer on the copper fine powder surface through continuous interpolation silver ion solution.As silver ion solution, can be as silver plating liquid and known any solution, but preferred liquor argenti nitratis ophthalmicus.Silver nitrate concentration can be set at 20 ~ 300g/L, is preferably 50 ~ 100g/L.In addition, less expensive because liquor argenti nitratis ophthalmicus forms complex compound easily, so preferably provide with the form of ammonia property liquor argenti nitratis ophthalmicus.Fluid temperature can be room temperature.
The speed that makes an addition to the silver ion solution in the copper fine powder slurry is set at below the 200mL/min, is preferably set to below the 100mL/min.Through to add speed more slowly, practical application is 20 ~ 200mL/min, adds the liquor argenti nitratis ophthalmicus of above-mentioned concentration range continuously, can be certain in the surface-coated silver layers of uniform of copper fine powder.Through slow interpolation silver ion solution, be prone to silver-plated with homogeneous thickness.If add soon, make that then silver-colored tunicle is inhomogeneous, the anxiety of interparticle deviation increase.Can help to form uniform silver-colored tunicle and reduce interparticle deviation through continuous interpolation silver ion solution.At this moment, preferably in reaction system, supply with silver ion solution with certain speed.
In addition, the silver ion solution time of adding can be set at 10 ~ 60 minutes according to silver-plated amount of coating, is preferably set to 20 ~ 40 minutes and finishes to add.If the interpolation of silver ion solution is fast, make that then silver-colored tunicle is inhomogeneous, the anxiety of interparticle deviation increase.In addition, if the interpolation of silver ion solution is slow, though then do not have problems in the reaction, the operation required time prolongs, and is unfavorable economically.Its result, if silver-plated amount of coating is many, then the silver ion solution interpolation speeds up, on the contrary if silver-plated amount of coating is few, it is slack-off that then silver ion solution adds speed.
Here; If the particle diameter of the copper fine powder before enforcement is silver-plated is more than the 0.4 μ m; The silver-plated tunicle that then when silver-plated, can not carry out the ultrasonic wave radiation and obtain to approach, but if less than 0.4 μ m then is prone to take place aggegation when silver-plated; The silver-plated copper micro mist of, even size fine for obtaining need carry out silver-plated in the ultrasonic wave radiation.If hyperacoustic frequency of oscillation is low excessively, then effect is insufficient, and on the other hand, if too high, then silver-plated tunicle is difficult on copper powder, grow, so be preferably 16 ~ 50kHz, 25 ~ 45kHz more preferably.From preventing the viewpoint of aggegation,, except that in adding the process of silver ion solution, hope still to continue radiation more than 10 minutes, preferred more than 20 minutes, for example 10 ~ 40 minutes after finishing adding about ultrasonic wave.
6. Separation of Solid and Liquid
Through the silver-plated copper micro mist slurry that in operation 5, obtains being carried out Separation of Solid and Liquid, can obtain silver-plated spherical copper fine powder with known any means.As the method for Separation of Solid and Liquid, for example can enumerate out electroplate liquid is separated through the decant processing with silver-plated spherical copper fine powder, silver-plated spherical copper fine powder is scattered in the water, after washing, filter and dry method.
< the 7. characteristic of silver-plated spherical copper fine powder >
The silver-plated spherical copper fine powder that obtains through said method can have following characteristic.
With regard to silver-plated spherical copper fine powder involved in the present invention, in one embodiment, the thickness of silver is 0.1nm ~ 0.2 μ m, is preferably 0.2nm ~ 0.05 μ m, for example is 0.01 ~ 0.05 μ m.Through silver-colored tunicle as thin as a wafer being arranged at the surface of copper, can in the oxidative resistance of improvement, obtain cheap conductive filler as the shortcoming of copper.
With regard to silver-plated spherical copper fine powder involved in the present invention, in one embodiment, the weight of silver is 1 ~ 25% quality.The conduction paste that can obtain electric conductivity, oxidative resistance excellence is thus used filler.Be preferably 1 ~ 20% quality, more preferably 2 ~ 15% quality.In the present invention, the weight ratio of the contained silver of silver-plated spherical copper fine powder is measured through ICP ICP Atomic Emission Spectrophotometer device.
