JP2003183703A - Production method for conductive powder, conductive powder, conductive paste, and laminated ceramic electronic part - Google Patents
Production method for conductive powder, conductive powder, conductive paste, and laminated ceramic electronic partInfo
- Publication number
- JP2003183703A JP2003183703A JP2001377455A JP2001377455A JP2003183703A JP 2003183703 A JP2003183703 A JP 2003183703A JP 2001377455 A JP2001377455 A JP 2001377455A JP 2001377455 A JP2001377455 A JP 2001377455A JP 2003183703 A JP2003183703 A JP 2003183703A
- Authority
- JP
- Japan
- Prior art keywords
- powder
- base metal
- conductive
- metal powder
- conductive powder
- 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
- 239000000843 powder Substances 0.000 title claims abstract description 300
- 239000000919 ceramic Substances 0.000 title claims abstract description 61
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 27
- 239000010953 base metal Substances 0.000 claims abstract description 99
- 229910000521 B alloy Inorganic materials 0.000 claims abstract description 57
- 239000000243 solution Substances 0.000 claims abstract description 37
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 15
- 239000012266 salt solution Substances 0.000 claims abstract description 15
- 150000003839 salts Chemical class 0.000 claims abstract description 11
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 10
- 239000000956 alloy Substances 0.000 claims abstract description 10
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 3
- 239000002245 particle Substances 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 23
- 238000001556 precipitation Methods 0.000 claims description 20
- 238000000151 deposition Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 4
- 238000010030 laminating Methods 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 abstract description 52
- 238000007254 oxidation reaction Methods 0.000 abstract description 52
- 230000001376 precipitating effect Effects 0.000 abstract description 2
- 229910052802 copper Inorganic materials 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 46
- 238000006243 chemical reaction Methods 0.000 description 22
- 239000003985 ceramic capacitor Substances 0.000 description 13
- 239000012298 atmosphere Substances 0.000 description 11
- 230000007547 defect Effects 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 229910052810 boron oxide Inorganic materials 0.000 description 9
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 9
- 239000011230 binding agent Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000010304 firing Methods 0.000 description 7
- 238000007772 electroless plating Methods 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 6
- 238000007747 plating Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 239000012279 sodium borohydride Substances 0.000 description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000001856 Ethyl cellulose Substances 0.000 description 2
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 2
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 229920001249 ethyl cellulose Polymers 0.000 description 2
- 235000019325 ethyl cellulose Nutrition 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000007847 structural defect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229940116411 terpineol Drugs 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910018104 Ni-P Inorganic materials 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- 229910018487 Ni—Cr Inorganic materials 0.000 description 1
- 229910018536 Ni—P Inorganic materials 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、耐酸化性を有する
導電粉末の製造方法、上述の製造方法によって得られる
導電粉末、上述の導電粉末を含有してなる導電性ペース
ト、および上述の導電性ペーストを用いて内部電極が形
成された積層セラミック電子部品に関するものであり、
特に、積層セラミックコンデンサの内部電極形成に好適
な導電性ペーストに用いられる耐酸化性を有する導電粉
末の製造方法、導電粉末、導電性ペーストおよび積層セ
ラミック電子部品に関する。TECHNICAL FIELD The present invention relates to a method for producing a conductive powder having oxidation resistance, a conductive powder obtained by the above-mentioned production method, a conductive paste containing the above-mentioned conductive powder, and the above-mentioned conductive powder. The present invention relates to a laminated ceramic electronic component in which internal electrodes are formed using a paste,
In particular, the present invention relates to a method for producing an electrically conductive powder having oxidation resistance, which is used as an electrically conductive paste suitable for forming an internal electrode of a laminated ceramic capacitor, an electrically conductive powder, an electrically conductive paste, and a laminated ceramic electronic component.
【０００２】[0002]
【従来の技術】従来、積層セラミック電子部品、例えば
積層セラミックコンデンサのように、生のセラミック積
層体とペースト塗布膜を同時焼成して焼結させる場合に
用いられる、内部電極形成用の導電性ペーストとして
は、高温下でも酸化に対して安定で、かつ素体セラミッ
ク焼成温度より融点の高いＰｄ、Ａｇ−Ｐｄ、Ｐｔ等の
貴金属粉末と、有機ビヒクルと、を含有してなる導電性
ペーストが用いられてきた。しかし、これら貴金属粉末
は高価であり、かつ価格が安定しないことから、近年で
はＮｉ粉末、Ｃｕ粉末、またはこれらを主成分として含
有する粉末等の卑金属粉末を含有してなる導電性ペース
トを用いて内部電極を形成した、低コストな積層セラミ
ックコンデンサや多層セラミック基板等の積層セラミッ
ク電子部品が生産されている。2. Description of the Related Art Conventionally, a conductive paste for forming internal electrodes, which is used when a raw ceramic laminate and a paste coating film are simultaneously fired and sintered, such as a monolithic ceramic electronic component such as a monolithic ceramic capacitor. As the conductive paste, a noble metal powder such as Pd, Ag-Pd, or Pt having a melting point higher than the firing temperature of the elemental ceramic and an organic vehicle, which is stable to oxidation even at high temperature, is used. Has been. However, since these precious metal powders are expensive and the price is not stable, in recent years, Ni powder, Cu powder, or a conductive paste containing a base metal powder such as a powder containing these as the main component is used. Multilayer ceramic electronic components such as low-cost monolithic ceramic capacitors and multilayer ceramic substrates on which internal electrodes are formed are produced.
【０００３】上述のような積層セラミック電子部品の製
造工程においては、Ｎｉ粉末やＣｕ粉末の酸化を防止す
るため、脱バインダー工程および本焼成工程における雰
囲気制御が非常に重要となる。このうち、脱バインダー
工程においては、これら卑金属粉末の酸化を防止するた
め、窒素気流等の中性雰囲気か、もしくはこれら卑金属
粉末が酸化しない程度のごく低温の酸化雰囲気により、
有機物の分解を目的とした熱処理が行われている。In the manufacturing process of the above-mentioned monolithic ceramic electronic component, in order to prevent the oxidation of Ni powder and Cu powder, the atmosphere control in the debinding process and the main firing process is very important. Among these, in the binder removal step, in order to prevent the oxidation of these base metal powders, a neutral atmosphere such as a nitrogen stream, or an extremely low temperature oxidizing atmosphere such that these base metal powders are not oxidized,
Heat treatment for the purpose of decomposing organic substances is performed.
【０００４】[0004]
【発明が解決しようとする課題】有機物の熱分解のため
には、その燃焼のために必要な十分な酸素と温度が要求
される。しかしながら、従来の卑金属粉末を含有してな
る導電性ペーストを用いる場合には、上述したように、
窒素気流中等の中性雰囲気か、もしくはこれら卑金属粉
末が酸化しない程度のごく低温の酸化雰囲気中で脱バイ
ンダーを行わなければならなかった。この脱バインダー
工程における雰囲気にバラツキが生じ、有機物の分解や
除去が不十分となると、残留したカーボン成分が本焼成
時にセラミックの焼結を阻害し、セラミックが焼結不足
となってしまう。そのため、十分な静電容量や絶縁抵抗
が得られないという問題が発生する。For the thermal decomposition of organic matter, sufficient oxygen and temperature necessary for its combustion are required. However, when using a conventional conductive paste containing a base metal powder, as described above,
It has been necessary to perform the binder removal in a neutral atmosphere such as a nitrogen stream or in an oxidizing atmosphere at a very low temperature at which these base metal powders are not oxidized. If the atmosphere in the debinding step varies and the decomposition and removal of the organic matter becomes insufficient, the residual carbon component hinders the sintering of the ceramic during the main firing, resulting in insufficient sintering of the ceramic. Therefore, there arises a problem that sufficient capacitance and insulation resistance cannot be obtained.
【０００５】また、逆に、脱バインダー工程時に卑金属
が酸化してしまうと、卑金属粉末の酸化膨張による脱バ
インダー時の層剥がれといった構造不良や、酸化による
卑金属粉末の焼結不足による取得容量の低下や、等価直
列抵抗ならびにｔａｎδの増加等の不具合が発生する。
したがって、脱バインダー時において微妙な雰囲気管理
が必要となり、工程管理が煩雑となり、工程不良の原因
となる問題がある。On the contrary, if the base metal is oxidized during the debinding process, the structural capacity such as layer peeling during debinding due to the oxidative expansion of the base metal powder and the decrease in the acquired capacity due to insufficient sintering of the base metal powder due to oxidation will occur. And problems such as an increase in equivalent series resistance and tan δ occur.
Therefore, there is a problem that delicate atmosphere management is required at the time of binder removal, process management becomes complicated, and process defects occur.
【０００６】このような問題を解決する方法として、特
開平１−２５８３０６号公報、特開平１−２６５４０６
号公報及び特開平１−８０００８号公報において、卑金
属粉末の酸化防止のため、Ｎｉ粉末にＢ粉末またはＢ化
合物粉末の１種または１種以上を含ませるとともに、無
機質フィラーおよび有機ビヒクルを含有させた導電性ペ
ーストが開示されている。しかしながら、この方法で
は、ペースト混錬が不十分である場合、Ｂ粉末またはＢ
化合物粉末の分散状態が不十分となり、卑金属粉末の耐
酸化性にバラツキが生じるという問題がある。As a method for solving such a problem, Japanese Patent Laid-Open Nos. 1-258306 and 1-265406 are available.
