JP6210723B2 - Silver-coated nickel particles and method for producing the same - Google Patents
Silver-coated nickel particles and method for producing the same Download PDFInfo
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- JP6210723B2 JP6210723B2 JP2013098903A JP2013098903A JP6210723B2 JP 6210723 B2 JP6210723 B2 JP 6210723B2 JP 2013098903 A JP2013098903 A JP 2013098903A JP 2013098903 A JP2013098903 A JP 2013098903A JP 6210723 B2 JP6210723 B2 JP 6210723B2
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims description 252
- 229910052709 silver Inorganic materials 0.000 title claims description 200
- 239000004332 silver Substances 0.000 title claims description 200
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims description 181
- 239000002245 particle Substances 0.000 title claims description 149
- 229910052759 nickel Inorganic materials 0.000 title claims description 120
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000007771 core particle Substances 0.000 claims description 53
- 239000003638 chemical reducing agent Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000002243 precursor Substances 0.000 claims description 20
- -1 silver ions Chemical class 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 238000007747 plating Methods 0.000 claims description 13
- 238000006073 displacement reaction Methods 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 9
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 6
- 230000001186 cumulative effect Effects 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 2
- 238000000691 measurement method Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000002002 slurry Substances 0.000 description 22
- 238000000034 method Methods 0.000 description 15
- 239000000243 solution Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 238000006722 reduction reaction Methods 0.000 description 12
- 229940100890 silver compound Drugs 0.000 description 11
- 150000003379 silver compounds Chemical class 0.000 description 11
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 10
- 238000001000 micrograph Methods 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000000428 dust Substances 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 230000001603 reducing effect Effects 0.000 description 5
- 229910001961 silver nitrate Inorganic materials 0.000 description 5
- 238000006467 substitution reaction Methods 0.000 description 5
- 229910000570 Cupronickel Inorganic materials 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000002211 L-ascorbic acid Substances 0.000 description 3
- 235000000069 L-ascorbic acid Nutrition 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229960005070 ascorbic acid Drugs 0.000 description 3
- 238000010908 decantation Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 239000010946 fine silver Substances 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine hydrate Chemical compound O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 239000002683 reaction inhibitor Substances 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- CIWBSHSKHKDKBQ-DUZGATOHSA-N D-araboascorbic acid Natural products OC[C@@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-DUZGATOHSA-N 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
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 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
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 239000004318 erythorbic acid Substances 0.000 description 1
- 235000010350 erythorbic acid Nutrition 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229940026239 isoascorbic acid Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- XNRABACJWNCNEQ-UHFFFAOYSA-N silver;azane;nitrate Chemical compound N.[Ag+].[O-][N+]([O-])=O XNRABACJWNCNEQ-UHFFFAOYSA-N 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/06—Metallic powder characterised by the shape of the particles
-
- 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
Description
本発明は、銀コートニッケル粒子及びその製造方法に関する。 The present invention relates to silver-coated nickel particles and a method for producing the same.
導体間の電気的導通を図ることを目的として、金属粉末を含む導電性ペーストや導電性接着剤などが用いられている。金属粉末としては、金や銀などの貴金属、及びニッケルや銅などの卑金属が用いられている。貴金属は酸化されにくく、導電性も高いので、導電性粉末としては好適な材料ではあるが、経済的な面から不都合がある。そこで、安価な金属であるニッケルや銅の表面に金や銀を薄くコートすることで、貴金属の使用を削減しつつ、導電性粉末の電気伝導性を高める試みが種々提案されている。 For the purpose of achieving electrical continuity between conductors, conductive pastes and conductive adhesives containing metal powder are used. As the metal powder, noble metals such as gold and silver and base metals such as nickel and copper are used. Since noble metals are difficult to oxidize and have high conductivity, they are suitable materials for conductive powders, but they are disadvantageous in terms of economy. Thus, various attempts have been proposed to increase the electrical conductivity of the conductive powder while reducing the use of noble metal by thinly coating gold or silver on the surface of inexpensive metals such as nickel and copper.
例えばニッケルの表面に銀を被覆した導電性粉末が提案されている（特許文献１及び２参照）。特許文献１においては、ニッケル粉及び錯化剤を含むスラリーと、銀の錯体溶液とを含む混合スラリーを撹拌しながら、ニッケル粉の表面に銀を析出させている。銀の析出は置換反応を利用している。特許文献２においては、ニッケル粉末及び還元剤を含む溶液Ａと、硝酸銀アンモニア錯体及び反応抑制剤を含む溶液Ｂとを反応させて、ニッケル粉末に銀を被覆している。銀の析出は還元反応を利用している。 For example, a conductive powder having a nickel surface coated with silver has been proposed (see Patent Documents 1 and 2). In Patent Document 1, silver is deposited on the surface of nickel powder while stirring a slurry containing nickel powder and a complexing agent and a mixed slurry containing a silver complex solution. The precipitation of silver utilizes a substitution reaction. In Patent Document 2, a solution A containing nickel powder and a reducing agent and a solution B containing a silver nitrate ammonia complex and a reaction inhibitor are reacted to coat the nickel powder with silver. Silver precipitation utilizes a reduction reaction.
特許文献１に記載されている置換反応を利用した銀の析出は、これを均一に行うことが容易でなく、その結果、銀コートニッケル粉の電気伝導性を高めることが容易でないという問題がある。また、置換反応を利用して銀を還元すると、還元した銀の代わりに溶出するニッケルによって、銀コート層中に多数の細孔が形成されてしまい、その細孔を通じてニッケルが外部へ露出してしまう。その結果、時間の経過とともに酸化が進行して粉の導電性が低下してしまう。 The precipitation of silver using the substitution reaction described in Patent Document 1 is not easy to uniformly perform, and as a result, it is difficult to increase the electrical conductivity of the silver-coated nickel powder. . In addition, when silver is reduced using a substitution reaction, a large number of pores are formed in the silver coat layer due to nickel that elutes instead of the reduced silver, and nickel is exposed to the outside through the pores. End up. As a result, oxidation progresses with the passage of time and the conductivity of the powder decreases.
特許文献２においては、還元反応を利用して、還元によって析出した銀の表面が平滑になるように銀を被覆しているが、銀の表面が平滑になることに起因して、銀コートニッケル粒子どうしの接点を増やすことが容易でない。その結果、電気伝導性を高めることが容易でないという問題がある。 In Patent Document 2, the reduction reaction is used to coat silver so that the surface of silver deposited by reduction becomes smooth, but the silver surface becomes smooth due to the smoothness of the silver surface. It is not easy to increase the number of contacts between particles. As a result, there is a problem that it is not easy to increase electrical conductivity.
したがって本発明の課題は、前述した従来技術が有する種々の欠点を解消し得る銀コートニッケル粒子を提供することにある。 Therefore, the subject of this invention is providing the silver coat nickel particle which can eliminate the various fault which the prior art mentioned above has.
