JP2020164898A - Method for producing metal particle, and metal particle - Google Patents
Method for producing metal particle, and metal particle Download PDFInfo
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 27
- 239000002923 metal particle Substances 0.000 title abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 119
- 239000002002 slurry Substances 0.000 claims abstract description 73
- 239000002245 particle Substances 0.000 claims abstract description 31
- 238000004108 freeze drying Methods 0.000 claims abstract description 7
- 239000010419 fine particle Substances 0.000 claims description 135
- 229910052751 metal Inorganic materials 0.000 claims description 123
- 239000002184 metal Substances 0.000 claims description 122
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 44
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 31
- 229910052717 sulfur Inorganic materials 0.000 claims description 27
- 239000011593 sulfur Substances 0.000 claims description 27
- 229910052759 nickel Inorganic materials 0.000 claims description 19
- 239000010949 copper Substances 0.000 claims description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 12
- 229910052802 copper Inorganic materials 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 230000000007 visual effect Effects 0.000 claims description 9
- HBNHCGDYYBMKJN-UHFFFAOYSA-N 2-(4-methylcyclohexyl)propan-2-yl acetate Chemical compound CC1CCC(C(C)(C)OC(C)=O)CC1 HBNHCGDYYBMKJN-UHFFFAOYSA-N 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000001856 Ethyl cellulose Substances 0.000 claims description 5
- 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 claims description 5
- 229920001249 ethyl cellulose Polymers 0.000 claims description 5
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 5
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 230000003287 optical effect Effects 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 235000007586 terpenes Nutrition 0.000 claims description 3
- 239000002994 raw material Substances 0.000 abstract description 10
- 230000000052 comparative effect Effects 0.000 description 58
- 238000000034 method Methods 0.000 description 24
- 239000003985 ceramic capacitor Substances 0.000 description 11
- 239000000843 powder Substances 0.000 description 10
- 238000001035 drying Methods 0.000 description 8
- 239000012808 vapor phase Substances 0.000 description 8
- 230000002776 aggregation Effects 0.000 description 7
- 238000004220 aggregation Methods 0.000 description 6
- 239000003125 aqueous solvent Substances 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000007710 freezing Methods 0.000 description 4
- 230000008014 freezing Effects 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229910000881 Cu alloy Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910001111 Fine metal Inorganic materials 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 2
- 229910002113 barium titanate Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- -1 polyethylene terephthalate Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
Abstract
Description
本発明は、金属微粒子の製造方法および金属微粒子に関する。 The present invention relates to a method for producing metal fine particles and metal fine particles.
従来、金属微粒子が、積層セラミックコンデンサの内部電極層に用いられる。この場合、金属微粒子を含む導電ペーストが、誘電体グリーンシート上に塗布される。導電ペーストと誘電体グリーンシートとを交互に積層させた積層体を焼成することにより、積層セラミックコンデンサを製造する。 Conventionally, metal fine particles are used for the internal electrode layer of a multilayer ceramic capacitor. In this case, a conductive paste containing metal fine particles is applied onto the dielectric green sheet. A monolithic ceramic capacitor is manufactured by firing a laminate in which a conductive paste and a dielectric green sheet are alternately laminated.
このような導電ペーストに用いる金属微粒子を製造する技術が、特許文献１に開示されている。特許文献１の段落［００２２］には、以下の記載がある。
「気相反応で得たニッケル粉を水スラリーにし、超音波振動子による分散機を用いて、ニッケル超微粉を水中で十分に分散させた後、スキミングパイプ付き無孔壁バスケット型遠心分離機（内容積３Ｌ、バスケット内径３００ｍｍ、水スラリー供給速度２．５Ｌ／分、回転数１８００ｒｐｍ）を用いて分級し、スキミングパイプから排出される水スラリーを回収した。この水スラリーは粗粒を除去したニッケル粉を含むものである。回収したスラリーを加圧脱水し、真空乾燥してニッケル粉を回収した。」
Patent Document 1 discloses a technique for producing metal fine particles used for such a conductive paste. Paragraph [0022] of Patent Document 1 has the following description.
"The nickel powder obtained by the gas phase reaction is made into a water slurry, and after sufficiently dispersing the nickel ultrafine powder in water using a disperser using an ultrasonic transducer, a non-perforated wall basket type centrifuge with a skimming pipe ( The water slurry was classified using an internal volume of 3 L, a basket inner diameter of 300 mm, a water slurry supply speed of 2.5 L / min, and a rotation speed of 1800 rpm), and the water slurry discharged from the skimming pipe was recovered. This water slurry was nickel from which coarse particles had been removed. It contains powder. The recovered slurry was pressure dehydrated and vacuum dried to recover nickel powder. "
近年、電子機器の小型化が進展しており、電子機器の構成部品である積層セラミックコンデンサについても、一層の小型化が求められている。このため、積層セラミックコンデンサの内部電極層を薄層化し、積層数を増加させる技術が開発されている。
このような技術として、内部電極層に用いられる金属微粒子を小径化する技術が開発されている。凝集体の個数が少ない金属微粒子を得ることが要請されている。
In recent years, the miniaturization of electronic devices has progressed, and further miniaturization of multilayer ceramic capacitors, which are components of electronic devices, is required. Therefore, a technique has been developed in which the internal electrode layer of the multilayer ceramic capacitor is thinned to increase the number of layers.
As such a technique, a technique for reducing the diameter of metal fine particles used in the internal electrode layer has been developed. It is required to obtain metal fine particles having a small number of aggregates.
本発明者らが検討したところ、水スラリーを真空乾燥して得られた金属微粒子（特許文献１を参照）は、凝集体の個数が多い場合があることを明らかにした。 As a result of studies by the present inventors, it has been clarified that the metal fine particles (see Patent Document 1) obtained by vacuum-drying the water slurry may have a large number of aggregates.
そこで、本発明は、凝集体の個数が少ない金属微粒子が得られる、金属微粒子の製造方法を提供することを目的とする。 Therefore, an object of the present invention is to provide a method for producing metal fine particles, which can obtain metal fine particles having a small number of aggregates.