In Japanese Patent Laid-Open Publication No. 1-80008 and Japanese Patent Application Laid-Open No. 1-80008, Ni powder contains one or more kinds of B powder or B compound powder and an inorganic filler and an organic vehicle in order to prevent oxidation of the base metal powder. A conductive paste is disclosed. However, in this method, when the paste kneading is insufficient, B powder or B powder
There is a problem that the dispersion state of the compound powder becomes insufficient and the base metal powder varies in oxidation resistance.
【０００７】また、無電解めっき反応によって、Ａｇ粉
末あるいはＣｕ粉末表面にＮｉ−Ｂ合金を析出させる技
術が特開昭６３−２７５６７号公報に開示されている。
しかし、この公報において開示されている従来の無電解
めっきの方法である、金属塩、還元剤、錯化剤、ｐＨ調
整剤などで調整された１液の無電解めっき液に被めっき
物である粉末を浸漬する方法では、板のような被めっき
物と比べて被面積が大きいため、めっき反応速度が異常
に速く、所望の金属析出量の制御が困難である。また、
通常の無電解めっき液は、金属塩濃度が希薄であり、粉
末のような比表面積が大きな被めっき物では、粉末投入
時にめっき液の分解が急速に進み、粉末表面への金属の
析出が不十分になるといった問題があった。Further, Japanese Unexamined Patent Publication (Kokai) No. 63-27567 discloses a technique for depositing a Ni-B alloy on the surface of Ag powder or Cu powder by electroless plating reaction.
However, a conventional electroless plating method disclosed in this publication, which is a one-electroless plating solution adjusted with a metal salt, a reducing agent, a complexing agent, a pH adjusting agent, etc., is an object to be plated. In the method of immersing the powder, since the area to be plated is larger than that of the object to be plated such as a plate, the plating reaction rate is abnormally fast, and it is difficult to control the desired metal deposition amount. Also,
Ordinary electroless plating solution has a low metal salt concentration, and for an object to be plated having a large specific surface area such as powder, decomposition of the plating solution progresses rapidly when the powder is charged, and metal deposition on the powder surface does not occur. There was a problem that it would be enough.
【０００８】本発明は、上記従来の問題に鑑みなされた
ものであり、その目的は、導電性ペーストに用いられる
耐酸化性を有する導電粉末の製造方法、導電粉末、導電
性ペーストおよび積層セラミック電子部品を提供するこ
とにある。The present invention has been made in view of the above conventional problems, and an object thereof is a method for producing an electrically conductive powder having oxidation resistance used in an electrically conductive paste, an electrically conductive powder, an electrically conductive paste and a laminated ceramic electronic. It is to provide parts.
【０００９】[0009]
【課題を解決するための手段】こうした粉末への金属無
電解めっきの問題を解決する方法として、本発明者は、
被めっき物である卑金属粉末と、金属塩とを混合した溶
液に、還元剤溶液を添加して、卑金属粉末表面にＮｉ−
Ｂ合金を析出させる方法を見出した。これにより、耐酸
化性を有する導電粉末を得ることができる。この導電粉
末を用いた導電性ペーストは、高温下でも酸化に対して
安定であるため、焼成工程を経る積層セラミック電子部
品の内部電極の形成等に好適に用いることができる。As a method of solving the problem of metal electroless plating on such powder, the present inventor has
A reducing agent solution is added to a solution in which a base metal powder that is an object to be plated and a metal salt are mixed, and Ni- is added to the surface of the base metal powder.
The method of precipitating B alloy was discovered. Thereby, a conductive powder having oxidation resistance can be obtained. Since the conductive paste using this conductive powder is stable against oxidation even at high temperatures, it can be suitably used for forming internal electrodes of a laminated ceramic electronic component that undergoes a firing process.
【００１０】さらに、本発明者は、耐酸化性を有する卑
金属粉末を作製するのに、好適な卑金属粉末の溶液濃度
や反応温度などの反応条件を見出した。Further, the present inventor has found suitable reaction conditions such as a solution concentration of the base metal powder and a reaction temperature for producing the base metal powder having oxidation resistance.
【００１１】すなわち、本発明の耐酸化性を備える導電
粉末の製造方法は、Ｎｉ粉末、Ｃｕ粉末、Ｎｉまたは／
およびＣｕを主成分とする合金粉末からなる群から選ば
れる少なくとも１種の卑金属粉末と、Ｎｉ塩とを含む金
属塩溶液に、水素化硼化物を含む還元剤溶液を混合し、
前記卑金属粉末の表面にＮｉ−Ｂ合金粉末を析出させる
析出工程を備える。析出工程では、前記Ｎｉ塩が還元剤
溶液により液相還元されることにより、Ｎｉ−Ｂ合金粉
末が卑金属粉末の表面に析出する。また、金属塩溶液に
おける卑金属粉末の溶液濃度が４００ｇ／Ｌ以上である
ことを特徴としている。Ｌとは１０3ｃｍ3を示す。That is, the method for producing an electrically conductive powder having oxidation resistance according to the present invention is applied to Ni powder, Cu powder, Ni or /
And a reducing agent solution containing a borohydride is mixed with a metal salt solution containing at least one base metal powder selected from the group consisting of alloy powders containing Cu as a main component and a Ni salt,
A deposition step of depositing the Ni-B alloy powder on the surface of the base metal powder is provided. In the precipitation step, the Ni salt is liquid-phase reduced by the reducing agent solution, so that the Ni-B alloy powder is deposited on the surface of the base metal powder. In addition, the solution concentration of the base metal powder in the metal salt solution is 400 g / L or more. L means 10 3 cm 3 .
【００１２】上記の方法によれば、金属塩溶液と卑金属
粉末とを混合することにより、還元剤溶液の投入時に還
元剤が卑金属粉末表面の触媒作用により分解し電子を放
出し、卑金属粉末近傍には金属イオンが高濃度で存在す
るため、金属イオンの還元がすぐに起こり、卑金属粉末
表面に金属が析出する。そのため、卑金属粉末溶液に金
属塩溶液と還元剤溶液とを同時に添加する方法や、卑金
属粉末を混合した還元剤溶液に金属塩溶液を添加する方
法に比べて、卑金属粉末表面で金属が析出しやすく、Ｎ
ｉ−Ｂ合金粉末を析出させる場合は、卑金属粉末の耐酸
化性を高くすることができる。According to the above method, by mixing the metal salt solution and the base metal powder, the reducing agent is decomposed by the catalytic action of the surface of the base metal powder to release electrons when the reducing agent solution is charged, and electrons are emitted in the vicinity of the base metal powder. Since the metal ions are present at a high concentration, the reduction of the metal ions occurs immediately and the metal is deposited on the base metal powder surface. Therefore, compared with the method of adding the metal salt solution and the reducing agent solution to the base metal powder solution at the same time, or the method of adding the metal salt solution to the reducing agent solution in which the base metal powder is mixed, the metal is more likely to precipitate on the base metal powder surface. , N
When depositing the i-B alloy powder, the oxidation resistance of the base metal powder can be increased.
【００１３】なお、上述の製造方法は、析出工程の反応
温度が、０℃以上、５０℃以下であることが好ましい。In the above manufacturing method, the reaction temperature in the precipitation step is preferably 0 ° C. or higher and 50 ° C. or lower.
【００１４】また、上述の製造方法は、析出工程の後
に、Ｎｉ−Ｂ合金粉末が表面に析出した卑金属粉末を１
００℃以上で熱処理する熱処理工程をさらに備えること
が好ましい。Further, in the above-mentioned manufacturing method, after the precipitation step, the base metal powder having the Ni-B alloy powder deposited on the surface is
It is preferable to further include a heat treatment step of heat treatment at 00 ° C. or higher.
【００１５】また、上述の製造方法は、前記析出工程の
後に、前記Ｎｉ−Ｂ合金粉末が表面に析出した前記卑金
属粉末を粉砕処理する粉砕処理工程をさらに備えること
が好ましい。Further, it is preferable that the above-mentioned manufacturing method further comprises, after the precipitation step, a crushing step of crushing the base metal powder having the Ni-B alloy powder deposited on its surface.
【００１６】また、上述の製造方法は、前記卑金属粉末
の平均粒径より小さく、かつ、前記卑金属粉末１００重
量部に対して５０重量部以下の量のＮｉ−Ｂ合金粉末を
析出させることが好ましい。Further, in the above-mentioned manufacturing method, it is preferable that the Ni-B alloy powder is deposited in an amount smaller than the average particle size of the base metal powder and 50 parts by weight or less with respect to 100 parts by weight of the base metal powder. .
【００１７】また、上述の製造方法は、前記卑金属粉末
の平均粒径が、１．０μｍ以下であることが好ましい。In the above manufacturing method, it is preferable that the base metal powder has an average particle size of 1.0 μm or less.
【００１８】また、上述の製造方法は、前記Ｎｉ−Ｂ合
金粉末の平均粒径は、０．１μｍ以下であり、かつ、前
記卑金属粉末の平均粒径の１／２以下であることが好ま
しい。Further, in the above-mentioned manufacturing method, it is preferable that the Ni-B alloy powder has an average particle diameter of 0.1 μm or less and 1/2 or less of the average particle diameter of the base metal powder.