本発明は、ニッケルを含むコア粒子の表面に銀が被覆されてなる銀コートニッケル粒子において、
前記銀コートニッケル粒子は、その表面の全域にわたって、多数の凸部が形成されており、それによって前記表面は凹凸形状をしており、
平面視での前記凸部の大きさが０．０５μｍ以上１μｍ以下であり、
前記銀コートニッケル粒子中の銀の被覆率が５０％以上である銀コートニッケル粒子を提供するものである。
The present invention provides silver-coated nickel particles in which the surface of core particles containing nickel is coated with silver.
The silver-coated nickel particles have a large number of convex portions formed over the entire surface thereof, whereby the surface has an uneven shape,
The size of the convex part in plan view is 0.05 μm or more and 1 μm or less,
The present invention provides silver-coated nickel particles having a silver coverage of 50% or more in the silver-coated nickel particles.
また本発明は、前記の銀コートニッケル粒子の好適な製造方法として、
銀イオンと、ニッケルを含むコア粒子とを水中で接触させて置換めっきを行い、該コア粒子の表面に銀を析出させて前駆体粒子を得、次いで
前記前駆体粒子と、銀イオンと、銀イオンの還元剤とを水中で接触させて、該前駆体粒子の表面に更に銀を析出させる、銀コートニッケル粒子の製造方法を提供するものである。
The present invention also provides a method for producing the silver-coated nickel particles as described above.
Silver ion and nickel-containing core particles are contacted in water to perform displacement plating, and silver is deposited on the surface of the core particles to obtain precursor particles, and then the precursor particles, silver ions, and silver The present invention provides a method for producing silver-coated nickel particles, wherein an ionic reducing agent is brought into contact with water to further precipitate silver on the surface of the precursor particles.
本発明の銀コートニッケル粒子は、粒子間の電気的導通が高いものである。 The silver-coated nickel particles of the present invention have high electrical continuity between the particles.
以下本発明を、その好ましい実施形態に基づき説明する。本発明の銀コートニッケル粒子は、ニッケルを含むコア粒子の表面が、銀からなる層（以下「銀コート層」ともいう。）で被覆されて構成されている。本明細書において、銀コートニッケル粒子とは、文脈に応じ、個々の粒子を指す場合と、粒子の集合体からなる粉体を指す場合とがある。銀は、ニッケル粒子の表面をその全域にわたって被覆していることが好ましい。換言すれば、銀は、ニッケル粒子の表面を満遍なく被覆しており、ニッケルは銀コートニッケル粒子の表面に露出していないことが好ましい。 Hereinafter, the present invention will be described based on preferred embodiments thereof. The silver-coated nickel particles of the present invention are constituted by coating the surface of core particles containing nickel with a layer made of silver (hereinafter also referred to as “silver coat layer”). In the present specification, silver-coated nickel particles may refer to individual particles or a powder composed of an aggregate of particles depending on the context. Silver preferably covers the entire surface of the nickel particles. In other words, it is preferable that the silver uniformly covers the surface of the nickel particles, and the nickel is not exposed on the surface of the silver-coated nickel particles.
ニッケルを含むコア粒子は、実質的にニッケルのみからなるか、又はニッケルを含む金属からなるものである。コア粒子がニッケルを含む金属からなるものである場合、コア粒子に占めるニッケルの割合は３質量％以上１００質量％未満であることが好ましく、ニッケル以外の金属元素の割合は０質量％超９７質量％以下であることが好ましい。ニッケルの割合が３質量％未満になると、銀コートニッケル粒子表面に凸部が形成されにくくなる場合がある。ニッケル以外の金属元素としては、例えば銅、錫、亜鉛、鉄、クロム、パラジウム、金、銀等の元素が挙げられる。これらの金属元素は１種又は２種以上を用いることができる。なお、コア粒子に、その製造過程や保存中に、酸素等の非金属元素が不可避的に少量混入することは許容される。本明細書においては、簡便のため、ニッケルからなるコア粒子、及びニッケルを含む金属のコア粒子の表面に銀がコートされてなる粒子の両者を総称して「銀コートニッケル粒子」という。 The core particle containing nickel is made of only nickel or a metal containing nickel. When the core particles are made of a metal containing nickel, the proportion of nickel in the core particles is preferably 3% by mass or more and less than 100% by mass, and the proportion of metal elements other than nickel is more than 0% by mass and 97% by mass. % Or less is preferable. When the proportion of nickel is less than 3% by mass, it may be difficult to form convex portions on the surface of the silver-coated nickel particles. Examples of metal elements other than nickel include elements such as copper, tin, zinc, iron, chromium, palladium, gold, and silver. These metal elements can be used alone or in combination of two or more. In addition, it is allowed that non-metallic elements such as oxygen are inevitably mixed in the core particles during the production process and storage. In the present specification, for the sake of simplicity, both the core particles made of nickel and the particles obtained by coating silver on the surface of nickel-containing metal core particles are collectively referred to as “silver-coated nickel particles”.
ニッケルを含むコア粒子は、その形状に特に制限はない。例えばコア粒子として球形、多面体、扁平体（フレーク）、デンドライトなどの形状をしているものを用いることができる。なお、コア粒子の表面を被覆する銀は、その被覆厚みが小さいので、銀コートニッケル粒子の形状は、コア粒子の形状と実質的に同じである。 The core particle containing nickel is not particularly limited in its shape. For example, a core particle having a spherical shape, a polyhedron shape, a flat shape (flakes), a dendrite shape, or the like can be used. In addition, since the silver which coat | covers the surface of a core particle has the small coating thickness, the shape of a silver coat nickel particle is substantially the same as the shape of a core particle.
本発明の銀コートニッケル粒子は、ニッケルを含むコア粒子の表面を被覆している銀コート層に特徴の一つを有している。詳細には、この銀コート層は、微小な銀の粒子の凝集体からなるものである。このような構造の銀コート層によって、ニッケルを含むコア粒子の表面が被覆されていることで、ニッケルの酸化が極力抑制される。その結果、長期間の保存の後であっても、本発明の銀コートニッケル粒子は、電気抵抗の低下が極力抑えられたものとなる。これに対して、銀コート層が多数の細孔を有していると考えられる特許文献１に記載の銀コートニッケル粒子においては、ニッケルを含むコア粒子の表面が、細孔を通じて外界に接しやすくなることから、長期間の保存によってニッケルが酸化される傾向にあり、そのことに起因して電気抵抗が低下しやすい。微小な銀の粒子の凝集体からなる銀コート層を形成する方法については後述する。 The silver-coated nickel particles of the present invention have one of the characteristics of a silver-coated layer that covers the surface of core particles containing nickel. Specifically, the silver coat layer is composed of an aggregate of fine silver particles. The surface of the core particle containing nickel is covered with the silver coat layer having such a structure, so that oxidation of nickel is suppressed as much as possible. As a result, even after long-term storage, the silver-coated nickel particles of the present invention are those in which the decrease in electrical resistance is suppressed as much as possible. In contrast, in the silver-coated nickel particles described in Patent Document 1 in which the silver-coated layer is considered to have a large number of pores, the surface of the core particles containing nickel is likely to come into contact with the outside through the pores. Therefore, nickel tends to be oxidized by long-term storage, and the electrical resistance is likely to decrease due to this. A method for forming a silver coat layer composed of an aggregate of fine silver particles will be described later.