With regard to silver-plated copper micro mist involved in the present invention, in one embodiment, utilizing the accumulating weight of laser diffraction and scattering formula particle size distribution to reach 50% particle diameter (D50) is less than 1 μ m, and it is above and below the 0.9 μ m typically to be 0.05 μ m.Directly as raw material, can obtain the silver-plated copper micro mist that when being raw material, is beyond one's reach fine through the pulp-like sub-micron powder that will obtain by Wet Method Reaction with atomized powder or electrolytic powder.The D50 of silver-plated spherical copper fine powder is preferably 0.05 ~ 0.5 μ m, more preferably 0.05 ~ 0.3 μ m.Here the D50 that measures is the average grain diameter of offspring.
With regard to silver-plated copper micro mist involved in the present invention, in one embodiment, the BET specific area is 1.0 ~ 10.0m
2/ g.Can infer thus and can obtain the spherical silver-plated copper micro mist of the good submicron order of dispersity.If silver-plated with the state of aggegation, then the BET specific area is lower than above-mentioned scope.The BET specific area is preferably 3.0 ~ 10.0m
2/ g, more preferably 5.0 ~ 10.0m
2/ g.
With regard to silver-plated copper micro mist involved in the present invention, in one embodiment, tap density is greater than apparent density, and apparent density is 1.0 ~ 3.0g/cm
3, tap density is 2.0 ~ 4.0g/cm
3The high powder of tap density is because the packed density can improve preparation when sticking with paste, calcining the time, so favourable.Therefore, tap density is preferably 2.5 ~ 4.0g/cm
3, 3.0 ~ 4.0g/cm more preferably
3
In the present invention, apparent density is measured according to the method for JISZ2504.
In the present invention, tap density is measured according to the method for JISZ2512.
Can be through silver-plated copper micro mist involved in the present invention be added resin and solvent, mediate and gelatinization (pasting) prepares conduction and sticks with paste.This conduction is stuck with paste because copper is fine and close with the interface of silver, so electric conductivity (volume intrinsic resistance value (than resistance value)) excellence.
Embodiment
Below embodiments of the invention and comparative example are together illustrated, but these embodiment are for a better understanding of the present invention and advantage and providing, and are not to be intended to limit the present invention.
Embodiment 1 (no ultrasonic wave radiation)
The Arabic gum of 8g is dissolved in 7 liters the pure water, and the cuprous oxide that when stirring, adds 1000g makes it suspendible, and the cuprous oxide slurry is remained in 7 ℃.Cuprous oxide concentration in the slurry is about 143g/L, and the Arabic gum concentration in the slurry is about 1.14g/L.
Then, when stirring, last 7 ℃ dilute sulfuric acid (concentration 24% quality: 9N, the mol ratio (aqueous acid/slurry): 1.3), still continue to stir 10 minutes after finishing adding of remaining in of adding 2000cc in 16 minutes.Mixing speed is set at 500rpm, does not carry out the ultrasonic wave radiation.Confirm that through the FE-SEM observation copper powder that is generated is spherical.Gather the part of the spherical copper fine powder slurry that is generated, when measuring average grain diameter (D50) through laser diffraction formula particle size distribution device ((strain) Shimadzu Seisakusho Ltd. system, model SALD-2100), the average grain diameter of spherical copper fine powder is 0.79 μ m.The output of spherical copper fine powder is 440g according to calculating.
The spherical copper fine powder slurry of this of 440g is added in 1% potassium hydroxide aqueous solution of 880mL and stirred 20 minutes, then carry out a decant and handle, further add the pure water stirred for several minute of 880mL.
Then, carry out the secondary decant and handle, the sulfuric acid concentration that adds 2200mL is that the aqueous sulfuric acid of 15g/L stirred 30 minutes.
And then carry out three decants and handle, add the pure water stirred for several minute of 2200mL.
Then, carry out four decants and handle, add the 1% potassium sodium tartrate solution stirring number minute of 2200mL, form copper slurry.
In this copper slurry, add dilute sulfuric acid or potassium hydroxide solution, the pH of adjustment copper slurry makes it to reach 3.5 ~ 4.5.
The silver nitrate ammonia solution that in the copper slurry of adjusting pH, lasts 30 minutes the slow 880mL of interpolation of time (makes an addition to the silver nitrate of 77.0g in the water; Add ammoniacal liquor; Be adjusted into the solution that 880mL obtains), meanwhile, carry out displacement reaction processing and reduction reaction and handle; Further stirred 30 minutes, obtain the slurry of silver-plated copper micro mist.
Then, carry out five decants and handle, add the pure water stirred for several minute of 3500mL.