【００１９】本発明の導電粉末は、上述の本発明の導電
粉末の製造方法によって得られたことを特徴としてい
る。これにより、耐酸化性を有する導電粉末を得ること
ができる。The conductive powder of the present invention is characterized by being obtained by the above-mentioned method for producing a conductive powder of the present invention. Thereby, a conductive powder having oxidation resistance can be obtained.
【００２０】本発明の導電性ペーストは、上述の本発明
の導電粉末と、有機ビヒクルと、を含有してなることを
特徴としている。The conductive paste of the present invention is characterized by containing the above-mentioned conductive powder of the present invention and an organic vehicle.
【００２１】本発明の積層セラミック電子部品は、複数
のセラミック層が積層されてなるセラミック積層体と、
前記セラミック層間に形成された複数の内部電極とを備
える積層セラミック電子部品であって、前記内部電極
は、上記導電性ペーストを用いて形成されていることを
特徴としている。The laminated ceramic electronic component of the present invention comprises a ceramic laminated body formed by laminating a plurality of ceramic layers,
A multilayer ceramic electronic component including a plurality of internal electrodes formed between the ceramic layers, wherein the internal electrodes are formed using the conductive paste.
【００２２】[0022]
【発明の実施の形態】本発明の一実施の形態について図
１および図２に基づいて説明すれば、以下の通りであ
る。BEST MODE FOR CARRYING OUT THE INVENTION An embodiment of the present invention will be described below with reference to FIGS. 1 and 2.
【００２３】本実施の形態にかかる導電粉末について、
図１（ａ）および図１（ｂ）に基づいて詳細に説明す
る。図１（ａ）に示すように、導電粉末１は、卑金属粉
末２と、Ｎｉ−Ｂ合金粉末３ａとからなる。Regarding the conductive powder according to the present embodiment,
A detailed description will be given based on FIGS. 1A and 1B. As shown in FIG. 1A, the conductive powder 1 is composed of a base metal powder 2 and a Ni-B alloy powder 3a.
【００２４】卑金属粉末２は、例えば、Ｎｉ粉末、Ｃｕ
粉末、Ｎｉ−Ｐ合金粉末、Ｎｉ−Ｃｒ合金粉末、Ｃｕ−
Ｚｎ合金粉末、Ｐｄ粉末が付着したＮｉ粉末、Ａｇ粉末
が付着したＮｉ粉末、Ｐｄ−Ａｇ合金粉末が付着したＮ
ｉ粉末、Ｐｔ粉末が付着したＮｉ粉末、Ｐｄ粉末が付着
したＣｕ粉末、Ａｇ粉末が付着したＣｕ粉末、Ｐｄ−Ａ
ｇ合金粉末が付着したＣｕ粉末、Ｐｔ粉末が付着したＣ
ｕ粉末等が挙げられ、積層セラミック電子部品のセラミ
ック特性に合わせて適宜選択される。The base metal powder 2 is, for example, Ni powder or Cu.
Powder, Ni-P alloy powder, Ni-Cr alloy powder, Cu-
Zn alloy powder, Ni powder with Pd powder attached, Ni powder with Ag powder attached, N with Pd-Ag alloy powder attached
i powder, Ni powder with Pt powder attached, Cu powder with Pd powder attached, Cu powder with Ag powder attached, Pd-A
Cu powder to which g alloy powder adheres, C to which Pt powder adheres
u powder or the like may be used and is appropriately selected according to the ceramic characteristics of the multilayer ceramic electronic component.
【００２５】Ｎｉ−Ｂ合金粉末３ａは、卑金属粉末２の
表面に析出している。Ｎｉ−Ｂ合金粉末３ａを卑金属粉
末２表面に析出させる方法は、被めっき物である卑金属
粉末２とＮｉ塩とを混合した溶液に、水素化硼化物を含
む還元剤溶液を添加する方法である。本発明では、卑金
属粉末２とＮｉ塩とを混合した溶液に、上記還元剤溶液
を添加する条件を詳細に検討し、卑金属粉末２の溶液濃
度及び反応温度を制御することによって、同じ析出量の
Ｎｉ−Ｂ合金粉末３ａで耐酸化性を向上させる条件を見
出した。Ｎｉ−Ｂ合金粉末３ａの析出時における溶液中
の卑金属粉末２濃度が高いほど、卑金属粉末２表面でＮ
ｉ−Ｂ合金粉末３ａが析出する割合が高くなり、卑金属
粉末２の耐酸化性が向上する。卑金属粉末２の溶液濃度
は４００ｇ／Ｌ以上が必要であり、これより濃度が低い
場合はＮｉ−Ｂ合金粉末が卑金属粉末表面以外において
単独で析出するため、耐酸化性が低下する。また、卑金
属粉末２の溶液濃度の上限値は、特に限定されるもので
はないが、１０００ｇ／Ｌ以下が好ましく、８００ｇ／
Ｌ以下がより好ましい。The Ni-B alloy powder 3a is deposited on the surface of the base metal powder 2. The method of depositing the Ni-B alloy powder 3a on the surface of the base metal powder 2 is a method of adding a reducing agent solution containing a borohydride to a solution in which the base metal powder 2 as the object to be plated and a Ni salt are mixed. . In the present invention, the conditions under which the reducing agent solution is added to the solution in which the base metal powder 2 and the Ni salt are mixed are studied in detail, and the solution concentration of the base metal powder 2 and the reaction temperature are controlled to obtain the same precipitation amount. The conditions for improving the oxidation resistance have been found with the Ni-B alloy powder 3a. The higher the concentration of the base metal powder 2 in the solution during the precipitation of the Ni-B alloy powder 3a, the more N the surface of the base metal powder 2 has.
The proportion of the i-B alloy powder 3a precipitated is increased, and the oxidation resistance of the base metal powder 2 is improved. The solution concentration of the base metal powder 2 needs to be 400 g / L or more, and when the concentration is lower than this, the Ni-B alloy powder alone precipitates on the surface other than the base metal powder surface, and the oxidation resistance decreases. The upper limit of the solution concentration of the base metal powder 2 is not particularly limited, but is preferably 1000 g / L or less, and 800 g / L.
L or less is more preferable.
【００２６】また、反応温度の下限値については、０℃
以上であることが好ましく、２０℃以上であることがよ
り好ましい。反応温度が低いほどＮｉ−Ｂ合金粉末３ａ
の急激な析出を制御することができ、卑金属粉末２表面
でのＮｉ−Ｂ合金粉末３ａの析出が起こりやすくなるた
め、耐酸化性を向上させることができる。また、反応温
度の上限値については、５０℃以下であることが好まし
い。反応温度が５０℃を超えると、Ｎｉ−Ｂ合金粉末３
ａの急激な析出が起こり、卑金属粉末２表面以外で単独
に析出するため、耐酸化性が低下する。The lower limit of the reaction temperature is 0 ° C.
It is preferably at least 20 ° C., more preferably at 20 ° C. or higher. The lower the reaction temperature, the more Ni-B alloy powder 3a.
Of the Ni-B alloy powder 3a is likely to occur on the surface of the base metal powder 2, so that the oxidation resistance can be improved. The upper limit of the reaction temperature is preferably 50 ° C or lower. When the reaction temperature exceeds 50 ° C, Ni-B alloy powder 3
Since a rapid precipitation of a occurs, and it precipitates independently on the surface other than the surface of the base metal powder 2, the oxidation resistance decreases.
【００２７】次に、上記導電粉末１に熱を加えた場合に
ついて、図１（ｂ）に基づいて詳細に説明する。図１
（ｂ）に示すように、加熱された導電粉末１ａは、卑金
属粉末２が、酸化硼素膜３ｂにより略被覆された構成と
なる。Next, the case where heat is applied to the conductive powder 1 will be described in detail with reference to FIG. Figure 1
As shown in (b), the heated conductive powder 1a has a configuration in which the base metal powder 2 is substantially covered with the boron oxide film 3b.
【００２８】酸化硼素膜３ｂは、Ｎｉ−Ｂ合金粉末３ａ
に含まれるＢ成分が酸化した後、熔融して卑金属粉末２
の表面を略被覆するように残留させたものである。Ｎｉ
−Ｂ合金粉末３ａは、特開昭５６−８４８０６号公報に
記載されているように、温度が上昇すると、まずＢ成分
が酸化して酸化硼素となり、さらに温度が上昇すると、
酸化硼素が熔融する。この酸化硼素は、卑金属粉末２の
表面を略被覆する酸化硼素膜３ｂとなり、卑金属粉末２
の酸化を防止する。The boron oxide film 3b is a Ni-B alloy powder 3a.
After the B component contained in is oxidized, it is melted to form the base metal powder 2
Is left so as to substantially cover the surface. Ni
In the -B alloy powder 3a, as described in JP-A-56-84806, when the temperature rises, the B component is first oxidized to boron oxide, and when the temperature further rises,
Boron oxide melts. This boron oxide becomes a boron oxide film 3b which substantially covers the surface of the base metal powder 2, and the base metal powder 2
To prevent the oxidation of.