本発明者らは、上記目的を達するために鋭意検討した。その結果、含水率を特定値まで低減した水スラリーを特定の方法で乾燥することにより、得られる金属微粒子において、凝集体の個数が少なくなることを見出し、本発明を完成させた。 The present inventors have diligently studied to achieve the above object. As a result, they have found that the number of agglomerates in the obtained metal fine particles is reduced by drying the water slurry having the water content reduced to a specific value by a specific method, and completed the present invention.
すなわち、本発明は、以下の［１］〜［６］を提供する。
［１］粒子径が１μｍ以下である原料金属微粒子を含有し、かつ、含水率が３０質量％以下である水スラリーを準備し、上記水スラリーを、凍結乾燥することにより、金属微粒子を得る、金属微粒子の製造方法。
［２］上記水スラリーの含水率が１２質量％以下である、上記［１］に記載の金属微粒子の製造方法。
［３］上記原料金属微粒子が、ニッケルおよび銅からなる群から選ばれる少なくとも１種を含有する、上記［１］または［２］に記載の金属微粒子の製造方法。
［４］上記原料金属微粒子が、０．０５質量％以上の硫黄を含有する、上記［１］〜［３］のいずれかに記載の金属微粒子の製造方法。
［５］上記原料金属微粒子が、０．１質量％以上の硫黄を含有する、上記［４］に記載の金属微粒子の製造方法。
［６］下記条件１で測定される最小径５μｍ以上である凝集体の個数が、５視野の平均値で２０個以下である、金属微粒子。
条件１：下記条件２で作製されるペーストを、厚さ１０μｍで塗布し、１００℃で１分間乾燥して乾燥膜を得る。得られた乾燥膜を、光学顕微鏡を用いて、倍率２００倍で観察する。視野面積が２８．３ｍｍ２である１視野あたりの最小径５μｍ以上である凝集体の個数を測定する。
条件２：上記金属微粒子を５０質量％、樹脂としてダウ・ケミカル日本社製のエチルセルロースを０．３質量％、溶剤として日本テルペン社製のジヒドロターピニルアセテートを４８．８質量％、分散剤として日油社製のエスリーム２２１Ｐを０．９質量％配合して、組成物を得る。得られた組成物を、３本ロールミルとしてビューラー社製のＳＤＹ３００を用いて、８ｂａｒ、１０ｂａｒ、１２ｂａｒおよび１４ｂａｒの圧力でそれぞれ１パスずつ分散させて、ペーストを作製する。
That is, the present invention provides the following [1] to [6].
[1] A water slurry containing raw metal fine particles having a particle size of 1 μm or less and a water content of 30% by mass or less is prepared, and the water slurry is freeze-dried to obtain metal fine particles. Method for producing fine metal particles.
[2] The method for producing metal fine particles according to the above [1], wherein the water content of the water slurry is 12% by mass or less.
[3] The method for producing metal fine particles according to the above [1] or [2], wherein the raw material metal fine particles contain at least one selected from the group consisting of nickel and copper.
[4] The method for producing metal fine particles according to any one of [1] to [3] above, wherein the raw metal fine particles contain 0.05% by mass or more of sulfur.
[5] The method for producing metal fine particles according to the above [4], wherein the raw metal fine particles contain 0.1% by mass or more of sulfur.
[6] Metal fine particles in which the number of aggregates having a minimum diameter of 5 μm or more measured under the following condition 1 is 20 or less on average in five visual fields.
Condition 1: The paste prepared under the following condition 2 is applied to a thickness of 10 μm and dried at 100 ° C. for 1 minute to obtain a dry film. The obtained dry film is observed at a magnification of 200 times using an optical microscope. The number of aggregates having a minimum diameter of 5 μm or more per visual field having a visual field area of 28.3 mm 2 is measured.
Condition 2: 50% by mass of the above metal fine particles, 0.3% by mass of ethyl cellulose manufactured by Dow Chemical Japan as a resin, 48.8% by mass of dihydroterpinyl acetate manufactured by Nippon Terpen as a solvent, and 48.8% by mass as a dispersant. A composition is obtained by blending 0.9% by mass of Eslim 221P manufactured by Nichiyu Co., Ltd. The obtained composition is dispersed in 1 pass each at pressures of 8 bar, 10 bar, 12 bar and 14 bar using SDY300 manufactured by Buehler as a 3-roll mill to prepare a paste.
本発明によれば、凝集体の個数が少ない金属微粒子が得られる。 According to the present invention, metal fine particles having a small number of aggregates can be obtained.
［金属微粒子の製造方法］
本発明の金属微粒子の製造方法（以下、単に「本発明の製造方法」ともいう）は、粒子径が１μｍ以下である原料金属微粒子を含有し、かつ、含水率が３０質量％以下である水スラリーを準備し、上記水スラリーを、凍結乾燥することにより、金属微粒子を得る、金属微粒子の製造方法である。
[Manufacturing method of metal fine particles]
The method for producing metal fine particles of the present invention (hereinafter, also simply referred to as “the production method of the present invention”) contains water containing raw metal fine particles having a particle size of 1 μm or less and a water content of 30% by mass or less. This is a method for producing metal fine particles, wherein a slurry is prepared and the water slurry is freeze-dried to obtain metal fine particles.
まず、上述したように、従来は、例えば真空乾燥（特許文献１）によって、水スラリーの水分を除去している。
しかし、粒子を含有する水スラリーを真空乾燥する場合、粒子どうしが水で架橋（液架橋）して近接した状態となり、この状態で水分除去されるため、粒子どうしが凝集しやすいと考えられる。粒子径が小さくなるに従い、近接する粒子が増加し、より強固な凝集体が生成する。水の表面張力は７２．７ｍＮ／ｍと高いため、水溶媒を用いる水スラリーを乾燥する場合は、特に、凝集体を作りやすい。
First, as described above, conventionally, the water content of the water slurry is removed by, for example, vacuum drying (Patent Document 1).
However, when the water slurry containing particles is vacuum-dried, the particles are crosslinked (liquid crosslinked) with water and become close to each other, and water is removed in this state, so that it is considered that the particles are likely to aggregate. As the particle size becomes smaller, the number of adjacent particles increases, and stronger agglomerates are formed. Since the surface tension of water is as high as 72.7 mN / m, agglomerates are likely to be formed especially when the water slurry using an aqueous solvent is dried.