本発明の銀コートニッケル粒子は、粒子表面の形状にも特徴の一つを有している。詳細には、本発明の銀コートニッケル粒子は、その表面に多数の凸部が形成されている。その結果、本発明の銀コートニッケル粒子はその表面が、凸部と、凸部間に位置する凹部に起因する凹凸形状を有している。このような凹凸形状を有していることに起因して、本発明の銀コートニッケル粒子は、表面が平滑な銀コートニッケル粒子、例えば特許文献２に記載のものに比べて粒子どうしの接触面積が大きくなる。そのことに起因して本発明の銀コートニッケル粒子は、粒子間での電気伝導性が高いものとなる。特にニッケルは、導電性粒子に用いられる他の金属、例えば銅に比べて硬い金属なので、圧力を加えても変形しづらいことから、表面が凹凸形状であることは、粒子間での電気伝導性の向上に極めて有利である。 The silver-coated nickel particles of the present invention have one of the characteristics of the particle surface shape. Specifically, the silver-coated nickel particles of the present invention have a large number of convex portions formed on the surface thereof. As a result, the surface of the silver-coated nickel particles of the present invention has a concavo-convex shape due to the convex portions and the concave portions located between the convex portions. Due to having such a concavo-convex shape, the silver-coated nickel particles of the present invention have a contact area between particles as compared with silver-coated nickel particles having a smooth surface, for example, those described in Patent Document 2. Becomes larger. As a result, the silver-coated nickel particles of the present invention have high electrical conductivity between the particles. In particular, nickel is a hard metal compared to other metals used in conductive particles, such as copper, so it is difficult to deform even when pressure is applied. It is extremely advantageous to improve
上述した凸部の大きさは、銀コートニッケル粒子間での電気伝導性の向上に影響を与える要因である。この観点から、平面視での個々の凸部の大きさは、平均して０．０５μｍ以上１μｍ以下であることが好ましく、０．１μｍ以上０．８μｍ以下であることが更に好ましく、０．２μｍ以上０．５μｍ以下であることが一層好ましい。このような大きさの凸部が形成されていることで、粒子どうしの接触面積を容易に大きくすることができる。 The size of the protrusions described above is a factor that affects the improvement in electrical conductivity between silver-coated nickel particles. From this viewpoint, the size of each convex portion in plan view is preferably 0.05 μm or more and 1 μm or less on average, more preferably 0.1 μm or more and 0.8 μm or less, and more preferably 0.2 μm. More preferably, it is 0.5 μm or less. By forming the convex portion having such a size, the contact area between the particles can be easily increased.
平面視での凸部の大きさは、銀コートニッケル粒子表面を電子顕微鏡によって観察し、観察像を画像解析することによって求められる。画像解析には例えば、走査型電子顕微鏡を用いることができる。これを用い、具体的には、ニッケルを含むコア粒子の表面に存在している銀粒子の平面視での面積を計測し、その面積と同じ面積の円の直径を算出する。この直径の値を、凸部の大きさとする。 The size of the convex portion in plan view is determined by observing the surface of the silver-coated nickel particles with an electron microscope and analyzing the image of the observed image. For example, a scanning electron microscope can be used for the image analysis. Specifically, the area of the silver particles existing on the surface of the core particle containing nickel is measured in plan view, and the diameter of a circle having the same area as the area is calculated. The value of this diameter is taken as the size of the convex portion.
平面視での凸部の大きさは上述のとおりであるところ、平面視での凸部の形状は、例えば略円形や多角形などの異方性の小さい形状であり得る。これらの形状を有する凸部が形成されていることで、粒子どうしの接触面積を容易に大きくすることができる。異方性が小さいとは、長径／短径の値が５以下である形状をいう。 Although the size of the convex portion in plan view is as described above, the shape of the convex portion in plan view may be a shape with small anisotropy such as a substantially circular shape or a polygonal shape. By forming the convex portions having these shapes, the contact area between the particles can be easily increased. “Small anisotropy” refers to a shape having a major axis / minor axis value of 5 or less.
凸部の大きさは、銀コートニッケル粒子の大きさとも関係している。この観点から、銀コートニッケル粒子は、その粒径が０．０５μｍ以上１００μｍ以下であることが好ましく、０．５μｍ以上５０μｍ以下であることが更に好ましく、１μｍ以上２０μｍ以下であることが一層好ましい。銀コートニッケル粒子の粒径をこの範囲に設定することで、粒子どうしの接触面積を容易に大きくすることができる。なお、銀コートニッケル粒子において、ニッケルを含むコア粒子の表面を被覆する銀は、その被覆厚みが小さいので、コア粒子の粒径は、銀コートニッケル粒子の形状と実質的に同じになる。 The size of the convex portion is also related to the size of the silver-coated nickel particles. In this respect, the silver-coated nickel particles preferably have a particle size of 0.05 μm to 100 μm, more preferably 0.5 μm to 50 μm, and still more preferably 1 μm to 20 μm. By setting the particle diameter of the silver-coated nickel particles within this range, the contact area between the particles can be easily increased. In the silver-coated nickel particles, the silver covering the surface of the core particles containing nickel has a small coating thickness, so that the particle diameter of the core particles is substantially the same as the shape of the silver-coated nickel particles.
銀コートニッケル粒子の粒径は、レーザー回折散乱式粒度分布測定法によって測定することができる。この方法で測定された累積体積５０容量％における体積累積粒径Ｄ50を前記の粒径とする。 The particle size of the silver-coated nickel particles can be measured by a laser diffraction / scattering particle size distribution measurement method. The cumulative volume particle diameter D 50 in the cumulative volume 50% by volume measured by this method to the particle size of the.
一つの粒子に着目した場合、該粒子中に存在する凸部の数は１μｍ2あたり２個以上５００個以下であることが好ましく、５個以上５００個以下であることが更に好ましく、１０個以上５００個以下であることが一層好ましい。凸部の数をこのようにすることで、粒子どうしの接触面積を容易に大きくすることができる。 When focusing on one particle, the number of convex portions present in the particle is preferably 2 or more and 500 or less, more preferably 5 or more and 500 or less per 1 μm 2. More preferably, it is 500 or less. By making the number of convex portions in this way, the contact area between particles can be easily increased.