【００２９】つまり、Ｎｉ−Ｂ合金粉末３ａを卑金属粉
末２表面に析出させた導電粉末１を含有する導電性ペー
ストは、ペースト中にＢ粉末またはＢ化合物を添加して
分散させた導電性ペーストに比べて、ペースト中にＮｉ
−Ｂ合金粉末が均一に分散されているため、卑金属粉末
の耐酸化性のバラツキを少なくすることができる。ま
た、卑金属粉末２の近傍にＮｉ−Ｂ合金粉末３ａが存在
しているので、例えば導電性ペーストを焼成した場合、
酸化硼素膜３ｂが卑金属粉末２を被覆する割合がより高
くなる。このような導電粉末１を含有してなる導電性ペ
ーストを用いて内部電極を形成した積層セラミック電子
部品は、その製造過程である焼成工程において、酸化硼
素膜３ｂが卑金属粉末２の表面を略被覆することから、
卑金属粉末２の耐酸化性が高まる。That is, the conductive paste containing the conductive powder 1 in which the Ni-B alloy powder 3a is deposited on the surface of the base metal powder 2 is a conductive paste in which the B powder or the B compound is added and dispersed in the paste. Compared to Ni in the paste
Since the -B alloy powder is uniformly dispersed, it is possible to reduce variations in the oxidation resistance of the base metal powder. Further, since the Ni-B alloy powder 3a is present in the vicinity of the base metal powder 2, for example, when the conductive paste is fired,
The ratio of the boron oxide film 3b covering the base metal powder 2 becomes higher. In the multilayer ceramic electronic component in which the internal electrodes are formed by using the conductive paste containing the conductive powder 1, the boron oxide film 3b substantially covers the surface of the base metal powder 2 in the firing step which is a manufacturing process thereof. From doing
The oxidation resistance of the base metal powder 2 is enhanced.
【００３０】なお、卑金属粉末２の表面にＮｉ−Ｂ合金
粉末３ａを析出させた後に１００℃以上で熱処理を行
い、さらに粉砕処理を行うことが好ましい。熱処理を行
うことにより、粉末の粉砕処理時ならびにペースト作製
時にＮｉ−Ｂ合金粉末３ａが卑金属粉末２から離脱する
ことを抑制することができるため、本発明の効果をより
顕著なものとすることができる。また、Ｎｉ−Ｂ合金粉
末３ａの析出や熱処理を行うことで、卑金属粉末２の凝
集が起こる可能性があるため、熱処理後に粉砕処理を行
うことが好ましい。It is preferable that after the Ni-B alloy powder 3a is deposited on the surface of the base metal powder 2, heat treatment is performed at 100 ° C. or higher, and further pulverization treatment is performed. By performing the heat treatment, it is possible to prevent the Ni—B alloy powder 3a from being separated from the base metal powder 2 during the pulverizing process of the powder and during the paste preparation, so that the effect of the present invention can be more remarkable. it can. Further, the precipitation of the Ni-B alloy powder 3a and the heat treatment may cause aggregation of the base metal powder 2. Therefore, it is preferable to perform the pulverization treatment after the heat treatment.
【００３１】また、Ｎｉ−Ｂ合金粉末３ａの平均粒径
は、卑金属粉末２の平均粒径よりも小さいことが好まし
い。Ｎｉ−Ｂ合金粉末３ａの平均粒径が卑金属粉末２の
平均粒径よりも小さい場合に、上述した酸化硼素膜３ｂ
が卑金属粉末２を被覆し、卑金属粉末２の耐酸化性を高
めることができるという本発明の効果を得られる。他
方、Ｎｉ−Ｂ合金粉末３ａの平均粒径が卑金属粉末２の
平均粒径以上であると、この導電粉末を含有してなる導
電性ペーストを用いて内部電極を形成した積層セラミッ
ク電子部品は、脱バインダー時における卑金属粉末の酸
化膨張による層剥がれといった構造不良や、酸化による
卑金属粉末の焼結不足による取得容量の低下や、等価直
列抵抗ならびにｔａｎδの増加等の不具合が発生するこ
とがある。The average particle size of the Ni-B alloy powder 3a is preferably smaller than that of the base metal powder 2. When the average particle size of the Ni-B alloy powder 3a is smaller than the average particle size of the base metal powder 2, the above-mentioned boron oxide film 3b.
The base metal powder 2 can be coated to improve the oxidation resistance of the base metal powder 2. On the other hand, when the average particle diameter of the Ni-B alloy powder 3a is equal to or larger than the average particle diameter of the base metal powder 2, the laminated ceramic electronic component in which the internal electrode is formed by using the conductive paste containing the conductive powder, There may occur problems such as a structural defect such as layer peeling due to oxidative expansion of the base metal powder during debinding, a decrease in acquisition capacity due to insufficient sintering of the base metal powder due to oxidation, and an increase in equivalent series resistance and tan δ.
【００３２】また、Ｎｉ−Ｂ合金粉末３ａの卑金属粉末
２表面への析出量は、卑金属粉末１００重量部に対し
て、５０重量部以下であることが好ましい。Ｎｉ−Ｂ合
金粉末の析出量が５０重量部を超えると、多量のＮｉ−
Ｂ合金粉末が熔融し、内部電極の電極として機能が損な
われることがある。なお、Ｎｉ−Ｂ合金粉末の析出量の
下限値は特に限定しないが、Ｎｉ−Ｂ合金粉末３ａの析
出量が０．１重量部程度であればよい。この程度の量が
析出していれば、導電粉末の酸化開始温度が上昇し、す
なわち卑金属粉末の耐酸化性を向上させる効果を得るこ
とができる。この導電粉末を含有してなる導電性ペース
トを用いて内部電極を形成した積層セラミック電子部品
において、脱バインダー時における導電粉末の酸化膨張
による層剥がれといった構造不良の発生、酸化による導
電粉末の焼結不足による取得容量の低下、等価直列抵抗
ならびにｔａｎδの増加等の不具合が発生することを抑
制することができる。The amount of the Ni-B alloy powder 3a deposited on the surface of the base metal powder 2 is preferably 50 parts by weight or less with respect to 100 parts by weight of the base metal powder. When the amount of precipitation of the Ni-B alloy powder exceeds 50 parts by weight, a large amount of Ni-
The B alloy powder may melt and the function of the internal electrode as an electrode may be impaired. The lower limit of the precipitation amount of the Ni-B alloy powder is not particularly limited, but the precipitation amount of the Ni-B alloy powder 3a may be about 0.1 part by weight. If the amount of this amount is deposited, the oxidation start temperature of the conductive powder rises, that is, the effect of improving the oxidation resistance of the base metal powder can be obtained. In a multilayer ceramic electronic component in which internal electrodes are formed using a conductive paste containing this conductive powder, structural defects such as layer peeling due to oxidative expansion of the conductive powder during debinding, and sintering of the conductive powder due to oxidation It is possible to prevent problems such as a decrease in acquisition capacity, an increase in equivalent series resistance, and an increase in tan δ due to a shortage.
【００３３】また、卑金属粉末の平均粒径は、１．０μ
ｍ以下であることが好ましい。一般的に、卑金属粉末は
平均粒径が小さくなるほど比表面積が増えて活性にな
り、酸化が起こりやすくなる。特に、卑金属粉末の平均
粒径が１．０μｍ以下の場合に酸化が起こりやすくなる
傾向がある。そのため、本発明において、卑金属粉末の
平均粒径が１．０μｍ以下である場合に本発明の耐酸化
効果が十分に発揮される。卑金属粉末の平均粒径が１．
０μｍを超える場合も本発明の耐酸化効果は得られる
が、もともと比表面積が小さく酸化に対して敏感でない
ため、その耐酸化効果は１．０μｍ以下の粉末ほど顕著
ではない。The average particle size of the base metal powder is 1.0 μm.
It is preferably m or less. Generally, as the average particle size of the base metal powder becomes smaller, the specific surface area increases and becomes active, so that oxidation easily occurs. In particular, when the average particle size of the base metal powder is 1.0 μm or less, oxidation tends to occur. Therefore, in the present invention, the oxidation resistance effect of the present invention is sufficiently exhibited when the average particle size of the base metal powder is 1.0 μm or less. The average particle size of the base metal powder is 1.
Even if it exceeds 0 μm, the oxidation resistance effect of the present invention can be obtained, but since the specific surface area is originally small and it is not sensitive to oxidation, the oxidation resistance effect is not so remarkable as that of the powder having a particle size of 1.0 μm or less.
【００３４】また、Ｎｉ−Ｂ合金粉末の平均粒径は、
０．１０μｍ以下で、かつ、卑金属粉末の平均粒径の１
／２以下であることが好ましい。上述する範囲内である
場合、Ｎｉ−Ｂ合金粉末が卑金属粉末の表面をより均一
に被覆することができるため、卑金属粉末の耐酸化性が
十分得られる。The average particle size of the Ni-B alloy powder is
0.10 μm or less and 1 of the average particle size of the base metal powder
It is preferably / 2 or less. Within the above range, the Ni-B alloy powder can coat the surface of the base metal powder more uniformly, so that sufficient oxidation resistance of the base metal powder can be obtained.
【００３５】得られたＮｉ−Ｂ合金粉末を分析した結
果、この粉末は、非晶質であり、また、粉末中に含まれ
ているＢ成分の構成割合は、約２５モル％であった。な
お、Ｎｉ−Ｂ合金粉末中に含まれるＢ成分の構成割合に
ついては、特に限定されるものではない。As a result of analyzing the obtained Ni-B alloy powder, this powder was amorphous, and the composition ratio of the B component contained in the powder was about 25 mol%. The composition ratio of the B component contained in the Ni-B alloy powder is not particularly limited.