And then carry out six decants and handle, add the pure water stirred for several minute of 3500mL.Then, with silver-plated copper micro mist and solution isolated by filtration, the silver-plated copper micro mist carried out 2 hours drying through suction filtration under 90 ℃ temperature.
Measure the average grain diameter (D50) of this silver-plated spherical copper fine powder through laser diffraction formula particle size distribution device ((strain) Shimadzu Seisakusho Ltd. system, model SALD-2100), the result is 0.85 μ m.Obtain spherical copper fine powder through disproportionated reaction; Spherical copper fine powder filtration washing, suction dehydration are not directly carried out with slurry form continuously silver-plated, thereby can effectively obtain particle diameter and silver-plated spherical copper fine powder as the spherical copper fine powder of material powder basic identical (is about 107% with respect to material powder).Apparent density is 2.35g/cm
3, tap density is 3.51g/cm
3, the BET specific area is 1.68m
2/ g.The % quality of silver is 10.4% quality.
Embodiment 2 (no ultrasonic wave radiation)
The peptization that makes 8g is in 7 liters pure water, and the cuprous oxide that when stirring, adds 1000g makes it suspendible, and the cuprous oxide slurry is remained in 7 ℃.Cuprous oxide concentration in the slurry is about 143g/L, and the gum concentration in the slurry is about 1.14g/L.
Then, in 16 minutes, add 7 ℃ dilute sulfuric acid (concentration 24% quality: 9N, the mol ratio (aqueous acid/slurry): 1.3) of remaining in of 2000cc.Gather the part of the spherical copper fine powder slurry that is generated, measure average grain diameter (D50) through laser diffraction formula particle size distribution device ((strain) Shimadzu Seisakusho Ltd. system, model SALD-2100), the result is that the average grain diameter of spherical copper fine powder is 0.53 μ m.The output of spherical copper fine powder is 440g according to calculating.
Below carry out silver-plated equally with embodiment 1.
Measure the average grain diameter (D50) of this silver-plated spherical copper fine powder through laser diffraction formula particle size distribution device ((strain) Shimadzu Seisakusho Ltd. system, model SALD-2100), the result is 0.68 μ m.Obtain spherical copper fine powder through disproportionated reaction; Spherical copper fine powder filtration washing, suction dehydration are not directly carried out with slurry form continuously silver-plated, thereby can effectively obtain particle diameter and silver-plated spherical copper fine powder as the spherical copper fine powder of material powder basic identical (is about 128% with respect to material powder).Apparent density is 2.08g/cm
3, tap density is 2.79g/cm
3, the BET specific area is 3.96m
2/ g.The % quality of silver is 10.1% quality.
Embodiment 3 (the ultrasonic wave radiation is arranged)
The peptization that makes 8g is in 7 liters pure water, and the cuprous oxide that when stirring, adds 1000g makes it suspendible, and the cuprous oxide slurry is remained in 7 ℃.Cuprous oxide concentration in the slurry is about 143g/L, and the gum concentration in the slurry is about 1.14g/L.
Then, in 5 seconds, add 7 ℃ dilute sulfuric acid (concentration 24% quality: 9N, the mol ratio (aqueous acid/slurry): 1.3) of remaining in of 2000cc.Gather the part of the spherical copper fine powder slurry that is generated, measure average grain diameter (D50) through laser diffraction formula particle size distribution device ((strain) Shimadzu Seisakusho Ltd. system, model SALD-2100), the average grain diameter of the spherical copper fine powder of result is 0.10 μ m.The output of spherical copper fine powder is 440g according to calculating.
Below, carry out silver-plated equally with embodiment 1 except that in 60 minutes frequency of oscillation being set at 40kHz and carrying out the ultrasonic wave radiation 30 minutes continuous interpolation time of silver nitrate ammonia solution and after this 30 minutes mixings time being merged count.
When passing through laser diffraction formula particle size distribution device ((strain) Shimadzu Seisakusho Ltd. system, model SALD-2100) when measuring the average grain diameter (D50) of this silver-plated spherical copper fine powder, the result is 0.12 μ m.Obtain spherical copper fine powder through disproportionated reaction; Spherical copper fine powder filtration washing, suction dehydration are not directly carried out with slurry form continuously silver-plated, thereby can effectively obtain particle diameter and silver-plated spherical copper fine powder as the spherical copper fine powder of material powder basic identical (is about 120% with respect to material powder).Apparent density is 2.23g/cm
3, tap density is 3.09g/cm
3, the BET specific area is 6.05m
2/ g.The % quality of silver is 10.2% quality.