コア粒子の表面を被覆している銀コート層は、その被覆率が５０％以上であり、６０％以上であることが好ましく、７０％以上であることが更に好ましい。最も好ましくは、銀コート層は、コア粒子の表面の全域を満遍なく被覆している（つまり被覆率が１００％である。）。被覆率は、例えば走査型電子顕微鏡を用い、銀コートニッケル粒子について銀及びコア粒子を構成する元素を対象とした元素マッピングを行い、銀が占める面積及びコア粒子を構成する元素が占める面積を求める。これらの面積に基づき、｛銀が占める面積／（銀が占める面積＋コア粒子を構成する元素が占める面積）｝×１００から被覆率を算出する。あるいは、走査型電子顕微鏡を用い、銀コートニッケル粒子について反射電子像のコントラストの違いに基づく銀が占める面積及びコア粒子を構成する元素が占める面積を求める。これらの面積に基づき、｛銀が占める面積／（銀が占める面積＋コア粒子を構成する元素が占める面積）｝×１００から被覆率を算出する。反射電子像のコントラストにおいては、原子量が大きい元素は明るく写り、小さい元素は暗く写る。例えば、コア粒子にニッケルを用いた場合、銀は明るく写り、ニッケルは暗く写る。 The silver coat layer covering the surface of the core particles has a coverage of 50% or more, preferably 60% or more, and more preferably 70% or more. Most preferably, the silver coat layer uniformly covers the entire surface of the core particle (that is, the coverage is 100%). The coverage is obtained by, for example, using a scanning electron microscope, performing element mapping on the silver-coated nickel particles with respect to the elements constituting the silver and the core particles, and determining the area occupied by the silver and the area occupied by the elements constituting the core particle. . Based on these areas, the coverage is calculated from {area occupied by silver / (area occupied by silver + area occupied by elements constituting core particles)} × 100. Alternatively, by using a scanning electron microscope, the area occupied by silver and the area occupied by the elements constituting the core particles are determined for the silver-coated nickel particles based on the difference in contrast of the reflected electron image. Based on these areas, the coverage is calculated from {area occupied by silver / (area occupied by silver + area occupied by elements constituting core particles)} × 100. In the contrast of the reflected electron image, an element with a large atomic weight appears bright and a small element appears dark. For example, when nickel is used for the core particles, silver appears bright and nickel appears dark.
凸部は、少なくともその表面が銀から構成されている。好ましくは、凸部はその全体が実質的に銀から構成されている。凸部の全体が実質的に銀から構成されていることで、粒子間での電気伝導性を高くすることができる。凸部の全体が実質的に銀から構成されていることは、例えば銀コートニッケル粒子の断面について元素分析を行うことで確認することができる。この元素分析によって凸部における銀の割合が８０質量％以上である場合、凸部は実質的に銀から形成されているということができる。 At least the surface of the convex portion is made of silver. Preferably, the whole convex part is substantially comprised from silver. Since the entire convex portion is substantially made of silver, electrical conductivity between particles can be increased. The fact that the entire convex portion is substantially composed of silver can be confirmed, for example, by conducting elemental analysis on the cross section of the silver-coated nickel particles. When the ratio of silver in the convex portion is 80% by mass or more by this elemental analysis, it can be said that the convex portion is substantially formed of silver.
本発明の銀コートニッケル粒子において、銀が占める割合は０．５質量％以上５０質量％以下であることが好ましく、５質量％以上２０質量％以下であることが更に好ましい。この範囲の割合で銀が含まれていることで、本発明の銀コートニッケル粒子は、経済性と電気伝導性とのバランスを図ることができる。銀コートニッケル粒子において銀が占める割合は、例えば銀コートニッケル粒子を、酸等を用いて溶解させ、その溶液を用いＩＣＰ発光分光分析法によって測定することができる。 In the silver-coated nickel particles of the present invention, the proportion of silver is preferably 0.5% by mass or more and 50% by mass or less, and more preferably 5% by mass or more and 20% by mass or less. By containing silver at a ratio in this range, the silver-coated nickel particles of the present invention can achieve a balance between economic efficiency and electrical conductivity. The proportion of silver in the silver-coated nickel particles can be measured, for example, by dissolving the silver-coated nickel particles with an acid or the like and using the resulting solution by ICP emission spectroscopy.
本発明の銀コートニッケル粒子は、上述のとおりの凸部を有していることで、粒子間での電気伝導性が高いものとなる。電気伝導性は、銀コートニッケル粒子の粒径や、銀の含有量及び被覆率等に応じて異なる。例えば銀コートニッケル粒子の粒径が６〜８μｍであり、銀の含有量が１０〜１１質量％であり、被覆率が５０％以上である場合、１０２ｋｇｆ／ｃｍ2圧力下での圧粉抵抗が、好ましくは５．０×１０-5Ω・ｃｍ以上５．０×１０-3Ω・ｃｍ以下、更に好ましくは５．０×１０-5Ω・ｃｍ以上１．０×１０-3Ω・ｃｍ以下という高電気伝導性を示す。これに対して、コア粒子と銀粒子を単に混合したものは、銀粒子とコア粒子と間の密着性が、銀コートニッケル粒子よりも劣るので、接触抵抗が増してしまう。そのことに起因して、コア粒子と銀粒子を単に混合しただけでは、電気抵抗が高くなってしまう。 The silver coat nickel particle of this invention becomes a thing with high electrical conductivity between particle | grains by having the convex part as mentioned above. The electrical conductivity varies depending on the particle diameter of the silver-coated nickel particles, the silver content, the coverage, and the like. For example, when the particle diameter of the silver-coated nickel particles is 6 to 8 μm, the silver content is 10 to 11% by mass, and the coverage is 50% or more, the dust resistance under 102 kgf / cm 2 pressure is , Preferably 5.0 × 10 −5 Ω · cm to 5.0 × 10 −3 Ω · cm, more preferably 5.0 × 10 −5 Ω · cm to 1.0 × 10 −3 Ω · cm It shows the following high electrical conductivity. On the other hand, since the adhesiveness between the silver particles and the core particles is inferior to that of the silver-coated nickel particles, the contact resistance increases when the core particles and the silver particles are simply mixed. As a result, simply mixing the core particles and silver particles increases the electrical resistance.
前記の圧粉抵抗は、例えば三菱化学アナリテック製の粉体抵抗測定システム ＭＣＰ−ＰＤ５１を用いて４端子４探針法に従い測定できる。 The dust resistance can be measured according to a 4-terminal 4-probe method using, for example, a powder resistance measurement system MCP-PD51 manufactured by Mitsubishi Chemical Analytech.