これに対して、本発明の製造方法においては、水スラリーを凍結乾燥する。ここで、凍結乾燥とは、水を凍結させた後に水を昇華して乾燥させることである。これにより、液架橋を最小限に抑えた状態で乾燥でき、その結果、粒子どうしの凝集を抑制できると考えられる。
もっとも、粒子径が小さい場合は、液架橋が強固に生じて、凍結の途上でも凝集が発生しやすい。
そこで、本発明者ら鋭意研究を進めた。その結果、凍結乾燥する前の水スラリーの含水率を３０質量％以下まで低減することにより、粒子径が１μｍ以下と小さい場合であっても、凍結時における液架橋に起因する凝集を抑制できることを見出した。
On the other hand, in the production method of the present invention, the water slurry is freeze-dried. Here, freeze-drying means freezing water and then sublimating and drying the water. It is considered that this enables drying with the liquid cross-linking minimized, and as a result, the aggregation of particles can be suppressed.
However, when the particle size is small, liquid cross-linking occurs strongly, and aggregation is likely to occur even during freezing.
Therefore, the present inventors have carried out diligent research. As a result, by reducing the water content of the water slurry before freeze-drying to 30% by mass or less, aggregation due to liquid cross-linking during freezing can be suppressed even when the particle size is as small as 1 μm or less. I found it.
すなわち、本発明の製造方法によれば、凝集体の個数が少ない金属微粒子が得られる。
凝集体が少ない金属微粒子を、積層セラミックコンデンサの内部電極層に用いることにより、内部電極層を薄層化できる。その結果、良好な静電容量が得られる。
That is, according to the production method of the present invention, metal fine particles having a small number of aggregates can be obtained.
By using metal fine particles having few aggregates for the internal electrode layer of the multilayer ceramic capacitor, the internal electrode layer can be thinned. As a result, good capacitance can be obtained.
以下、本発明の製造方法をより詳細に説明する。 Hereinafter, the production method of the present invention will be described in more detail.
〈原料金属微粒子〉
原料金属微粒子は、水スラリーに含有される金属微粒子であり、以下、単に「粒子」という場合がある。
<Material metal fine particles>
The raw material metal fine particles are metal fine particles contained in the water slurry, and may be simply referred to as "particles" below.
《粒子径》
原料金属微粒子の粒子径は、１μｍ以下である。
原料金属微粒子を積層セラミックコンデンサの内部電極層に用いる場合、内部電極層を薄層化しやすいという理由から、原料金属微粒子の粒子径は、０．８μｍ以下が好ましく、０．６μｍ以下がより好ましく、０．４μｍ以下が更に好ましい。下限は特に限定されず、原料金属微粒子の粒子径は、例えば、０．０５μｍ以上である。
"Particle size"
The particle size of the raw metal fine particles is 1 μm or less.
When the raw metal fine particles are used for the internal electrode layer of the multilayer ceramic capacitor, the particle size of the raw metal fine particles is preferably 0.8 μm or less, more preferably 0.6 μm or less, because the internal electrode layer is easily thinned. It is more preferably 0.4 μm or less. The lower limit is not particularly limited, and the particle size of the raw metal fine particles is, for example, 0.05 μm or more.
粒子径は、次のように求める。
まず、粒子を、走査型電子顕微鏡（ＳＥＭ）を用いて、倍率１５０００倍で観察して、ＳＥＭ画像を得る。得られたＳＥＭ画像から、無作為に１０００個以上の粒子を抽出する。画像解析ソフトを用いて、抽出した粒子の投影面積円相当径（ＳＥＭ画像上の粒子の面積と同一の面積の円の直径）を得て、粒度分布における個数基準累積度数が５０％となる粒子径を求める。
The particle size is calculated as follows.
First, the particles are observed with a scanning electron microscope (SEM) at a magnification of 15,000 to obtain an SEM image. From the obtained SEM image, 1000 or more particles are randomly extracted. Using image analysis software, obtain the projected area circle-equivalent diameter (diameter of a circle with the same area as the particle area on the SEM image) of the extracted particles, and the number-based cumulative frequency in the particle size distribution is 50%. Find the diameter.
《構成元素》
（金属元素）
原料金属微粒子に含有される金属元素は、特に限定されず、例えば、ニッケル（Ｎｉ）、コバルト（Ｃｏ）、銀（Ａｇ）、金（Ａｕ）、プラチナ（Ｐｔ）、銅（Ｃｕ）、アルミニウム（Ａｌ）などが挙げられる。
これらのうち、原料金属微粒子を積層セラミックコンデンサの内部電極層に用いる観点からは、原料金属微粒子は、ニッケルおよび銅からなる群から選ばれる少なくとも１種を含有することが好ましい。原料金属微粒子がニッケルおよび銅を含有する場合、銅とニッケルとの質量比（Ｃｕ／Ｎｉ）は、１０／９０〜９０／１０が好ましく、２０／８０〜８０／２０がより好ましく、３０／７０〜７０／３０が更に好ましい。
この場合、原料金属微粒子は、焼結特性の改善を目的として、更に、バナジウム（Ｖ）、クロム（Ｃｒ）、ジルコニウム（Ｚｒ）、ニオブ（Ｎｂ）、ケイ素（Ｓｉ）、モリブデン（Ｍｏ）、タングステン（Ｗ）、タンタル（Ｔａ）などの元素を含有していてもよい。
原料金属微粒子における各金属元素の含有量は、高周波プラズマ発光分析装置（ＩＣＰＥ−９０００、島津製作所社製）を用いて計測する。
《Constituent elements》
(Metallic element)
The metal element contained in the raw metal fine particles is not particularly limited, and for example, nickel (Ni), cobalt (Co), silver (Ag), gold (Au), platinum (Pt), copper (Cu), and aluminum ( Al) and the like.
Of these, from the viewpoint of using the raw metal fine particles in the internal electrode layer of the multilayer ceramic capacitor, the raw metal fine particles preferably contain at least one selected from the group consisting of nickel and copper. When the raw metal fine particles contain nickel and copper, the mass ratio (Cu / Ni) of copper to nickel is preferably 10/90 to 90/10, more preferably 20/80 to 80/20, and 30/70. ~ 70/30 is more preferable.