【００３６】本発明の導電性ペーストは、上述の導電粉
末と、有機ビヒクルとを含有してなる。有機ビヒクルの
材料は、特に限定されるものではないが、従来より積層
セラミック電子部品内部電極形成に好適な導電性ペース
トに一般的に用いられている有機ビヒクル、具体的に
は、スクリーン印刷法、グラビア印刷法、スプレー法等
によって、積層セラミックコンデンサ、多層セラミック
基板、チップバリスタ、チップＬＣフィルタ、チップイ
ンダクタ等の内部電極形成に好適な導電性ペーストに用
いられる有機ビヒクル、より具体的には、例えば、エチ
ルセルロース樹脂をテルピネオール等の溶剤に溶解させ
たもの等を適宜用いることができる。The conductive paste of the present invention contains the above-mentioned conductive powder and an organic vehicle. The material of the organic vehicle is not particularly limited, but an organic vehicle that is generally used in a conductive paste suitable for forming a multilayer ceramic electronic component internal electrode from the past, specifically, a screen printing method, An organic vehicle used for a conductive paste suitable for forming internal electrodes such as a multilayer ceramic capacitor, a multilayer ceramic substrate, a chip varistor, a chip LC filter, and a chip inductor by a gravure printing method, a spray method, or the like, more specifically, for example, It is possible to appropriately use a solution of ethyl cellulose resin dissolved in a solvent such as terpineol.
【００３７】本発明の積層セラミック電子部品につい
て、図２に基づいて詳細に説明する。図２に示すよう
に、本実施形態にかかる積層セラミック電子部品１１
は、略直方体型であり、セラミック積層体１２と、内部
電極１３・１３と、端子電極１４・１４と、めっき膜１
５・１５とから構成されている。The multilayer ceramic electronic component of the present invention will be described in detail with reference to FIG. As shown in FIG. 2, the monolithic ceramic electronic component 11 according to the present embodiment.
Is a substantially rectangular parallelepiped type, and has a ceramic laminate 12, internal electrodes 13 and 13, terminal electrodes 14 and 14, and a plating film 1.
It is composed of 5 and 15.
【００３８】セラミック積層体１２は、ＢａＴｉＯ3を
主成分とする誘電体材料からなるセラミック層１２ａが
複数積層された生のセラミック積層体が焼成されてな
る。The ceramic laminated body 12 is formed by firing a raw ceramic laminated body in which a plurality of ceramic layers 12a made of a dielectric material containing BaTiO 3 as a main component are laminated.
【００３９】各内部電極１３・１３は、セラミック積層
体１２内の各セラミック層１２ａ・１２ａ間にあって、
複数の生のセラミック層１２ａ上に本発明の導電性ペー
ストが印刷され、生のセラミック層とともに積層されて
なる生のセラミック積層体と同時に焼成されてなる。ま
た、各内部電極１３・１３のそれぞれの端縁は、セラミ
ック積層体１２のいずれかの端面に露出するように形成
されている。The internal electrodes 13 and 13 are located between the ceramic layers 12a and 12a in the ceramic laminate 12,
The conductive paste of the present invention is printed on a plurality of raw ceramic layers 12a and fired at the same time as a raw ceramic laminate that is laminated with the raw ceramic layers. Further, the respective end edges of the respective inner electrodes 13, 13 are formed so as to be exposed on either end surface of the ceramic laminate 12.
【００４０】端子電極１４・１４は、セラミック積層体
１２の端面に露出した各内部電極１３・１３の一端と電
気的かつ機械的に接合されるように、端子電極形成用の
導電性ペーストがセラミック積層体１２の端面に塗布さ
れ焼き付けられてなる。The conductive paste for forming the terminal electrodes is made of ceramic so that the terminal electrodes 14 and 14 are electrically and mechanically bonded to the ends of the internal electrodes 13 and 13 exposed at the end faces of the ceramic laminate 12. It is applied to the end surface of the laminate 12 and baked.
【００４１】めっき膜１５・１５は、例えば、ＳｎやＮ
ｉ等の無電解めっきや、はんだめっき等からなり、端子
電極１４・１４上に少なくとも１層形成されてなる。The plating films 15 and 15 are made of, for example, Sn or N.
At least one layer is formed on the terminal electrodes 14 and 14 by electroless plating such as i or solder plating.
【００４２】なお、本発明の積層セラミック電子部品の
セラミック積層体１２の材料は、上述の実施形態に限定
されることはなく、例えば、ＰｂＺｒＯ3等その他の誘
電体材料や、絶縁体、磁性体、半導体材料からなっても
構わない。また、本発明の積層セラミック電子部品の内
部電極１３の枚数は、上述の実施形態に限定されること
はなく、何層形成されていても構わない。また、端子電
極１４の形成位置ならびに個数は、上述の実施形態に限
定されるものではない。また、めっき膜１５・１５は、
必ずしも備えている必要はなく、また何層形成されてい
ても構わない。The material of the ceramic laminated body 12 of the laminated ceramic electronic component of the present invention is not limited to the above-mentioned embodiment, and for example, other dielectric materials such as PbZrO 3 and insulators and magnetic materials can be used. It may be made of a semiconductor material. Further, the number of the internal electrodes 13 of the monolithic ceramic electronic component of the present invention is not limited to that in the above embodiment, and any number of layers may be formed. Further, the formation position and the number of the terminal electrodes 14 are not limited to those in the above embodiment. Also, the plating films 15 and 15 are
It does not necessarily have to be provided, and any number of layers may be formed.
【００４３】[0043]
【実施例】〔実施例１〕Ｎｉ粉末にＮｉ−Ｂ合金粉末を
析出させた実施例を示す。Ｎｉ−Ｂ合金粉末量は、Ｎｉ
−Ｂ合金粉末析出後にＮｉ粉末１００重量部に対して、
Ｎｉ−Ｂ合金粉末として０．９０重量部になるように、
Ｂ量としては０．０５重量部になるようにＮｉ−Ｂ合金
粉末を析出させた。Example 1 An example in which Ni-B alloy powder is deposited on Ni powder will be described. The amount of Ni-B alloy powder is Ni
After depositing the B alloy powder, 100 parts by weight of the Ni powder,
Ni-B alloy powder to be 0.90 parts by weight,
The Ni-B alloy powder was deposited so that the amount of B was 0.05 parts by weight.
【００４４】硫酸ニッケルＮｉＳＯ4・６Ｈ2Ｏ（Ｎｉ
塩）１５ｇを純水１Ｌに溶解させ、液温を３０℃に設定
した。次に、このＮｉ塩溶液に、粒径０．５μｍのＮｉ
粉末４００ｇを、Ｎｉ塩溶液を攪拌しながら添加し、Ｎ
ｉ粉末をＮｉ塩溶液に分散させ、Ｎｉ粉末濃度として４
００ｇ／Ｌの溶液Ａを調整した。以下、Ｎｉ粉末をＮｉ
塩溶液に分散させた溶液のことを溶液Ａという。一方、
水素化硼素ナトリウム５ｇと、水酸化ナトリウム５ｇと
を純水１Ｌに溶解し、液温を３０℃に設定した還元剤溶
液を調整した。[0044] nickel sulfate NiSO 4 · 6H 2 O (Ni
15 g of salt) was dissolved in 1 L of pure water, and the liquid temperature was set to 30 ° C. Next, in this Ni salt solution, Ni having a particle size of 0.5 μm is added.
400 g of powder was added while stirring the Ni salt solution,
i powder was dispersed in a Ni salt solution to obtain a Ni powder concentration of 4
A solution A of 00 g / L was prepared. Hereinafter, Ni powder is referred to as Ni
The solution dispersed in the salt solution is referred to as solution A. on the other hand,
Sodium borohydride (5 g) and sodium hydroxide (5 g) were dissolved in pure water (1 L) to prepare a reducing agent solution having a liquid temperature of 30 ° C.
【００４５】次いで、上記還元剤溶液を、溶液Ａに、溶
液Ａを攪拌しながら添加し、Ｎｉ粉末表面へのＮｉ−Ｂ
合金粉末の還元析出反応を行った。析出反応後のＮｉ粉
末を水洗し、アセトン置換を行った後乾燥させ、粉末試
料（試料）１を得た。Next, the above reducing agent solution was added to Solution A while stirring Solution A, and Ni-B on the surface of Ni powder was added.
The reduction precipitation reaction of the alloy powder was performed. The Ni powder after the precipitation reaction was washed with water, replaced with acetone, and then dried to obtain a powder sample (Sample) 1.
【００４６】〔実施例２〕実施例２についてそれぞれ、
実施例１におけるＮｉ粉末濃度を、２倍に変更して、す
なわち８００ｇ／Ｌにして、実施例１と同様にＮｉ粉末
表面にＮｉ−Ｂ合金粉末の還元析出反応を行った。この
とき、硫酸ニッケル、水素化硼素ナトリウム、水酸化ナ
トリウムの濃度も、それぞれ２倍にした。濃度以外の条
件は、実施例１と同じにした。[Embodiment 2] Regarding Embodiment 2, respectively,
The Ni powder concentration in Example 1 was doubled, that is, 800 g / L, and the reduction precipitation reaction of the Ni-B alloy powder was performed on the Ni powder surface in the same manner as in Example 1. At this time, the concentrations of nickel sulfate, sodium borohydride and sodium hydroxide were also doubled. The conditions other than the concentration were the same as in Example 1.