上述した種々の特徴を有する本発明の銀コートニッケル粒子は、好適には置換めっき法と還元めっき法とをこの順で組み合わせた銀被覆方法によって製造される。初めに行う置換めっき法においては、銀イオンと、ニッケルを含むコア粒子とを水中で接触させて置換めっきを行い、該コア粒子の表面に銀を析出させて前駆体粒子を得る（工程１）。次に行う還元めっき法では、前記前駆体粒子と、銀イオンと、銀イオンの還元剤とを水中で接触させて、該前駆体粒子の表面に更に銀を析出させる（工程２）。以下、それぞれの工程について説明する。 The silver-coated nickel particles of the present invention having the various characteristics described above are preferably produced by a silver coating method in which a displacement plating method and a reduction plating method are combined in this order. In the displacement plating method that is performed first, silver ions and nickel-containing core particles are contacted in water to perform displacement plating, and silver is deposited on the surface of the core particles to obtain precursor particles (step 1). . In the subsequent reduction plating method, the precursor particles, silver ions, and a silver ion reducing agent are brought into contact in water to further precipitate silver on the surfaces of the precursor particles (step 2). Hereinafter, each process will be described.
工程１において用いるニッケルを含むコア粒子は、種々の方法で製造することができる。例えばコア粒子がニッケルからなる場合には、該コア粒子は、各種の還元剤を用い、ニッケル化合物を湿式で還元することでコア粒子を得ることができる。あるいは、ニッケルの溶湯を用い、アトマイズ法によってコア粒子を得ることができる。このようにして得られたコア粒子の好ましい粒子径や形状は先に述べたとおりである。これらの方法によって得られたコア粒子を水中で銀イオンと接触させる。 The core particles containing nickel used in Step 1 can be produced by various methods. For example, when the core particles are made of nickel, the core particles can be obtained by using various reducing agents and reducing the nickel compound wet. Alternatively, core particles can be obtained by an atomizing method using a molten nickel. The preferable particle diameter and shape of the core particles thus obtained are as described above. The core particles obtained by these methods are contacted with silver ions in water.
銀イオンは、銀源となる銀化合物から生成させる。銀化合物としては、例えば硝酸銀等の水溶性銀化合物を用いることができる。水中における銀イオンの濃度は、０.０１ｍｏｌ／Ｌ以上５ｍｏｌ／Ｌ以下、特に０．０５ｍｏｌ／Ｌ以上０．５ｍｏｌ／Ｌ以下に設定することが、望ましい量の銀をコア粒子の表面に析出させ得る観点と量産性の観点から好ましい。 Silver ions are generated from a silver compound serving as a silver source. As the silver compound, for example, a water-soluble silver compound such as silver nitrate can be used. The concentration of silver ions in water is set to 0.01 mol / L or more and 5 mol / L or less, particularly 0.05 mol / L or more and 0.5 mol / L or less, so that a desired amount of silver is deposited on the surface of the core particles. From the viewpoint of obtaining and mass productivity.
一方、水中におけるコア粒子の量は、１０ｇ／Ｌ以上１０００ｇ／Ｌ以下、特に５０ｇ／Ｌ以上５００ｇ／Ｌ以下とすることが、やはり望ましい量の銀をコア粒子の表面に析出させ得る観点と量産性の観点から好ましい。 On the other hand, the amount of core particles in water is 10 g / L or more and 1000 g / L or less, and particularly 50 g / L or more and 500 g / L or less, so that a desirable amount of silver can be deposited on the surface of the core particles and mass production. From the viewpoint of sex.
コア粒子と銀イオンとの添加の順序に特に制限はない。例えばコア粒子と銀イオンとを同時に水中に添加することができる。置換めっきによる銀の析出のコントロールのしやすさの観点からは、水中にコア粒子を予め分散させてスラリーを調製し、このスラリーに銀源となる銀化合物を添加することが好ましい。この場合、スラリーは２０℃〜２５℃の常温でもよく、あるいはそれ以外の０℃〜８０℃の温度範囲でもよい。また、銀化合物の添加に先立ち、スラリー中にエチレンジアミン四酢酸、トリエチレンジアミン、イミノ二酢酸、クエン酸若しくは酒石酸、又はそれらの塩等の錯化剤を添加しておき、銀の還元をコントロールするようにしてもよい。 There are no particular restrictions on the order of addition of the core particles and silver ions. For example, core particles and silver ions can be simultaneously added to water. From the viewpoint of easy control of silver deposition by displacement plating, it is preferable to prepare a slurry by dispersing core particles in water in advance and add a silver compound as a silver source to the slurry. In this case, the slurry may have a room temperature of 20 ° C. to 25 ° C., or other temperature range of 0 ° C. to 80 ° C. Prior to the addition of the silver compound, a complexing agent such as ethylenediaminetetraacetic acid, triethylenediamine, iminodiacetic acid, citric acid or tartaric acid, or a salt thereof is added to the slurry to control the reduction of silver. It may be.
銀化合物の添加は、水溶液の状態で行うことが好ましい。この水溶液は、スラリー中に一括添加することもでき、あるいは所定の時間にわたって連続的に又は不連続に添加することもできる。置換めっきの反応を制御しやすい点から、銀化合物の水溶液は、所定の時間にわたってスラリーに添加することが好ましい。 The addition of the silver compound is preferably performed in the state of an aqueous solution. This aqueous solution can be added all at once in the slurry, or can be added continuously or discontinuously over a predetermined time. From the viewpoint of easily controlling the reaction of displacement plating, it is preferable to add the aqueous silver compound solution to the slurry over a predetermined time.
置換めっきによってコア粒子の表面に銀が析出して前駆体粒子が得られる。前駆体粒子における銀の析出量は、最終的に得られる銀コートニッケル粒子における銀の量の０．１〜５０質量％、特に１〜２０質量％とすることが、目的とする凸部を有し、かつ緻密な銀コート層を形成し得る点から好ましい。 Silver is deposited on the surface of the core particles by displacement plating to obtain precursor particles. The amount of silver deposited on the precursor particles is 0.1 to 50% by weight, particularly 1 to 20% by weight, based on the amount of silver in the finally obtained silver-coated nickel particles. And it is preferable from the point which can form a precise | minute silver coat layer.
工程２においては、工程１で得られた前駆体粒子を含むスラリーに、銀イオン及び銀イオンの還元剤を添加する。この場合、工程１で得られた前駆体粒子を一旦固液分離した後に水に分散させてスラリーとなしてもよく、あるいは工程１で得られた前駆体粒子のスラリーをそのまま工程２に供してもよい。後者の場合、スラリー中に、工程１で添加した銀イオンが残存していてもよく、あるいは残存していなくてもよい。 In step 2, silver ions and a silver ion reducing agent are added to the slurry containing the precursor particles obtained in step 1. In this case, the precursor particles obtained in step 1 may be solid-liquid separated and then dispersed in water to form a slurry, or the precursor particle slurry obtained in step 1 may be directly used in step 2. Also good. In the latter case, the silver ions added in step 1 may or may not remain in the slurry.