In this case, the raw metal fine particles are further used for the purpose of improving the sintering properties, such as vanadium (V), chromium (Cr), zirconium (Zr), niobium (Nb), silicon (Si), molybdenum (Mo), and tungsten. It may contain elements such as (W) and tantalum (Ta).
The content of each metal element in the raw metal fine particles is measured using a high-frequency plasma emission spectrometer (ICPE-9000, manufactured by Shimadzu Corporation).
（硫黄）
また、本発明者らは、原料金属微粒子に特定量の硫黄（Ｓ）が含まれることにより、粒子どうしの近接がより抑制されることを見出した。
すなわち、凝集の発生をより抑制できるという理由から、原料金属微粒子において、硫黄の含有量は、０．０５質量％以上が好ましく、０．１質量％以上がより好ましい。上限は特に限定されないが、１．０％質量％以下が好ましく、０．８質量％以下がより好ましく、０．５質量％以下が更に好ましい。
原料金属微粒子における硫黄の含有量は、炭素・硫黄分析装置（ＣＳ８４４、ＬＥＣＯジャパン社製）を用いて、燃焼法により計測する。
(sulfur)
Further, the present inventors have found that the proximity of particles to each other is further suppressed by containing a specific amount of sulfur (S) in the raw metal fine particles.
That is, the sulfur content in the raw metal fine particles is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, because the occurrence of aggregation can be further suppressed. The upper limit is not particularly limited, but 1.0% by mass or less is preferable, 0.8% by mass or less is more preferable, and 0.5% by mass or less is further preferable.
The sulfur content in the raw metal fine particles is measured by a combustion method using a carbon / sulfur analyzer (CS844, manufactured by LECO Japan).
《製法》
原料金属微粒子の製造方法は、特に限定されない。例えば、従来公知の気相法（例えば、特開２００８−２０８４６５号公報、特開２０１１−２１９８３０号公報、特開２０１３−１７０３０３号公報、国際公開第２０１４／０８０６００号などを参照）を用いて、原料金属微粒子を製造できる。
《Manufacturing method》
The method for producing the raw metal fine particles is not particularly limited. For example, using a conventionally known vapor phase method (see, for example, JP-A-2008-208465, JP-A-2011-219830, JP-A-2013-170303, International Publication No. 2014/080600, etc.), Raw metal fine particles can be produced.
〈水スラリー〉
水スラリーは、原料金属微粒子が水溶媒に分散した分散液である。
<Water slurry>
A water slurry is a dispersion in which raw metal fine particles are dispersed in an aqueous solvent.
《含水率》
水スラリーの含水率は、上述したように凝集を抑制できるという理由から、３０質量％以下であり、２４質量％以下が好ましく、１８質量％以下がより好ましく、凝集をより抑制できるという理由から、１２質量％以下が更に好ましい。
下限は特に限定されず、例えば、５質量％以上であり、８質量％以上が好ましい。
《Moisture content》
The water content of the water slurry is 30% by mass or less, preferably 24% by mass or less, more preferably 18% by mass or less, and more preferably agglomeration because it can suppress aggregation as described above. More preferably, it is 12% by mass or less.
The lower limit is not particularly limited, and is, for example, 5% by mass or more, preferably 8% by mass or more.
水スラリーの含水率は、微量水分測定装置（ＡＱ−２１００、平沼産業社製）および水分気化装置（ＥＶ−２０００、平沼産業社製）を用いて、カールフィッシャー法により、３００℃での水分量を測定することにより求める。
ただし、水スラリーの含水率が高い（例えば、含水率が５０質量％以上である）場合は、カールフィッシャー法による水分量の測定ができない。この場合は、水スラリーを乾燥し、乾燥前の質量と乾燥後の質量とから、水分量を概算する。
The water content of the water slurry is determined by the Karl Fischer method using a trace moisture measuring device (AQ-2100, manufactured by Hiranuma Sangyo Co., Ltd.) and a water vaporizer (EV-2000, manufactured by Hiranuma Sangyo Co., Ltd.). Is obtained by measuring.
However, when the water content of the water slurry is high (for example, the water content is 50% by mass or more), the water content cannot be measured by the Karl Fischer method. In this case, the water slurry is dried, and the water content is estimated from the mass before drying and the mass after drying.
なお、水スラリーは、水溶媒以外に、更に、有機溶媒を含有していてもよい。水スラリーが有機溶媒を含有する場合、有機溶媒の含有量は、水スラリー中で２０質量％までとすることが好ましい。
有機溶媒としては、例えば、例えば、エタノール、テルペン系アルコール、t−ブタノール、アセトン、酢酸などが挙げられ、これらを１種単独で用いてもよく、２種以上を併用してもよい。
The water slurry may further contain an organic solvent in addition to the water solvent. When the water slurry contains an organic solvent, the content of the organic solvent is preferably up to 20% by mass in the water slurry.
Examples of the organic solvent include ethanol, terpene alcohol, t-butanol, acetone, acetic acid and the like, and these may be used alone or in combination of two or more.
《製法》
水スラリーは、原料金属微粒子を、溶媒に分散させることにより得られる。
このとき、例えば、まず、含水率が高め（例えば約９０質量％）の水スラリーを得る。その後、遠心脱水機を用いた脱水等を行なうことにより、水スラリーを濃縮して、含水率を低減する。こうして、含水率が３０質量％以下の水スラリーが得られる。
水スラリーを濃縮することなく、じかに、含水率が３０質量％以下の水スラリーを得てもよい。
《Manufacturing method》
The water slurry is obtained by dispersing the raw metal fine particles in a solvent.
At this time, for example, first, a water slurry having a high water content (for example, about 90% by mass) is obtained. Then, the water slurry is concentrated and the water content is reduced by performing dehydration or the like using a centrifugal dehydrator. In this way, a water slurry having a water content of 30% by mass or less can be obtained.
A water slurry having a water content of 30% by mass or less may be directly obtained without concentrating the water slurry.