【００４７】〔比較例１・２〕比較例１・２について、
それぞれ実施例１におけるＮｉ粉末濃度を、１／２倍、
１／４倍に変更して、すなわち２００ｇ／Ｌ、１００ｇ
／Ｌにして、実施例１と同様にＮｉ粉末表面にＮｉ−Ｂ
合金粉末の還元析出反応を行った。このとき、硫酸ニッ
ケル、水素化硼素ナトリウム、水酸化ナトリウムの濃度
も、それぞれ１／２倍、１／４倍にした。濃度以外の条
件は、実施例１と同じにした。[Comparative Examples 1 and 2] Regarding Comparative Examples 1 and 2,
The Ni powder concentration in Example 1 was 1/2 times,
Change to 1/4 times, that is, 200g / L, 100g
/ L, and Ni-B was formed on the surface of the Ni powder as in Example 1.
The reduction precipitation reaction of the alloy powder was performed. At this time, the concentrations of nickel sulfate, sodium borohydride, and sodium hydroxide were also made 1/2 times and 1/4 times, respectively. The conditions other than the concentration were the same as in Example 1.
【００４８】〔実施例３〜５〕実施例３〜５についてそ
れぞれ、実施例２における液温を３０℃から２０℃、４
０℃、５０℃にして、実施例２と同様にＮｉ−Ｂ合金粉
末の還元析出反応を行った。液温以外の条件は、実施例
２と同じにした。[Examples 3 to 5] Regarding Examples 3 to 5, the liquid temperatures in Example 2 were changed from 30 ° C to 20 ° C and 4 respectively.
The reduction precipitation reaction of the Ni-B alloy powder was performed in the same manner as in Example 2 at 0 ° C and 50 ° C. The conditions other than the liquid temperature were the same as in Example 2.
【００４９】実施例１〜５、比較例１〜２の反応条件に
ついて表１にまとめて示す。このような反応条件で作製
した試料１〜７に含まれるＢ量を発光分光で分析した。
その結果、いずれの試料についてもＢ量として０．０５
重量％含まれることが示され、Ｂ量に違いは見られなか
った。The reaction conditions for Examples 1-5 and Comparative Examples 1-2 are summarized in Table 1. The amount of B contained in Samples 1 to 7 produced under such reaction conditions was analyzed by emission spectroscopy.
As a result, the B content of all samples was 0.05.
The content of B was shown to be the same, and no difference was found in the amount of B.
【００５０】[0050]
【表１】 [Table 1]
【００５１】次に、Ｎｉ−Ｂ合金粉末を析出させたＮｉ
粉末の耐酸化性の確認のため、試料１〜７の導電粉末の
酸化開始温度を、示差熱天秤を用いて空気気流中で室温
より１０００℃までの質量変化を測定した。導電粉末の
酸化による重量増加が始まる温度を酸化開始温度と規定
して、酸化開始温度を表２にまとめた。なお、比較例３
において、Ｎｉ−Ｂ合金粉末を析出させていない粒径
０．５μｍのＮｉ粉末を試料８として示す。Next, the Ni containing the Ni-B alloy powder was deposited.
In order to confirm the oxidation resistance of the powder, the oxidation start temperature of the conductive powders of Samples 1 to 7 was measured for the mass change from room temperature to 1000 ° C. in an air stream using a differential thermal balance. The temperature at which the weight increase due to the oxidation of the conductive powder starts is defined as the oxidation start temperature, and the oxidation start temperature is summarized in Table 2. Comparative Example 3
In, a Ni powder having a grain size of 0.5 μm, in which the Ni—B alloy powder is not deposited, is shown as a sample 8.
【００５２】[0052]
【表２】 [Table 2]
【００５３】表２から、Ｎｉ粉末濃度を変更した試料１
〜４で比較すると、Ｎｉ粉末濃度が８００ｇ／Ｌである
溶液Ａから得られた試料２の酸化開始温度が最も高く、
Ｎｉ粉末濃度が低くなるほど耐酸化性が低くなることが
判った。特に、Ｎｉ粉末濃度が２００ｇ／Ｌ以下になる
と、耐酸化性の低下が著しいことが判った。これらの結
果から、Ｎｉ粉末濃度は、４００ｇ／Ｌ以上が好ましい
ことが示された。From Table 2, Sample 1 with different Ni powder concentration
4 to 4, the oxidation start temperature of the sample 2 obtained from the solution A having a Ni powder concentration of 800 g / L is the highest,
It was found that the lower the Ni powder concentration, the lower the oxidation resistance. In particular, it was found that when the Ni powder concentration was 200 g / L or less, the oxidation resistance was significantly reduced. From these results, it was shown that the Ni powder concentration is preferably 400 g / L or more.
【００５４】また、反応温度を変更した試料２および試
料５〜７によると、反応温度は５０℃以下が好ましいこ
とが示された。Further, according to Sample 2 and Samples 5 to 7 in which the reaction temperature was changed, it was shown that the reaction temperature is preferably 50 ° C. or lower.
【００５５】〔実施例６〜１０〕次いで、試料１、２、
５〜７の導電粉末を用いて、導電性ペーストを作製し
た。すなわち、表３に示すように、導電粉末５０重量％
と、エチルセルロース樹脂２０重量％とテルピネオール
８０重量％とを混合してなる有機ビヒクル５０重量％
と、を混合した後、三本ロールにて分散処理を行い、ペ
ースト試料（導電性ペースト）、、〜を作成し
た。[Examples 6 to 10] Next, samples 1, 2 and
A conductive paste was prepared using 5 to 7 conductive powders. That is, as shown in Table 3, conductive powder 50% by weight
50% by weight of an organic vehicle obtained by mixing 20% by weight of ethyl cellulose resin and 80% by weight of terpineol
After mixing and, dispersion treatment was performed with a triple roll to prepare paste samples (conductive paste) ,.
【００５６】[0056]
【表３】 [Table 3]
【００５７】次いで、導電性ペースト、、〜を
用いて、内部電極を形成した、設計段階の静電容量が
１．０μＦである積層セラミックコンデンサを作製し
た。すなわち、ＢａＴｉＯ3を主成分とするセラミック
グリーンシートを準備し、所定枚数のセラミックグリー
ンシートの表面上に一方の端縁がセラミックグリーンシ
ートのいずれかの端面側に露出するように、導電性ペー
スト、、〜を用いて内部電極となるべき電極膜
を印刷した。次いで、これら複数のセラミックグリーン
シートを所定枚数積層し圧着して、試料１、２、５〜７
（導電性ペースト、、〜）の生のセラミック積
層体を複数準備した。Next, using conductive pastes, and, a multilayer ceramic capacitor having internal electrodes formed and having a capacitance of 1.0 μF at the design stage was produced. That is, a ceramic green sheet containing BaTiO 3 as a main component is prepared, and a conductive paste, such that one edge is exposed on either end surface side of the ceramic green sheet on the surface of a predetermined number of ceramic green sheets, , To were used to print an electrode film to be an internal electrode. Next, a predetermined number of these ceramic green sheets are laminated and pressure-bonded to each other, and samples 1, 2, 5 to 7 are attached.
A plurality of raw ceramic laminates of (conductive paste, ...) were prepared.
【００５８】次いで、試料１、２、５〜７（導電性ペー
スト、、〜）の生のセラミック積層体を脱バイ
ンダーさせるにあたり、条件を表４の条件Ａのように設
定した。すなわち、耐酸化性のない導電粉末を用いた導
電性ペーストの場合に導電粉末の酸化が生じ易い条件と
して、保持温度４００℃、保持時間６０分、Ａｉｒ雰囲
気と設定し、これを脱バインダー条件Ａとした。他方、
導電粉末の酸化は生じにくいが、有機バインダーの熱分
解が不十分となり易い条件として、保持温度２５０℃、
保持時間６０分、Ｎ2雰囲気と設定し、これを脱バイン
ダー条件Ｂとした。これら条件Ａ、Ｂを表４に示す。Next, in debinding the raw ceramic laminates of Samples 1, 2, 5 to 7 (conductive paste, ...), the conditions were set as Condition A in Table 4. That is, in the case of a conductive paste using a conductive powder having no oxidation resistance, a holding temperature of 400 ° C., a holding time of 60 minutes, and an Air atmosphere were set as conditions under which oxidation of the conductive powder was likely to occur. And On the other hand,
Oxidation of the conductive powder is unlikely to occur, but as a condition that thermal decomposition of the organic binder tends to be insufficient, a holding temperature of 250 ° C
The holding time was set to 60 minutes and the atmosphere was set to N 2 , and this was set as the binder removal condition B. Table 4 shows these conditions A and B.