工程２において添加する銀イオンは、工程１と同じく水溶性銀化合物から生成させる。銀化合物は、水溶液の状態でスラリーに添加することが好ましい。銀水溶液中の銀イオンの濃度は好ましくは０．０１ｍｏｌ／Ｌ以上１０ｍｏｌ／Ｌ以下、更に好ましくは０．１ｍｏｌ／Ｌ以上１.０ｍｏｌ／Ｌ以下である。この範囲の濃度を有する銀水溶液を、１０ｇ／Ｌ以上１０００ｇ／Ｌ以下、特に５０ｇ／Ｌ以上５００ｇ／Ｌ以下の前駆体粒子を含む前記スラリーにおける該前駆体粒子１００質量部に対して１質量部以上５０質量部以下、特に５質量部以上３０質量部以下添加することが、目的とする凸部を有し、かつ緻密な銀コート層を形成し得る点から好ましい。 The silver ion added in the step 2 is generated from a water-soluble silver compound as in the step 1. The silver compound is preferably added to the slurry in the form of an aqueous solution. The concentration of silver ions in the aqueous silver solution is preferably 0.01 mol / L or more and 10 mol / L or less, more preferably 0.1 mol / L or more and 1.0 mol / L or less. 1 mass part of silver aqueous solution which has the density | concentration of this range with respect to 100 mass parts of said precursor particle | grains in the said slurry containing the precursor particle of 10 g / L or more and 1000 g / L or less, especially 50 g / L or more and 500 g / L or less. It is preferable to add 50 parts by mass or less, particularly 5 parts by mass or more and 30 parts by mass or less from the viewpoint of forming a target silver convex part and forming a dense silver coat layer.
工程２において添加する還元剤としては、銀の置換めっき及び還元めっきを同時に進行させ得る程度の還元力を有するものを用いることが有利である。このような還元剤を用いることで、目的とする凸部を有し、かつ緻密な銀コート層を首尾よく形成することができる。還元性の強い還元剤を用いると、銀が単独で析出してしまい、コア粒子を被覆しにくくなるという不都合がある。一方、還元性の弱い還元剤を用いると、還元剤による銀の還元反応が起こりにくくなり、その代わりに置換反応が優先的に起きてしまい、コア粒子を均一に被覆しにくくなるという不都合がある。以上の観点から、還元剤としては、還元剤の水溶液の標準電極電位が−１．５〜０．８Ｖ（ＮＨＥ）を示すものが好ましい。具体的
には、蟻酸、シュウ酸、Ｌ−アスコルビン酸、エリソルビン酸、ホルムアルデヒド、チオ硫酸ナトリウム、ヒドラジン、水素化ホウ素ナトリウムなどがある。これらの有機還元剤は１種を単独で用いてもよく、あるいは２種以上を組み合わせて用いてもよい。その中でも、Ｌ−アスコルビン酸を用いることが好ましい。
As the reducing agent to be added in the step 2, it is advantageous to use a reducing agent having such a reducing power that the silver displacement plating and the reduction plating can proceed simultaneously. By using such a reducing agent, it is possible to successfully form a dense silver coat layer having a target convex portion. When a reducing agent having a strong reducing property is used, silver is precipitated alone, which makes it difficult to coat the core particles. On the other hand, when a reducing agent having a weak reducing property is used, it is difficult for the reducing agent to cause a silver reduction reaction. Instead, a substitution reaction occurs preferentially, which makes it difficult to uniformly coat the core particles. . From the above viewpoint, the reducing agent is preferably one in which the standard electrode potential of the reducing agent aqueous solution is -1.5 to 0.8 V (NHE). Specific examples include formic acid, oxalic acid, L-ascorbic acid, erythorbic acid, formaldehyde, sodium thiosulfate, hydrazine, and sodium borohydride. These organic reducing agents may be used individually by 1 type, or may be used in combination of 2 or more type. Among these, it is preferable to use L-ascorbic acid.
還元剤の添加量は、添加する銀溶液中の銀イオンに対して０．５〜５.０当量、特に１.０〜２.０当量とすることが、目的とする凸部を有し、かつ緻密な銀コート層を形成し得る点から好ましい。 The amount of the reducing agent to be added is 0.5 to 5.0 equivalents, particularly 1.0 to 2.0 equivalents with respect to the silver ions in the silver solution to be added, and has a target convex portion. And it is preferable from the point which can form a precise | minute silver coat layer.
前駆体粒子を含むスラリーに還元剤及び銀イオンを添加するときの順序に特に制限はない。銀イオンの還元を制御して、凸部を有し、かつ緻密な銀コート層を形成する観点からは、スラリー中に還元剤を添加した後に銀イオンを添加することが好ましい。銀源となる銀化合物は、スラリー中に一括添加することもでき、あるいは所定の時間にわたって連続的に又は不連続に添加することもできる。銀イオンの還元を制御しやすい点から、銀化合物はその水溶液の状態で、所定の時間にわたってスラリーに添加することが好ましい。 There is no particular limitation on the order in which the reducing agent and silver ions are added to the slurry containing the precursor particles. From the viewpoint of controlling the reduction of silver ions to form a dense silver coat layer having convex portions, it is preferable to add silver ions after adding a reducing agent to the slurry. The silver compound to be a silver source can be added all at once in the slurry, or can be added continuously or discontinuously over a predetermined time. From the viewpoint of easily controlling the reduction of silver ions, the silver compound is preferably added to the slurry in a state of an aqueous solution over a predetermined time.
工程２においては、スラリーを２０℃〜２５℃の常温の状態にしておいてもよく、あるいはそれ以外の０〜８０℃の温度範囲で加熱しておいてもよい。銀イオンの還元反応を十分に行う観点から、還元剤を添加した後、所定時間にわたってスラリーの撹拌を継続することが好ましい。 In step 2, the slurry may be kept at a room temperature of 20 ° C. to 25 ° C., or may be heated in the other temperature range of 0 to 80 ° C. From the viewpoint of sufficiently carrying out the silver ion reduction reaction, it is preferable to continue stirring the slurry for a predetermined time after adding the reducing agent.
工程２においては、反応時間や銀イオンの濃度を適宜調整することによって、目的とする凸部を有する銀コートニッケル粒子が得られる。 In step 2, by appropriately adjusting the reaction time and the concentration of silver ions, silver-coated nickel particles having a desired convex portion can be obtained.
このようにして得られた銀コートニッケル粒子は、これを含む導電性組成物の状態で好適に用いられる。例えば銀コートニッケル粒子をビヒクル及びガラスフリット等と混合して導電ペーストとなすことができる。あるいは、銀コート銅粉を有機溶媒等と混合してインクとなすことができる。このようにして得られた導電ペーストやインクを適用対象物の表面に施すことで、所望のパターンを有する導電性膜を得ることができる。 The silver-coated nickel particles thus obtained are preferably used in the state of a conductive composition containing the same. For example, silver-coated nickel particles can be mixed with a vehicle and glass frit to form a conductive paste. Alternatively, silver-coated copper powder can be mixed with an organic solvent or the like to form an ink. A conductive film having a desired pattern can be obtained by applying the conductive paste or ink thus obtained to the surface of the object to be applied.