〈凍結乾燥〉
水スラリーを凍結乾燥して、水分を除去する。これにより、凝集が抑制された金属微粒子が得られる。
凍結乾燥の方法は、従来公知の方法を適宜採用できる。
具体的には、例えば、まず、水スラリーを、溶媒の融点以下の温度まで冷却して、凍結する。水スラリーを冷却（凍結）する方法としては、特に限定されず、従来公知の方法を採用でき、例えば、水スラリーを収容した容器を冷却棚に設置する方法；冷却された気体や、液体窒素、液化炭酸ガスなどの液化ガスを用いて水スラリーを冷却する方法；等が挙げられる。
次いで、凍結した水スラリーを乾燥する。このとき、溶媒の融点以上の温度にならないよう制御して、真空（減圧）条件下で、乾燥することが好ましい。具体的には、水の三重点（６００Ｐａ、０．０１℃）以下の条件、すなわち、温度が０．０１℃以下、かつ、圧力が６００Ｐａ以下の高真空条件下で、乾燥することがより好ましい。こうして、凍結した水スラリーの溶媒を、昇華させて除去する。
<freeze drying>
The water slurry is lyophilized to remove water. As a result, metal fine particles in which aggregation is suppressed can be obtained.
As the freeze-drying method, a conventionally known method can be appropriately adopted.
Specifically, for example, first, the water slurry is cooled to a temperature equal to or lower than the melting point of the solvent and frozen. The method for cooling (freezing) the water slurry is not particularly limited, and a conventionally known method can be adopted. For example, a method of installing a container containing the water slurry on a cooling shelf; a cooled gas, liquid nitrogen, etc. A method of cooling the water slurry using a liquefied gas such as liquefied carbon dioxide gas; and the like.
The frozen water slurry is then dried. At this time, it is preferable to dry under vacuum (decompression) conditions by controlling the temperature so that the temperature does not exceed the melting point of the solvent. Specifically, it is more preferable to dry under the condition of the triple point of water (600 Pa, 0.01 ° C.) or less, that is, the high vacuum condition of the temperature of 0.01 ° C. or less and the pressure of 600 Pa or less. .. In this way, the solvent of the frozen water slurry is sublimated and removed.
水スラリーを凍結乾燥することにより乾燥体が得られる。得られた乾燥体は、適宜ふるい等をかけてもよい。こうして、乾燥粉の態様で、所望する金属微粒子が得られる。 A dried product is obtained by freeze-drying the water slurry. The obtained dried product may be appropriately sieved or the like. In this way, the desired metal fine particles can be obtained in the form of dry powder.
［金属微粒子］
本発明の金属微粒子は、上述した本発明の製造方法により得られる金属微粒子である。
より詳細には、本発明の金属微粒子は、下記条件１で測定される最小径５μｍ以上である凝集体の個数が、５視野の平均値で２０個以下である、金属微粒子である。
[Metal particles]
The metal fine particles of the present invention are metal fine particles obtained by the above-mentioned production method of the present invention.
More specifically, the metal fine particles of the present invention are metal fine particles in which the number of aggregates having a minimum diameter of 5 μm or more measured under the following condition 1 is 20 or less on average in five fields of view.
条件１：下記条件２で作製されるペーストを、厚さ１０μｍで塗布し、１００℃で１分間乾燥して乾燥膜を得る。得られた乾燥膜を、光学顕微鏡を用いて、倍率２００倍で観察する。視野面積が２８．３ｍｍ２である１視野あたりの最小径５μｍ以上である凝集体の個数を測定する。 Condition 1: The paste prepared under the following condition 2 is applied to a thickness of 10 μm and dried at 100 ° C. for 1 minute to obtain a dry film. The obtained dry film is observed at a magnification of 200 times using an optical microscope. The number of aggregates having a minimum diameter of 5 μm or more per visual field having a visual field area of 28.3 mm 2 is measured.
条件２：金属微粒子（本発明の金属微粒子）を５０質量％、樹脂としてダウ・ケミカル日本社製のエチルセルロースを０．３質量％、溶剤として日本テルペン社製のジヒドロターピニルアセテートを４８．８質量％、分散剤として日油社製のエスリーム２２１Ｐを０．９質量％配合して、組成物を得る。得られた組成物を、３本ロールミルとしてビューラー社製のＳＤＹ３００を用いて、８ｂａｒ、１０ｂａｒ、１２ｂａｒおよび１４ｂａｒの圧力でそれぞれ１パスずつ分散させて、ペーストを作製する。 Condition 2: 50% by mass of metal fine particles (metal fine particles of the present invention), 0.3% by mass of ethyl cellulose manufactured by Dow Chemical Japan Co., Ltd. as a resin, and 48.8 mass% of dihydroterpinyl acetate manufactured by Nippon Terpen Co., Ltd. as a solvent. A composition is obtained by blending 0.9% by mass and 0.9% by mass of Eslim 221P manufactured by Nichiyu Co., Ltd. as a dispersant. The obtained composition is dispersed in 1 pass each at pressures of 8 bar, 10 bar, 12 bar and 14 bar using SDY300 manufactured by Buehler as a 3-roll mill to prepare a paste.
ところで、特開２０１４−１２２３６８号公報の段落［００３８］および［００４５］では、溶剤としてターピネオールを用いて、凝集体を評価している。
しかし、特開平９−１７６８７号公報の段落［０００８］に記載されているように、ターピネオールは、積層体を焼成して積層セラミックコンデンサを得る際に、シートアタックが発生させ得る。
このため、上記条件２では、溶媒として、ターピネオールではなく、ジヒドロターピニルアセテートを用いて、ペーストを作製する。
ジヒドロターピニルアセテートは、ターピネオールと比べて、ペースト作製時の分散性が低下する。このため、ジヒドロターピニルアセテートを用いてペーストを作製する場合、ターピネオールを用いてペーストを作製する場合よりも、凝集体の個数が多くなり、密度も高くなる傾向にある。
By the way, in paragraphs [0038] and [0045] of JP-A-2014-122368, aggregates are evaluated using tarpineol as a solvent.
However, as described in paragraph [0008] of JP-A-9-17687, tarpineol may cause a sheet attack when the laminate is fired to obtain a multilayer ceramic capacitor.
Therefore, under the above condition 2, a paste is prepared using dihydroterpinyl acetate as a solvent instead of tarpineol.