Comparative example (no ultrasonic wave radiation)
The peptization that makes 8g is in 7 liters pure water, and the cuprous oxide that when stirring, adds 1000g makes it suspendible, and the cuprous oxide slurry is remained in 7 ℃.Cuprous oxide concentration in the slurry is about 143g/L, and the gum concentration in the slurry is about 1.14g/L.
Then, in 5 seconds, add 7 ℃ dilute sulfuric acid (concentration 24% quality: 9N, the mol ratio (aqueous acid/slurry): 1.3) of remaining in of 2000cc.Gather the part of the spherical copper fine powder slurry that is generated, measure average grain diameter (D50) through laser diffraction formula particle size distribution device ((strain) Shimadzu Seisakusho Ltd. system, model SALD-2100), the average grain diameter of the spherical copper fine powder of result is 0.10 μ m.The output of spherical copper fine powder is 440g according to calculating.
Below carry out silver-plated equally with embodiment 1.
Measure the average grain diameter (D50) of this silver-plated spherical copper fine powder through laser diffraction formula particle size distribution device ((strain) Shimadzu Seisakusho Ltd. system, model SALD-2100), the result is 0.78 μ m.Obtain spherical copper fine powder through disproportionated reaction; Spherical copper fine powder filtration washing, suction dehydration are not directly carried out with slurry form continuously silver-plated, thereby can effectively obtain particle diameter with respect to as the suitable silver-plated spherical copper fine powder of big (is about 780% with respect to material powder) of the spherical copper fine powder of material powder.Apparent density is 1.65g/cm
3, tap density is 2.44g/cm
3, the BET specific area is 11.06m
2/ g.The % quality of silver is 9.0% quality.
Above result is summarized in the table 1.Silver-plated thickness setting deducts the value that the average grain diameter of spherical copper fine powder obtains for the average grain diameter from silver-plated spherical copper fine powder.
[table 1]
Can know by these results, if the average grain diameter of the spherical copper fine powder of raw material is more than about 0.4 μ m, then can be through under the wet method condition silver-plated continuously, the ultra tiny copper fine powder surface that is provided at average grain diameter less than 1 μ m is formed with the silver-plated copper micro mist of silver coating as thin as a wafer.But if the not enough about 0.4 μ m of average grain diameter, then the aggegation degree raises, so the ultrasonic wave radiation treatment when needing continuous silver-plated and silver-plated under the wet method condition.
Claims (11)
1. silver-plated copper micro mist, it has silver-plated copper fine powder for implementing on the surface, and wherein, utilizing the accumulating weight of laser diffraction and scattering formula particle size distribution to reach 50% particle diameter (D50) is less than 1 μ m, and the thickness of silver-plated film is 0.1nm ~ 0.2 μ m.
2. the silver-plated copper micro mist of claim 1, it has silver-plated copper fine powder for implementing on the surface, it is characterized in that, and the weight of silver is 1 ~ 25% quality.
3. claim 1 or 2 silver-plated copper micro mist, wherein D50 is 0.05 ~ 0.5 μ m, the thickness of silver-plated film is 0.2nm ~ 0.05 μ m.
4. each silver-plated copper micro mist in the claim 1 ~ 3, wherein, the BET specific area is 3.0 ~ 10.0m
2/ g.
5. each silver-plated copper micro mist in the claim 1 ~ 4, wherein, tap density is greater than apparent density, and apparent density is 1.0 ~ 3.0g/cm
3, tap density is 2.0 ~ 4.0g/cm
3
6. the silver-plated copper micro mist of claim 1 ~ 5, wherein, implementing copper fine powder before silver-plated, to utilize the accumulating weight of laser diffraction and scattering formula particle size distribution to reach 50% particle diameter (D50) be 0.05 ~ 0.9 μ m.