以下、実施例により本発明を更に詳細に説明する。しかしながら本発明の範囲は、かかる実施例に制限されない。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the scope of the present invention is not limited to such examples.
〔実施例１〕
（１）第１工程
４０℃に加熱した１．５Ｌの純水中に、３００ｇのニッケル粉を投入し、スラリーとなした。このニッケル粉は、累積体積５０容量％における体積累積粒Ｄ50＝７μｍであるものを用いた。ここに、６０ｇの硫酸を加えて更に撹拌し、酸洗を行った。次いで、純水でのデカンテーションによりニッケル粉の洗浄を行い、乾燥させずに水中で保持した。
このニッケル粉に、４０℃に加熱した１．５Ｌの純水を加え、撹拌しながら、エチレンジアミン四酢酸二ナトリウム１２．８ｇを添加し、溶解させた。引き続き２０ｇのクエン酸を添加し、溶解させた。更にこのスラリーに、０．４ｍｏｌ／Ｌの硝酸銀水溶液２４ｍＬを１分間にわたって連続添加して、置換めっきを行い、ニッケル粒子の表面に銀を析出させて前駆体粒子を得た。
[Example 1]
(1) First Step 300 g of nickel powder was put into 1.5 L of pure water heated to 40 ° C. to form a slurry. The nickel powder used was a volume cumulative particle D 50 = 7 μm at a cumulative volume of 50% by volume. To this, 60 g of sulfuric acid was added and further stirred to carry out pickling. Next, the nickel powder was washed by decantation with pure water, and kept in water without being dried.
To this nickel powder, 1.5 L of pure water heated to 40 ° C. was added, and 12.8 g of disodium ethylenediaminetetraacetate was added and dissolved while stirring. Subsequently, 20 g of citric acid was added and dissolved. Further, 24 mL of a 0.4 mol / L silver nitrate aqueous solution was continuously added to this slurry for 1 minute to perform displacement plating, and silver was deposited on the surface of the nickel particles to obtain precursor particles.
（２）第２工程
還元剤としてのＬ−アスコルビン酸をスラリー中に添加し、溶解させた。添加量は銀イオンの還元に対して１．１５当量とした。更に、０．４ｍｏｌ／Ｌの硝酸銀水溶液６９６ｍＬを２９分間にわたって連続添加した。これによって、前駆体粒子の表面に銀を更に析出させ、目的とする銀コートニッケル粒子を得た。得られた銀コートニッケル粒子の走査型電子顕微鏡像を図１に示す。得られた粒子における銀が占める割合は１０．７質量％であった。また、得られた粒子の断面を元素分析したところ、凸部は銀のみから形成されていることが確認された。
(2) Second step L-ascorbic acid as a reducing agent was added to the slurry and dissolved. The amount added was 1.15 equivalents relative to the reduction of silver ions. Further, 696 mL of a 0.4 mol / L silver nitrate aqueous solution was continuously added over 29 minutes. As a result, silver was further deposited on the surface of the precursor particles, and target silver-coated nickel particles were obtained. A scanning electron microscope image of the obtained silver-coated nickel particles is shown in FIG. The proportion of silver in the obtained particles was 10.7% by mass. Moreover, when the cross section of the obtained particle was subjected to elemental analysis, it was confirmed that the convex portion was formed only from silver.
〔実施例２〕
ニッケル粒子の粒径を、Ｄ50＝２１μｍに変えた以外は実施例１と同じ工程を行い、銀コートニッケル粒子を得た。得られた銀コートニッケル粒子の走査型電子顕微鏡像を図２に示す。
[Example 2]
Except for changing the particle diameter of the nickel particles to D 50 = 21 μm, the same process as in Example 1 was performed to obtain silver-coated nickel particles. A scanning electron microscope image of the obtained silver-coated nickel particles is shown in FIG.
〔実施例３〕
コア粒子として、Ｄ50が２７μｍであり、ニッケル含有量が１０．８質量％の銅ニッケル合金からなる粒子を用いた。これ以外は実施例１と同じ工程を行い、銀コート銅ニッケル粒子を得た。得られた銀コート銅ニッケル粒子の走査型電子顕微鏡像を図３に示す。
Example 3
As the core particles, particles made of a copper nickel alloy having a D 50 of 27 μm and a nickel content of 10.8% by mass were used. Except this, the same process as Example 1 was performed and the silver coat copper nickel particle was obtained. A scanning electron microscope image of the obtained silver-coated copper-nickel particles is shown in FIG.
〔比較例１〕
本比較例は、実施例１の第１工程である置換反応を行ず前駆体粒子を製造しなかった例である。すなわち、実施例１において、硝酸銀の添加前に還元剤を添加した。それ以外は実施例１と同じ工程を行い、銀コートニッケル粒子を得た。得られた銀コートニッケル粒子の走査型電子顕微鏡像を図４に示す。
[Comparative Example 1]
This comparative example is an example in which the substitution reaction, which is the first step of Example 1, was performed and precursor particles were not produced. That is, in Example 1, the reducing agent was added before the addition of silver nitrate. Other than that performed the same process as Example 1, and obtained the silver coat nickel particle. A scanning electron microscope image of the obtained silver-coated nickel particles is shown in FIG.
〔比較例２〕
本比較例は、特許文献２（特開２０１１−１４４４４１号公報）の実施例１に相当するものである。
０．５Ｌのビーカーに、０．２８Ｌの純水を入れ、Ｄ50＝２１μｍのニッケル粉を投入し、撹拌した。ここに、３．６ｍｌの濃硝酸を加えて更に撹拌し、酸洗を行った。次いで、純水でのデカンテーションによりニッケル粉の洗浄を行い、乾燥させずに水中で保持した。
このニッケル粉末に、０．２Ｌの純水、３６ｍｌのアンモニア水、及び２．１ｇのヒドラジン一水和物を加えて撹拌し、溶液（Ａ）を調製した。
溶液（Ａ）とは別に、２６ｍｌの純水に、９．４５ｇの硝酸銀、及び０．１ｇの反応抑制剤（ビッグケミー・ジャパン（株）製Ｄｉｓｐｅｒｂｙｋ−１１１）、７２ｍｌのアンモニア水を加えて撹拌し、溶液（Ｂ）を調製した。
溶液（Ａ）を撹拌しながら、溶液（Ａ）中に、溶液（Ｂ）を、１０分間で滴下した。この後、ジェットアジターでの撹拌を１５分続けた後、上澄み液を除去した後、デカンテーションにより銀コートニッケル粒子を洗浄し、濾過脱水した。次いで、６０℃で１５時間の乾燥を行い、目的とする銀コートニッケル粒子を得た。得られた銀コートニッケル粒子の走査型電子顕微鏡像を図５に示す。得られた粒子における銀が占める割合は１０．１質量％であった。
[Comparative Example 2]
This comparative example corresponds to Example 1 of Japanese Patent Application Laid-Open No. 2011-144441.