【００５９】[0059]
【表４】 [Table 4]
【００６０】次いで、上述の脱バインダー処理後に焼成
し、さらにセラミック積層体の両端面にＡｇを導電成分
とする端子電極形成用の導電性ペーストを塗布し、乾燥
させた後これを焼き付けて、内部電極に電気的かつ機械
的に接合された１対の端子電極を備える、試料１、２、
５〜７の積層セラミックコンデンサを１００００個づつ
得た。Next, after the binder removal treatment described above, firing is carried out, and further, a conductive paste for forming a terminal electrode containing Ag as a conductive component is applied to both end faces of the ceramic laminated body, dried and then baked to form an internal component. Samples 1, 2, comprising a pair of terminal electrodes electrically and mechanically joined to the electrodes
10,000 laminated ceramic capacitors of 5 to 7 were obtained.
【００６１】そこで、試料１、２、５〜７の積層セラミ
ックコンデンサを１００個づつ抜き取り、静電容量（１
００個平均）、ショート不良発生率、層剥がれ不良発生
率を測定し、３項目を総合して評価した。Therefore, 100 monolithic ceramic capacitors of Samples 1, 2, 5 and 7 were extracted one by one, and the capacitance (1
(Average of 00 pieces), short-circuit failure occurrence rate, and layer peeling failure occurrence rate were measured, and three items were comprehensively evaluated.
【００６２】なお、評価は、静電容量が１．０±０．２
μＦ、ショート不良発生率が０％、層剥がれ不良発生率
が０％であり、本発明の範囲内である試料について○
を、本発明の範囲外である試料について×を付した。The evaluation is that the capacitance is 1.0 ± 0.2.
μF, 0% short circuit defect occurrence rate, 0% layer peeling defect occurrence rate, and within the scope of the present invention for samples
Is marked with x for samples that are outside the scope of the invention.
【００６３】〔比較例４〜７〕次いで、試料３、４、お
よび８の導電粉末を用いて、実施例６〜１０と同様に導
電性ペースト、、およびを作製し、試料３、４、
および８（導電性ペースト、、および）の積層セ
ラミックコンデンサを作成した。なお、試料８（導電性
ペースト）については、脱バインダー条件Ａ（比較例
６）および条件Ｂ（比較例７）で脱バインダーさせた。[Comparative Examples 4 to 7] Next, using the conductive powders of Samples 3, 4 and 8, conductive pastes and were prepared in the same manner as in Examples 6 to 10, and Samples 3, 4 and
And 8 (conductive paste, and) multilayer ceramic capacitors were prepared. Sample 8 (conductive paste) was debindered under debinding condition A (comparative example 6) and condition B (comparative example 7).
【００６４】そして、実施例６〜１０と同様に、試料
３、４、および８の積層セラミックコンデンサについ
て、静電容量（１００個平均）、ショート不良発生率、
層剥がれ不良発生率を測定し、３項目を総合して評価し
た。Then, in the same manner as in Examples 6 to 10, for the multilayer ceramic capacitors of Samples 3, 4, and 8, the capacitance (average of 100 capacitors), the short-circuit defect occurrence rate,
The layer peeling defect occurrence rate was measured, and the three items were comprehensively evaluated.
【００６５】上記実施例６〜１０および比較例４〜７の
結果を表５にまとめた。The results of Examples 6 to 10 and Comparative Examples 4 to 7 are summarized in Table 5.
【００６６】[0066]
【表５】 [Table 5]
【００６７】表５から明らかであるように、Ｎｉ粉末濃
度が４００ｇ／Ｌ以上の溶液Ａから得られた試料１、
２、５〜７の導電粉末（導電性ペースト、、〜
）を用いた積層セラミックコンデンサ（実施例６〜１
０）は、静電容量が１．０μＦであり、ショート不良発
生率、層剥がれ不良発生率がいずれも０％であり、良好
な特性が得られた。As is clear from Table 5, Sample 1 obtained from solution A having a Ni powder concentration of 400 g / L or more,
2, 5-7 conductive powder (conductive paste, ...
) Used multilayer ceramic capacitors (Examples 6 to 1)
In 0), the electrostatic capacity was 1.0 μF, and the occurrence rates of short circuit defects and layer peeling defects were both 0%, and good characteristics were obtained.
【００６８】これに対して、Ｎｉ粉末濃度が４００ｇ／
Ｌより低い溶液から得られた試料３、４の導電粉末（導
電性ペースト、）を用いた積層セラミックコンデン
サ（比較例４、５）は、層剥がれ不良が発生した。On the other hand, the Ni powder concentration is 400 g /
In the multilayer ceramic capacitors (Comparative Examples 4 and 5) using the conductive powders (conductive pastes) of Samples 3 and 4 obtained from the solutions lower than L, layer peeling failure occurred.
【００６９】また、反応温度が２０℃〜５０℃で得られ
た試料１、２、試料５〜７の導電粉末（導電性ペースト
、、、、）を用いた積層セラミックコンデン
サ（実施例６〜１０）は、静電容量が１．０μＦであ
り、ショート不良発生率、層剥がれ不良発生率がいずれ
も０％であり、良好な特性が得られた。A multilayer ceramic capacitor using the conductive powders (conductive paste, ...) Of Samples 1 and 2 and Samples 5 to 7 obtained at a reaction temperature of 20 to 50 ° C. (Examples 6 to 10) ), The electrostatic capacity was 1.0 μF, and the short-circuit defect occurrence ratio and the layer peeling defect occurrence ratio were both 0%, and good characteristics were obtained.
【００７０】また、従来のＮｉ粉末である試料８の導電
粉末（導電性ペースト）を用いた積層セラミックコン
デンサ（比較例６、７）は、脱バインダー条件がＡｉｒ
雰囲気中で保持温度が高い場合（条件Ａ）には、静電容
量が極端に低くなって層剥がれ不良発生率が高くなり、
Ｎ2雰囲気中で保持温度が低い場合（条件Ｂ）には、シ
ョート不良発生率が高くなる。Further, in the laminated ceramic capacitors (Comparative Examples 6 and 7) using the conductive powder (conductive paste) of Sample 8 which is a conventional Ni powder, the binder removal condition is Air.
When the holding temperature is high in the atmosphere (condition A), the electrostatic capacitance becomes extremely low and the layer peeling defect occurrence rate becomes high.
When the holding temperature is low in the N 2 atmosphere (condition B), the short-circuit defect occurrence rate becomes high.
【００７１】[0071]
【発明の効果】以上のように本発明の導電粉末の製造方
法によれば、Ｎｉ粉末、Ｃｕ粉末、Ｎｉまたは／および
Ｃｕを主成分とする合金粉末からなる群から選ばれる少
なくとも１種の卑金属粉末とＮｉ塩を含む金属塩溶液
に、水素化硼化物を含む還元剤溶液を混合して前記Ｎｉ
塩溶液を液層還元し、前記卑金属粉末の表面にＮｉ−Ｂ
合金粉末を析出させる反応において、卑金属粉末の溶液
濃度を４００ｇ／Ｌ以上にすることで、耐酸化性を有す
る導電粉末を提供することができる。また、このような
導電粉末を用いた導電性ペーストを提供することができ
る。これにより、有機物の分解ならびに除去に十分な温
度の酸化雰囲気中での脱バインダー処理を可能とし、こ
のような導電性ペーストを用いて内部電極を形成する積
層セラミック電子部品の歩留まりならびに生産性を向上
させることができる。As described above, according to the method for producing a conductive powder of the present invention, at least one base metal selected from the group consisting of Ni powder, Cu powder, and alloy powder containing Ni or / and Cu as a main component. The metal salt solution containing the powder and the Ni salt is mixed with the reducing agent solution containing the borohydride to form the Ni
The salt solution is subjected to liquid phase reduction, and Ni-B is applied to the surface of the base metal powder.
In the reaction for depositing the alloy powder, by setting the solution concentration of the base metal powder to 400 g / L or more, it is possible to provide a conductive powder having oxidation resistance. Further, a conductive paste using such a conductive powder can be provided. This enables debindering treatment in an oxidizing atmosphere at a temperature sufficient for decomposing and removing organic substances, and improves the yield and productivity of multilayer ceramic electronic components that form internal electrodes using such conductive paste. Can be made.
【００７２】また、上述の導電粉末の製造方法におい
て、反応温度を０℃以上、５０℃以下にすることで、よ
り確実に耐酸化性を有する導電粉末を提供することがで
きる。Further, in the above-mentioned method for producing a conductive powder, by setting the reaction temperature to 0 ° C. or higher and 50 ° C. or lower, it is possible to more reliably provide a conductive powder having oxidation resistance.
【００７３】また、上述の卑金属粉末の平均粒径は、
１．０μｍ以下であることが好ましい。これにより、一
般に卑金属粉末は、粒径が小さくなるほど比表面積が増
えて活性になり、酸化が起こり易くなるが、卑金属粉末
の耐酸化性を向上させるという本発明の効果が顕著とな
る。また、積層セラミック電子部品のさらなる薄層化や
多層化に貢献できる効果がある。The average particle size of the above base metal powder is
It is preferably 1.0 μm or less. As a result, in general, the base metal powder has a larger specific surface area and becomes more active as the particle size becomes smaller and becomes more active, so that oxidation easily occurs, but the effect of the present invention of improving the oxidation resistance of the base metal powder becomes remarkable. Further, there is an effect that it can contribute to further thinning and multilayering of the monolithic ceramic electronic component.