7. silver-plated copper micropowder preparing process; Said preparation method comprises and implements following operation successively: in the aqueous medium of the additive that contains natural resin, polysaccharide or derivatives thereof, add cuprous oxide and prepare slurry; Added acidic aqueous solution at 16 minutes in introversive this slurry; Carry out disproportionated reaction; It is the operation 1 of the copper fine powder slurry of 0.05 ~ 0.9 μ m that thereby the preparation accumulating weight reaches 50% particle diameter (D50), and said copper fine powder slurry is handled the organic operation 2 of removing the copper fine powder surface with alkaline solution, said copper fine powder is handled the operation 3 of the oxide of removing the copper fine powder surface with acid solution; Preparation makes said copper fine powder be scattered in the operation 4 of the copper fine powder slurry of pH3.5 ~ 4.5 in the reducing agent; Through in said copper fine powder slurry, adding silver ion solution continuously, utilize no electrolysis displacement plating and reduced form electroless plating to carry out the operation 6 of Separation of Solid and Liquid in the operation 5 of copper fine powder surface formation silver layer with to the silver-plated copper micro mist slurry that in operation 5, obtains.
8. the preparation method of claim 7, wherein, the preparation accumulating weight reaches 50% particle diameter (D50) and is the copper fine powder slurry of less than 0.4 μ m in operation 1, in operation 5 in the interpolation process of silver ion solution radiate supersonic wave.
9. the preparation method of claim 8 wherein, still continues the ultrasonic wave radiation more than 10 minutes after the interpolation of silver ion solution finishes in operation 5.
10. claim 8 or 9 preparation method, wherein, hyperacoustic frequency of oscillation of institute's radiation is 16 ~ 50kHz.
11. conduction is stuck with paste, said conduction is stuck with paste the silver-plated copper micro mist that contains in the claim 1 ~ 6 each.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010-083589 | 2010-03-31 | ||
| JP2010083589A JP5571435B2 (en) | 2010-03-31 | 2010-03-31 | Method for producing silver-plated copper fine powder |
| PCT/JP2011/057439 WO2011125556A1 (en) | 2010-03-31 | 2011-03-25 | Fine silver-plated copper powder and method for producing same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102811830A true CN102811830A (en) | 2012-12-05 |
| CN102811830B CN102811830B (en) | 2014-12-10 |
Family
ID=44762509
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201180016826.1A Expired - Fee Related CN102811830B (en) | 2010-03-31 | 2011-03-25 | Fine silver-plated copper powder and method for producing same |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP5571435B2 (en) |
| KR (1) | KR101424369B1 (en) |
| CN (1) | CN102811830B (en) |
| TW (1) | TWI468241B (en) |
| WO (1) | WO2011125556A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106925774A (en) * | 2017-03-16 | 2017-07-07 | 重庆云天化瀚恩新材料开发有限公司 | A kind of preparation method of silver-coated copper powder |
| CN113814396A (en) * | 2021-10-18 | 2021-12-21 | 苏州卡睿杰新材料科技有限公司 | Submicron silver-plated copper powder for heterojunction solar cell low-temperature slurry and preparation method thereof |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5563607B2 (en) * | 2012-01-20 | 2014-07-30 | 東洋アルミニウム株式会社 | Flaky conductive filler |
| JP5912663B2 (en) * | 2012-02-29 | 2016-04-27 | Ｊｘ金属株式会社 | Cobalt-plated copper fine powder, conductive paste produced using cobalt-plated copper fine powder, and method for producing cobalt-plated copper fine powder |
| JP5785532B2 (en) | 2012-11-30 | 2015-09-30 | 三井金属鉱業株式会社 | Silver-coated copper powder and method for producing the same |
| JP6309758B2 (en) * | 2013-12-26 | 2018-04-11 | 三井金属鉱業株式会社 | Silver-coated copper powder and method for producing the same |
| JP2016004659A (en) * | 2014-06-16 | 2016-01-12 | 株式会社村田製作所 | Conductive resin paste and ceramic electronic part |
| JP6549924B2 (en) * | 2015-07-23 | 2019-07-24 | 三井金属鉱業株式会社 | Silver-coated copper powder and method for producing the same |