Dihydroterpinyl acetate has lower dispersibility during paste preparation than tarpineol. Therefore, when the paste is prepared using dihydroterpinyl acetate, the number of aggregates tends to be larger and the density tends to be higher than when the paste is prepared using tarpineol.
以下に、実施例を挙げて本発明を具体的に説明する。ただし、本発明は以下に説明する実施例に限定されない。 Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to the examples described below.
〈金属微粒子の製造〉
以下のようにして、実施例１〜実施例７および比較例１〜比較例１０の金属微粒子を製造した。
<Manufacturing of fine metal particles>
The metal fine particles of Examples 1 to 7 and Comparative Examples 1 to 10 were produced as follows.
《実施例１〜実施例７》
（実施例１）
気相法により製造した、０．１３質量％の硫黄を含有するニッケル微粒子を、原料金属微粒子として準備した。原料金属微粒子の粒子径は、０．２μｍであった。
準備した原料金属微粒子を、水溶媒に分散させて、含水率が約９０質量％である水スラリーを得た。得られた水スラリーを、遠心脱水機を用いて脱水し、水スラリーの含水率を１１．３質量％まで低減した。
含水率を１１．３質量％まで低減した水スラリーを、凍結乾燥機（ＦＤＵ２１１０、ＤＲＣ１１１０−ＲＥＣ、東京理化器械社製）を用いて、−４０℃で凍結した。凍結した水スラリーを、−１０℃、２０Ｐａの真空条件下で、２４時間乾燥し、その後、更に、３０℃、２０Ｐａの真空条件下で、２４時間乾燥し、乾燥体を得た。
得られた乾燥体を、開口径が５００μｍのメッシュに通して、乾燥粉を得た。得られた乾燥粉を、実施例１の金属微粒子とした。
<< Examples 1 to 7 >>
(Example 1)
Nickel fine particles containing 0.13% by mass of sulfur produced by the vapor phase method were prepared as raw metal fine particles. The particle size of the raw material metal fine particles was 0.2 μm.
The prepared raw metal fine particles were dispersed in an aqueous solvent to obtain an aqueous slurry having a water content of about 90% by mass. The obtained water slurry was dehydrated using a centrifugal dehydrator to reduce the water content of the water slurry to 11.3% by mass.
A water slurry having a water content reduced to 11.3% by mass was frozen at −40 ° C. using a freeze dryer (FDU2110, DRC1110-REC, manufactured by Tokyo Rika Kikai Co., Ltd.). The frozen water slurry was dried under vacuum conditions of −10 ° C. and 20 Pa for 24 hours, and then further dried under vacuum conditions of 30 ° C. and 20 Pa for 24 hours to obtain a dried product.
The obtained dried product was passed through a mesh having an opening diameter of 500 μm to obtain dried powder. The obtained dry powder was used as the metal fine particles of Example 1.
（実施例２）
原料金属微粒子（ニッケル微粒子）における硫黄の含有量を０．０５質量％とした。
それ以外の点は、実施例１と同様にして、実施例２の金属微粒子を得た。
(Example 2)
The sulfur content in the raw metal fine particles (nickel fine particles) was set to 0.05% by mass.
Other than that, the metal fine particles of Example 2 were obtained in the same manner as in Example 1.
（実施例３）
原料金属微粒子（ニッケル微粒子）に硫黄を含有させなかった。
それ以外の点は、実施例１と同様にして、実施例３の金属微粒子を得た。
(Example 3)
Sulfur was not contained in the raw metal fine particles (nickel fine particles).
Other than that, the metal fine particles of Example 3 were obtained in the same manner as in Example 1.
（実施例４）
水スラリーの含水率を１７．３質量％まで低減した。
それ以外の点は、実施例１と同様にして、実施例４の金属微粒子を得た。
(Example 4)
The water content of the water slurry was reduced to 17.3% by mass.
Other than that, the metal fine particles of Example 4 were obtained in the same manner as in Example 1.
（実施例５）
水スラリーの含水率を２８．２質量％まで低減した。
それ以外の点は、実施例１と同様にして、実施例５の金属微粒子を得た。
(Example 5)
The water content of the water slurry was reduced to 28.2% by mass.
Other than that, the metal fine particles of Example 5 were obtained in the same manner as in Example 1.
（実施例６）
気相法により製造した、０．１３質量％の硫黄を含有する銅微粒子を、原料金属微粒子として準備した。原料金属微粒子の粒子径は、０．２μｍであった。
それ以外の点は、実施例１と同様にして、実施例６の金属微粒子を得た。
(Example 6)
Copper fine particles containing 0.13% by mass of sulfur produced by the vapor phase method were prepared as raw metal fine particles. The particle size of the raw material metal fine particles was 0.2 μm.
Other than that, the metal fine particles of Example 6 were obtained in the same manner as in Example 1.
（実施例７）
気相法により製造した、０．１３質量％の硫黄を含有し、かつ、銅とニッケルとの質量比（Ｃｕ／Ｎｉ）が４０／６０であるニッケル銅合金微粒子を、原料金属微粒子として準備した。原料金属微粒子の粒子径は、０．２μｍであった。
それ以外の点は、実施例１と同様にして、実施例７の金属微粒子を得た。
(Example 7)
Nickel-copper alloy fine particles produced by the vapor phase method, which contain 0.13% by mass of sulfur and have a mass ratio (Cu / Ni) of copper to nickel of 40/60, were prepared as raw metal fine particles. .. The particle size of the raw material metal fine particles was 0.2 μm.
Other than that, the metal fine particles of Example 7 were obtained in the same manner as in Example 1.