In a 0.5 L beaker, 0.28 L of pure water was added, nickel powder of D 50 = 21 μm was added and stirred. To this, 3.6 ml of concentrated nitric acid was added and further stirred to perform pickling. Next, the nickel powder was washed by decantation with pure water, and kept in water without being dried.
To the nickel powder, 0.2 L of pure water, 36 ml of ammonia water, and 2.1 g of hydrazine monohydrate were added and stirred to prepare a solution (A).
Separately from solution (A), 9.45 g of silver nitrate, 0.1 g of a reaction inhibitor (Disperbyk-111 manufactured by Big Chemie Japan Co., Ltd.) and 72 ml of aqueous ammonia are added to 26 ml of pure water and stirred. Solution (B) was prepared.
While the solution (A) was stirred, the solution (B) was dropped into the solution (A) over 10 minutes. Thereafter, stirring with a jet agitator was continued for 15 minutes, and after removing the supernatant, the silver-coated nickel particles were washed by decantation and filtered and dehydrated. Next, drying was performed at 60 ° C. for 15 hours to obtain target silver-coated nickel particles. A scanning electron microscope image of the obtained silver-coated nickel particles is shown in FIG. The proportion of silver in the obtained particles was 10.1% by mass.
〔評価〕
実施例及び比較例で得られた銀コートニッケル粒子について、上述した方法で平面視での凸部の大きさ及び形状を測定した。また、銀コートニッケル粒子の粒径Ｄ50を測定した。更に銀の被覆率及び圧粉抵抗を測定した。これらの結果を以下の表１に示す。
[Evaluation]
About the silver coat nickel particle obtained by the Example and the comparative example, the magnitude | size and shape of the convex part by planar view were measured by the method mentioned above. It was also measured particle diameter D 50 of the silver-coated nickel particles. Further, the silver coverage and dust resistance were measured. These results are shown in Table 1 below.
表１に示す結果から明らかなとおり、各実施例の銀コートニッケル粒子（本発明品）は、比較例１の銀コートニッケル粒子よりも圧粉抵抗が低いことが判る。特に、実施例１と比較例１との対比から明らかなとおり、粒径が同程度であり、かつ凸部の大きさが同程度であっても、被覆率が低い比較例１では圧粉抵抗が高くなることが判る。また、実施例２と比較例２との対比から明らかなとおり、銀コート層の被覆率が高くても、銀コート層が凹凸形状をしていない比較例２では圧粉抵抗が高くなることが判る。 As is apparent from the results shown in Table 1, it can be seen that the silver-coated nickel particles of the examples (products of the present invention) have a lower dust resistance than the silver-coated nickel particles of Comparative Example 1. In particular, as is clear from the comparison between Example 1 and Comparative Example 1, even if the particle size is about the same and the size of the convex portion is about the same, in Comparative Example 1 where the coverage is low, the dust resistance is low. It turns out that becomes high. Further, as is clear from the comparison between Example 2 and Comparative Example 2, even when the coverage of the silver coat layer is high, the dust resistance is high in Comparative Example 2 in which the silver coat layer is not uneven. I understand.
Claims (6)
前記銀コートニッケル粒子は、その表面の全域にわたって、多数の凸部が形成されており、それによって前記表面は凹凸形状をしており、
凸部における銀の割合が８０質量％以上であり、
平面視での前記凸部の大きさが０．２μｍ以上０．８μｍ以下であり、
前記銀コートニッケル粒子は、レーザー回折散乱式粒度分布測定法による累積体積５０容量％における体積累積粒径Ｄ 50 が１μｍ以上５０μｍ以下であり、
前記銀コートニッケル粒子中の銀の被覆率が５０％以上である銀コートニッケル粒子。 In silver-coated nickel particles in which the surface of core particles containing nickel is coated with silver,
The silver-coated nickel particles have a large number of convex portions formed over the entire surface thereof, whereby the surface has an uneven shape,
The proportion of silver in the convex part is 80% by mass or more,
The size of the convex portion in plan view is not less than 0.2 μm and not more than 0.8 μm ,
The silver-coated nickel particles have a volume cumulative particle diameter D 50 at a cumulative volume of 50% by volume measured by a laser diffraction / scattering particle size distribution measurement method of 1 μm to 50 μm,
Silver-coated nickel particles having a silver coverage of 50% or more in the silver-coated nickel particles.
銀イオンと、ニッケルを含むコア粒子とを水中で接触させて置換めっきを行い、該コア粒子の表面に銀を析出させて前駆体粒子を得、次いで
前記前駆体粒子と、銀イオンと、銀イオンの還元剤とを水中で接触させて、該前駆体粒子の表面に更に銀を析出させる、銀コートニッケル粒子の製造方法。 It is a manufacturing method of the silver coat nickel particle according to claim 1,
Silver ion and nickel-containing core particles are contacted in water to perform displacement plating, and silver is deposited on the surface of the core particles to obtain precursor particles, and then the precursor particles, silver ions, and silver A method for producing silver-coated nickel particles, wherein an ionic reducing agent is brought into contact with water to further precipitate silver on the surface of the precursor particles.
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| PCT/JP2013/080203 WO2014181486A1 (en) | 2013-05-08 | 2013-11-08 | Silver-coated nickel particles and method for producing same |
| CN201380064002.0A CN104837582A (en) | 2013-05-08 | 2013-11-08 | Silver-coated nickel particles and method for producing same |
| KR1020157014898A KR20160004991A (en) | 2013-05-08 | 2013-11-08 | Silver-coated nickel particles and method for producing same |
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| JP6846969B2 (en) * | 2016-03-31 | 2021-03-24 | Ｄｏｗａエレクトロニクス株式会社 | Silver-coated nickel powder and its manufacturing method |
| WO2018180286A1 (en) * | 2017-03-31 | 2018-10-04 | 富士フイルム株式会社 | Gold coated silver plate shaped particle, gold coated silver plate shaped particle dispersion fluid and method for manufacturing same, applied film, and antireflective optical member |
| CN108296478A (en) * | 2018-01-11 | 2018-07-20 | 宁波广新纳米材料有限公司 | Silver-nickel powder and preparation method thereof and electrocondution slurry containing the silver-nickel powder |
| CN110842190B (en) * | 2019-10-11 | 2021-10-15 | 云南大学 | Preparation method of silver-coated copper powder |
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| CN114783770B (en) * | 2022-06-20 | 2022-12-13 | 西安宏星电子浆料科技股份有限公司 | External electrode slurry of multilayer ceramic capacitor and preparation method thereof |
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