| TWI609381B (en) * | 2016-02-02 | 2017-12-21 | 國立成功大學 | Method of fabricating high-conductivity thick-film copper paste coated with nano-silver for being sintered in the air |
| JP6811080B2 (en) * | 2016-02-03 | 2021-01-13 | Ｄｏｗａエレクトロニクス株式会社 | Silver-coated copper powder and its manufacturing method |
| WO2018062527A1 (en) * | 2016-09-29 | 2018-04-05 | Ｊｘ金属株式会社 | Surface treatment metal powder for laser sintering |
| TWI792540B (en) * | 2020-09-15 | 2023-02-11 | 日商Ｊｘ金屬股份有限公司 | Copper powder and copper powder manufacturing method |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004256857A (en) * | 2003-02-25 | 2004-09-16 | Ishihara Sangyo Kaisha Ltd | Copper fine particles and manufacturing method therefor |
| JP2005023417A (en) * | 2003-07-04 | 2005-01-27 | Fukuda Metal Foil & Powder Co Ltd | Production method of ultra-fine copper powder |
| JP2005256012A (en) * | 2004-03-09 | 2005-09-22 | Nikko Materials Co Ltd | Production method for fine copper powder |
| CN1962957A (en) * | 2006-11-02 | 2007-05-16 | 中国地质大学（武汉） | Method for ultrasonic electroplating of diamond drilling bit |
| CN1974870A (en) * | 2006-11-23 | 2007-06-06 | 上海交通大学 | Supersonic method of lowering internal stress of electroplated copper film |
| CN101024246A (en) * | 2006-02-24 | 2007-08-29 | 三星电机株式会社 | Core-shell structure metall nanoparticles and its manufacturing method |
| WO2008059789A1 (en) * | 2006-11-17 | 2008-05-22 | Nippon Mining & Metals Co., Ltd. | Silver-plated fine copper powder, conductive paste produced from silver-plated fine copper powder, and process for producing silver-plated fine copper powder |
| WO2009001710A1 (en) * | 2007-06-28 | 2008-12-31 | Nippon Mining & Metals Co., Ltd. | Spherical copper fine powder and process for production of the same |
| JP4204849B2 (en) * | 2002-11-12 | 2009-01-07 | Ｄｏｗａエレクトロニクス株式会社 | Production method of fine copper powder |
| US20090095198A1 (en) * | 2006-05-11 | 2009-04-16 | Eugenijus Norkus | Electroless deposition from non-aqueous solutions |
| JP2010065260A (en) * | 2008-09-09 | 2010-03-25 | Tohoku Univ | Method for producing silver-coated copper fine powder |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2832247B2 (en) * | 1990-07-24 | 1998-12-09 | 三井金属鉱業株式会社 | Method for producing silver-coated copper powder |
| KR100719993B1 (en) | 2003-09-26 | 2007-05-21 | 히다치 가세고교 가부시끼가이샤 | Mixed Conductive Powder and Use Thereof |
| KR20050053040A (en) * | 2005-05-23 | 2005-06-07 | 이찬우 | Emi/emc shielding sheet and the method for making it |
| KR100695564B1 (en) | 2005-12-27 | 2007-03-16 | 제일모직 주식회사 | Silicone paste composition and emi shield gasket |
-
2010
- 2010-03-31 JP JP2010083589A patent/JP5571435B2/en active Active
-
2011
- 2011-03-23 TW TW100109837A patent/TWI468241B/en not_active IP Right Cessation
- 2011-03-25 CN CN201180016826.1A patent/CN102811830B/en not_active Expired - Fee Related
- 2011-03-25 KR KR1020127021829A patent/KR101424369B1/en active IP Right Grant
- 2011-03-25 WO PCT/JP2011/057439 patent/WO2011125556A1/en active Application Filing
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4204849B2 (en) * | 2002-11-12 | 2009-01-07 | Ｄｏｗａエレクトロニクス株式会社 | Production method of fine copper powder |
| JP2004256857A (en) * | 2003-02-25 | 2004-09-16 | Ishihara Sangyo Kaisha Ltd | Copper fine particles and manufacturing method therefor |
| JP2005023417A (en) * | 2003-07-04 | 2005-01-27 | Fukuda Metal Foil & Powder Co Ltd | Production method of ultra-fine copper powder |
| JP2005256012A (en) * | 2004-03-09 | 2005-09-22 | Nikko Materials Co Ltd | Production method for fine copper powder |
| CN101024246A (en) * | 2006-02-24 | 2007-08-29 | 三星电机株式会社 | Core-shell structure metall nanoparticles and its manufacturing method |
| US20090095198A1 (en) * | 2006-05-11 | 2009-04-16 | Eugenijus Norkus | Electroless deposition from non-aqueous solutions |
| CN1962957A (en) * | 2006-11-02 | 2007-05-16 | 中国地质大学（武汉） | Method for ultrasonic electroplating of diamond drilling bit |
| WO2008059789A1 (en) * | 2006-11-17 | 2008-05-22 | Nippon Mining & Metals Co., Ltd. | Silver-plated fine copper powder, conductive paste produced from silver-plated fine copper powder, and process for producing silver-plated fine copper powder |
| CN1974870A (en) * | 2006-11-23 | 2007-06-06 | 上海交通大学 | Supersonic method of lowering internal stress of electroplated copper film |