【００７４】また、上述のＮｉ−Ｂ合金粉末の平均粒径
は、０．１μｍ以下であり、かつ、卑金属粉末の平均粒
径の１／２以下であることが好ましい。これにより、Ｎ
ｉ−Ｂ合金粉末の表面をより均一に被覆することがで
き、卑金属粉末の耐酸化性が十分に得られるという効果
がある。The average particle size of the above Ni-B alloy powder is preferably 0.1 μm or less and 1/2 or less of the average particle size of the base metal powder. By this, N
The surface of the i-B alloy powder can be coated more uniformly, and the oxidation resistance of the base metal powder can be sufficiently obtained.
【図１】（ａ）は、本発明の一実施形態にかかる導電粉
末の図解的断面図であり、（ｂ）は、（ａ）の導電粉末
を熱処理した（焼結後の）ものの図解的断面図である。FIG. 1A is a schematic sectional view of a conductive powder according to an embodiment of the present invention, and FIG. 1B is a schematic cross-sectional view of the conductive powder of FIG. FIG.
【図２】本発明の一実施形態にかかる積層セラミック電
子部品の断面図である。FIG. 2 is a cross-sectional view of a monolithic ceramic electronic component according to an embodiment of the present invention.
１ 導電粉末 ２ 卑金属粉末 ３ａ Ｎｉ−Ｂ合金粉末 １１ 積層セラミック電子部品 １２ａ セラミック層 １２ セラミック積層体 １３ 内部電極 1 Conductive powder 2 Base metal powder 3a Ni-B alloy powder 11 Multilayer ceramic electronic components 12a ceramic layer 12 Ceramic laminate 13 internal electrodes
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｂ２２Ｆ 9/04 Ｂ２２Ｆ 9/04 Ｃ Ｈ０１Ｂ 1/00 Ｈ０１Ｂ 1/00 Ｂ 1/22 1/22 Ａ Ｈ０１Ｇ 4/12 ３６１ Ｈ０１Ｇ 4/12 ３６１ Ｆターム(参考） 4K017 AA04 BA03 BA05 BB13 CA07 DA07 EA03 4K018 BA02 BA04 BB04 BC01 BC08 BC24 BD04 5E001 AB03 AE02 AF06 AH01 AH06 AH09 AJ01 AJ02 5G301 DA06 DA10 DA22 DD01 ─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 7 Identification code FI theme code (reference) B22F 9/04 B22F 9/04 C H01B 1/00 H01B 1/00 B 1/22 1/22 A H01G 4 / 12 361 H01G 4/12 361 F term (reference) 4K017 AA04 BA03 BA05 BB13 CA07 DA07 EA03 4K018 BA02 BA04 BB04 BC01 BC08 BC24 BD04 5E001 AB03 AE02 AF06 AH01 AH06 AH09 AJ01 AJ02 5G301 DA06 DA10 DA22 DD01
Claims (10)
／およびＣｕを主成分とする合金粉末からなる群から選
ばれる少なくとも１種の卑金属粉末と、Ｎｉ塩とを含む
金属塩溶液に、水素化硼化物を含む還元剤溶液を混合
し、前記卑金属粉末の表面にＮｉ−Ｂ合金粉末を析出さ
せる析出工程を備える導電粉末の製造方法であって、前
記金属塩溶液における卑金属粉末濃度が、４００ｇ／Ｌ
以上であることを特徴とする導電粉末の製造方法。1. A metal salt solution containing at least one base metal powder selected from the group consisting of Ni powder, Cu powder, and alloy powder containing Ni and / or Cu as a main component, and a Ni salt, and hydrogenated. A method for producing a conductive powder, comprising a precipitation step of mixing a reducing agent solution containing a boride and depositing a Ni-B alloy powder on the surface of the base metal powder, wherein the base metal powder concentration in the metal salt solution is 400 g / L
The above is the method for producing a conductive powder.
５０℃以下であることを特徴とする請求項１記載の導電
粉末の製造方法。2. The temperature in the precipitation step is 0 ° C. or higher,
It is 50 degrees C or less, The manufacturing method of the electrically conductive powder of Claim 1 characterized by the above-mentioned.
末が表面に析出した前記卑金属粉末を、１００℃以上で
熱処理する熱処理工程をさらに備えることを特徴とする
請求項１または２記載の導電粉末の製造方法。3. The method according to claim 1, further comprising a heat treatment step of heat-treating the base metal powder having the Ni—B alloy powder deposited on the surface thereof at 100 ° C. or higher after the precipitation step. Method for producing conductive powder.
末が表面に析出した前記卑金属粉末を粉砕処理する粉砕
処理工程をさらに備えることを特徴とする請求項１ない
し３のいずれか１項に記載の導電粉末の製造方法。4. The crushing step of crushing the base metal powder having the Ni-B alloy powder deposited on its surface after the precipitation step, further comprising a crushing step. The method for producing a conductive powder according to.
つ、前記卑金属粉末１００重量部に対して５０重量部以
下の量のＮｉ−Ｂ合金粉末を析出させることを特徴とす
る請求項１ないし４のいずれか１項に記載の導電粉末の
製造方法。5. The Ni-B alloy powder, which is smaller than the average particle diameter of the base metal powder and which is 50 parts by weight or less with respect to 100 parts by weight of the base metal powder, is deposited. 4. The method for producing a conductive powder according to any one of 4 above.
以下であることを特徴とする請求項１ないし５のいずれ
か１項に記載の導電粉末の製造方法。6. The average particle diameter of the base metal powder is 1.0 μm.
It is the following, The manufacturing method of the electrically conductive powder of any one of Claim 1 thru | or 5 characterized by the above-mentioned.
１μｍ以下であり、かつ、前記卑金属粉末の平均粒径の
１／２以下であることを特徴とする請求項１ないし６の
いずれか１項に記載の導電粉末の製造方法。7. The average particle size of the Ni-B alloy powder is 0.
It is 1 micrometer or less, and is 1/2 or less of the average particle diameter of the said base metal powder, The manufacturing method of the electrically conductive powder of any one of Claim 1 thru | or 6 characterized by the above-mentioned.
導電粉末の製造方法によって得られたことを特徴とする
導電粉末。8. A conductive powder obtained by the method for manufacturing a conductive powder according to any one of claims 1 to 7.
ルとを含有してなることを特徴とする導電性ペースト。9. A conductive paste containing the conductive powder according to claim 8 and an organic vehicle.
ラミック積層体と、前記セラミック層間に形成された複
数の内部電極とを備える積層セラミック電子部品であっ
て、 前記内部電極は、請求項９に記載の導電性ペーストを用
いて形成されていることを特徴とする積層セラミック電
子部品。10. A monolithic ceramic electronic component comprising a ceramic laminated body formed by laminating a plurality of ceramic layers, and a plurality of internal electrodes formed between the ceramic layers, wherein the internal electrodes are the same as those in claim 9. A laminated ceramic electronic component formed by using the conductive paste as described above.
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| JP2001377455A JP3698098B2 (en) | 2001-12-11 | 2001-12-11 | Method for producing conductive powder, conductive powder, conductive paste, and multilayer ceramic electronic component |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008013846A (en) * | 2006-07-06 | 2008-01-24 | Samsung Electro-Mechanics Co Ltd | Method for producing metal nanoparticle, and metal nanoparticle |
| CN103611932A (en) * | 2013-12-18 | 2014-03-05 | 江苏科技大学 | Sonochemistry preparation method allowing surface of copper powder to be coated with nickel and phosphorus alloy layer |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6280206A (en) * | 1985-10-02 | 1987-04-13 | Murata Mfg Co Ltd | Production of nickel powder |
| JPS6327567A (en) * | 1986-07-18 | 1988-02-05 | Mitsubishi Electric Corp | Electrically conductive paste |
| JPH05195005A (en) * | 1992-01-13 | 1993-08-03 | Murata Mfg Co Ltd | Method for preventing oxidation of copper powder |
| JP2002080902A (en) * | 2000-07-05 | 2002-03-22 | Murata Mfg Co Ltd | Method for producing electrically conductive powder, electrically conductive powder, electrically conductive paste and laminated ceramic electronic parts |
-
2001
- 2001-12-11 JP JP2001377455A patent/JP3698098B2/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6280206A (en) * | 1985-10-02 | 1987-04-13 | Murata Mfg Co Ltd | Production of nickel powder |
| JPS6327567A (en) * | 1986-07-18 | 1988-02-05 | Mitsubishi Electric Corp | Electrically conductive paste |
| JPH05195005A (en) * | 1992-01-13 | 1993-08-03 | Murata Mfg Co Ltd | Method for preventing oxidation of copper powder |
| JP2002080902A (en) * | 2000-07-05 | 2002-03-22 | Murata Mfg Co Ltd | Method for producing electrically conductive powder, electrically conductive powder, electrically conductive paste and laminated ceramic electronic parts |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008013846A (en) * | 2006-07-06 | 2008-01-24 | Samsung Electro-Mechanics Co Ltd | Method for producing metal nanoparticle, and metal nanoparticle |
| US7785392B2 (en) | 2006-07-06 | 2010-08-31 | Samsung Electro-Mechanics Co., Ltd. | Method for manufacturing metal nanoparticles |
| CN103611932A (en) * | 2013-12-18 | 2014-03-05 | 江苏科技大学 | Sonochemistry preparation method allowing surface of copper powder to be coated with nickel and phosphorus alloy layer |
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| Publication number | Publication date |
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| JP3698098B2 (en) | 2005-09-21 |
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