《比較例１〜比較例１０》
（比較例１）
気相法により製造した、０．１３質量％の硫黄を含有するニッケル微粒子を、原料金属微粒子として準備した。原料金属微粒子の粒子径は、０．２μｍであった。
準備した原料金属微粒子を、水溶媒に分散させて、含水率が約９０質量％である水スラリーを得た。得られた水スラリーを、遠心脱水機を用いて脱水し、水スラリーの含水率を１１．３質量％まで低減した。
含水率を１１．３質量％まで低減した水スラリーを、真空乾燥機（ＶＯＳ−３０１ＳＤ、東京理化器械社製）を用いて、６０℃、−０．１ＭＰａの条件で、１２時間乾燥し、乾燥体を得た。
得られた乾燥体を、開口径が５００μｍのメッシュに通して、乾燥粉を得た。得られた乾燥粉を、比較例１の金属微粒子とした。
<< Comparative Examples 1 to 10 >>
(Comparative Example 1)
Nickel fine particles containing 0.13% by mass of sulfur produced by the vapor phase method were prepared as raw metal fine particles. The particle size of the raw material metal fine particles was 0.2 μm.
The prepared raw metal fine particles were dispersed in an aqueous solvent to obtain an aqueous slurry having a water content of about 90% by mass. The obtained water slurry was dehydrated using a centrifugal dehydrator to reduce the water content of the water slurry to 11.3% by mass.
A water slurry having a water content reduced to 11.3% by mass is dried for 12 hours at 60 ° C. and -0.1 MPa using a vacuum dryer (VOS-301SD, manufactured by Tokyo Rika Kikai Co., Ltd.) and dried. I got a body.
The obtained dried product was passed through a mesh having an opening diameter of 500 μm to obtain dried powder. The obtained dry powder was used as metal fine particles of Comparative Example 1.
（比較例２）
原料金属微粒子（ニッケル微粒子）における硫黄の含有量を０．０５質量％とした。
それ以外の点は、比較例１と同様にして、比較例２の金属微粒子を得た。
(Comparative Example 2)
The sulfur content in the raw metal fine particles (nickel fine particles) was set to 0.05% by mass.
Other than that, the metal fine particles of Comparative Example 2 were obtained in the same manner as in Comparative Example 1.
（比較例３）
原料金属微粒子（ニッケル微粒子）に硫黄を含有させなかった。
それ以外の点は、比較例１と同様にして、比較例３の金属微粒子を得た。
(Comparative Example 3)
Sulfur was not contained in the raw metal fine particles (nickel fine particles).
Other than that, the metal fine particles of Comparative Example 3 were obtained in the same manner as in Comparative Example 1.
（比較例４）
気相法により製造した、０．１３質量％の硫黄を含有するニッケル微粒子を、原料金属微粒子として準備した。原料金属微粒子の粒子径は、０．２μｍであった。
準備した原料金属微粒子を、水溶媒に分散させて、含水率が約９０質量％である水スラリーを得た。
含水率が約９０質量％である水スラリーを、凍結乾燥機（ＦＤＵ２１１０、ＤＲＣ１１１０−ＲＥＣ、東京理化器械社製）を用いて、−４０℃で凍結した。凍結した水スラリーを、−１０℃、２０Ｐａの真空条件下で、２４時間乾燥し、その後、更に、３０℃、２０Ｐａの真空条件下で、２４時間乾燥し、乾燥体を得た。
得られた乾燥体を、開口径が５００μｍのメッシュに通して、乾燥粉を得た。得られた乾燥粉を、比較例４の金属微粒子とした。
なお、水スラリーの含水率は、カールフィッシャー法による水分量の測定ができなかったので、乾燥前後の水スラリーの質量から概算した。
(Comparative Example 4)
Nickel fine particles containing 0.13% by mass of sulfur produced by the vapor phase method were prepared as raw metal fine particles. The particle size of the raw material metal fine particles was 0.2 μm.
The prepared raw metal fine particles were dispersed in an aqueous solvent to obtain an aqueous slurry having a water content of about 90% by mass.
A water slurry having a water content of about 90% by mass was frozen at −40 ° C. using a freeze dryer (FDU2110, DRC1110-REC, manufactured by Tokyo Rika Kikai Co., Ltd.). The frozen water slurry was dried under vacuum conditions of −10 ° C. and 20 Pa for 24 hours, and then further dried under vacuum conditions of 30 ° C. and 20 Pa for 24 hours to obtain a dried product.
The obtained dried product was passed through a mesh having an opening diameter of 500 μm to obtain dried powder. The obtained dry powder was used as metal fine particles of Comparative Example 4.
Since the water content of the water slurry could not be measured by the Karl Fischer method, it was estimated from the mass of the water slurry before and after drying.
（比較例５）
原料金属微粒子（ニッケル微粒子）における硫黄の含有量を０．０５質量％とした。
それ以外の点は、比較例４と同様にして、比較例５の金属微粒子を得た。
(Comparative Example 5)
The sulfur content in the raw metal fine particles (nickel fine particles) was set to 0.05% by mass.
Other than that, the metal fine particles of Comparative Example 5 were obtained in the same manner as in Comparative Example 4.
（比較例６）
原料金属微粒子（ニッケル微粒子）に硫黄を含有させなかった。
それ以外の点は、比較例４と同様にして、比較例６の金属微粒子を得た。
(Comparative Example 6)
Sulfur was not contained in the raw metal fine particles (nickel fine particles).
Other than that, the metal fine particles of Comparative Example 6 were obtained in the same manner as in Comparative Example 4.
（比較例７）
水スラリーの含水率を、遠心脱水機を用いた脱水により３５．２質量％まで低減した。水スラリーの含水率は、カールフィッシャー法により求めた。
それ以外の点は、比較例４と同様にして、比較例７の金属微粒子を得た。
(Comparative Example 7)
The water content of the water slurry was reduced to 35.2% by mass by dehydration using a centrifugal dehydrator. The water content of the water slurry was determined by the Karl Fischer method.
Other than that, the metal fine particles of Comparative Example 7 were obtained in the same manner as in Comparative Example 4.
（比較例８）
水スラリーの含水率を、遠心脱水機を用いた脱水により約５９質量％まで低減した。
それ以外の点は、比較例４と同様にして、比較例８の金属微粒子を得た。
なお、水スラリーの含水率は、カールフィッシャー法による水分量の測定ができなかったので、乾燥前後の水スラリーの質量から概算した。
(Comparative Example 8)
The water content of the water slurry was reduced to about 59% by mass by dehydration using a centrifugal dehydrator.
Other than that, the metal fine particles of Comparative Example 8 were obtained in the same manner as in Comparative Example 4.