| WO2009001710A1 (en) * | 2007-06-28 | 2008-12-31 | Nippon Mining & Metals Co., Ltd. | Spherical copper fine powder and process for production of the same |
| JP2010065260A (en) * | 2008-09-09 | 2010-03-25 | Tohoku Univ | Method for producing silver-coated copper fine powder |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106925774A (en) * | 2017-03-16 | 2017-07-07 | 重庆云天化瀚恩新材料开发有限公司 | A kind of preparation method of silver-coated copper powder |
| CN106925774B (en) * | 2017-03-16 | 2019-06-07 | 重庆云天化瀚恩新材料开发有限公司 | A kind of preparation method of silver-coated copper powder |
| CN113814396A (en) * | 2021-10-18 | 2021-12-21 | 苏州卡睿杰新材料科技有限公司 | Submicron silver-plated copper powder for heterojunction solar cell low-temperature slurry and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| KR101424369B1 (en) | 2014-07-31 |
| JP5571435B2 (en) | 2014-08-13 |
| CN102811830B (en) | 2014-12-10 |
| WO2011125556A1 (en) | 2011-10-13 |
| TWI468241B (en) | 2015-01-11 |
| TW201139012A (en) | 2011-11-16 |
| JP2011214080A (en) | 2011-10-27 |
| KR20120116004A (en) | 2012-10-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102811830B (en) | Fine silver-plated copper powder and method for producing same | |
| KR101945166B1 (en) | Copper powder for conductive paste and method for manufacturing same | |
| JP4868716B2 (en) | Flake copper powder and conductive paste | |
| CN101801568B (en) | Process for producing copper powder and copper powder | |
| KR101522738B1 (en) | Copper Powder For Conductive Paste and Method For Preparation Thereof | |
| US20050183543A1 (en) | Silver powder made of silver particles, each to which fine silver particles adhere and process of producing the same | |
| JPWO2008059789A1 (en) | Silver-plated copper fine powder, conductive paste produced using silver-plated copper fine powder, and method for producing silver-plated copper fine powder | |
| CN104703732A (en) | Silver-coated copper powder, and method for producing same | |
| CN107427912A (en) | Cover silver-bearing copper powder and the conductive paste, conductive coating paint, conductive sheet of silver-bearing copper powder are covered using this | |
| CN106604794A (en) | Silver-coated copper powder, and conductive paste, conductive coating material and conductive sheet, each of which uses said silver-coated copper powder | |
| CN107708893A (en) | Cover silver-bearing copper powder and using its copper cream, conductive coating paint, conductive sheet and the manufacture method for covering silver-bearing copper powder | |
| JP2018076603A (en) | Conductive particles, conductive resin composition containing the same, and coated material | |
| JP3751154B2 (en) | Silver powder manufacturing method | |
| CN104837582A (en) | Silver-coated nickel particles and method for producing same | |
| TWI273936B (en) | Slurry of ultrafine copper powder and method for producing the slurry | |
| JP5255580B2 (en) | Method for producing flake copper powder | |
| JP6159505B2 (en) | Flat copper particles | |
| JP2017039991A (en) | Silver-coated copper powder, method for producing the same, and conductive paste using the same | |
| TWI487581B (en) | Low carbon copper particles and methods for producing the same | |
| JP6549924B2 (en) | Silver-coated copper powder and method for producing the same | |
| JP5785433B2 (en) | Low carbon copper particles | |
| JP2013181177A (en) | Cobalt plated copper fine power, conductive paste produced by using the same, and method of producing the same | |
| TW201439377A (en) | Copper powders | |
| JP6031571B2 (en) | Copper powder for conductive paste and method for producing the same | |
| CN1667157A (en) | Chemically plated conductive powder and manufacturing method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: Tokyo, Japan, Japan Patentee after: JX NIPPON MINING & METALS CORPORATION Address before: Tokyo, Japan, Japan Patentee before: JX Nippon Mining & Metals Co., Ltd. |
|
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: Tokyo, Japan, Japan Patentee after: JX NIPPON MINING & METALS CORPORATION Address before: Tokyo, Japan, Japan Patentee before: JX NIPPON MINING & METALS CORPORATION |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20141210 Termination date: 20190325 |