Since the water content of the water slurry could not be measured by the Karl Fischer method, it was estimated from the mass of the water slurry before and after drying.
（比較例９）
気相法により製造した、０．１３質量％の硫黄を含有する銅微粒子を、原料金属微粒子として準備した。原料金属微粒子の粒子径は、０．２μｍであった。
それ以外の点は、比較例１と同様にして、比較例９の金属微粒子を得た。
(Comparative Example 9)
Copper fine particles containing 0.13% by mass of sulfur produced by the vapor phase method were prepared as raw metal fine particles. The particle size of the raw material metal fine particles was 0.2 μm.
Other than that, the metal fine particles of Comparative Example 9 were obtained in the same manner as in Comparative Example 1.
（比較例１０）
気相法により製造した、０．１３質量％の硫黄を含有し、かつ、銅とニッケルとの質量比（Ｃｕ／Ｎｉ）が４０／６０であるニッケル銅合金微粒子を、原料金属微粒子として準備した。原料金属微粒子の粒子径は、０．２μｍであった。
それ以外の点は、比較例１と同様にして、比較例１０の金属微粒子を得た。
(Comparative Example 10)
Nickel-copper alloy fine particles produced by the vapor phase method, which contain 0.13% by mass of sulfur and have a mass ratio (Cu / Ni) of copper to nickel of 40/60, were prepared as raw metal fine particles. .. The particle size of the raw material metal fine particles was 0.2 μm.
Other than that, the metal fine particles of Comparative Example 10 were obtained in the same manner as in Comparative Example 1.
〈導電ペーストの作製〉
実施例１〜実施例７および比較例１〜比較例１０の金属微粒子を用いて、導電ペーストを作製した。
具体的には、まず、金属微粒子を５０質量％、樹脂（エチルセルロース、ダウ・ケミカル日本社製）を０．３質量％、溶剤（ジヒドロターピニルアセテート、日本テルペン社製）を４８．８質量％、分散剤（エスリーム２２１Ｐ、日油社製）を０．９質量％配合して、組成物を得た。
次に、得られた組成物を、３本ロールミル（ＳＤＹ３００、ビューラー社製）を用いて、８ｂａｒ、１０ｂａｒ、１２ｂａｒおよび１４ｂａｒの圧力でそれぞれ１パスずつ分散させた。こうして、導電ペーストを得た。
<Making conductive paste>
A conductive paste was prepared using the metal fine particles of Examples 1 to 7 and Comparative Examples 1 to 10.
Specifically, first, 50% by mass of metal fine particles, 0.3% by mass of resin (ethyl cellulose, manufactured by Dow Chemical Japan), and 48.8% by mass of solvent (dihydroterpinyl acetate, manufactured by Nippon Terpen). % And a dispersant (Eslim 221P, manufactured by Nichiyu Co., Ltd.) were blended in an amount of 0.9% by mass to obtain a composition.
Next, the obtained composition was dispersed using a 3-roll mill (SDY300, manufactured by Buehler) at pressures of 8 bar, 10 bar, 12 bar and 14 bar, one pass each. In this way, a conductive paste was obtained.
〈評価〉
作製した導電ペーストを用いて、次の評価を行なった。結果を下記表１に示す。
<Evaluation>
The following evaluation was performed using the prepared conductive paste. The results are shown in Table 1 below.
《凝集体の個数》
作製した導電ペーストを、アプリケータを用いて、スライドガラス上に厚さ１０μｍで塗布し、１００℃で１分間乾燥して、ペースト乾燥膜を得た。得られたペースト乾燥膜を、光学顕微鏡を用いて、倍率２００倍で観察した。１視野（視野面積：２８．３ｍｍ２）あたりの最小径５μｍ以上である凝集体の個数を測定した。５視野の平均値を下記表１に記載した。
<< Number of aggregates >>
The prepared conductive paste was applied onto a slide glass to a thickness of 10 μm using an applicator and dried at 100 ° C. for 1 minute to obtain a paste dry film. The obtained dry paste film was observed at a magnification of 200 times using an optical microscope. The number of aggregates having a minimum diameter of 5 μm or more per visual field (visual field area: 28.3 mm 2 ) was measured. The average values of the five fields of view are shown in Table 1 below.
《密度》
作製した導電ペーストを、アプリケータを用いて、ＰＥＴ（ポリエチレンテレフタラート）フィルムに厚さ３００μｍで塗布し、１００℃で１５分間乾燥して、ペースト乾燥膜を得た。得られたペースト乾燥膜を、治具を使用して直径３０ｍｍの円盤状にくり抜いた。くり抜いたペースト乾燥膜の直径、高さおよび質量から、密度（単位：ｇ／ｃｍ３）を計測した。計測は２回行ない、２回の平均値を下記表１に記載した。
"density"
The prepared conductive paste was applied to a PET (polyethylene terephthalate) film to a thickness of 300 μm using an applicator, and dried at 100 ° C. for 15 minutes to obtain a paste-dried film. The obtained dry paste film was hollowed out into a disk shape having a diameter of 30 mm using a jig. The density (unit: g / cm 3 ) was measured from the diameter, height and mass of the hollowed-out paste dry film. The measurement was performed twice, and the average value of the two times is shown in Table 1 below.
〈評価結果まとめ〉
《実施例と比較例との対比》
上記表１に示す結果から明らかなように、含水率が３０質量％以下の水スラリーを凍結乾燥した実施例１〜実施例７は、凍結乾燥しなかった比較例１〜比較例３、比較例９および比較例１０、ならびに、水スラリーの含水率が３０質量％を超える比較例４〜比較例８よりも、凝集体の個数が少なく、かつ、高密度であった。
<Summary of evaluation results>
<< Comparison between Examples and Comparative Examples >>
As is clear from the results shown in Table 1 above, Examples 1 to 7 in which a water slurry having a water content of 30% by mass or less was freeze-dried were compared with Comparative Examples 1 to 3 and Comparative Examples which were not freeze-dried. The number of aggregates was smaller and the density was higher than that of Comparative Examples 9 and 10 and Comparative Examples 4 to 8 in which the water content of the water slurry exceeded 30% by mass.
具体的には、例えば、乾燥方法のみ異なる実施例１と比較例１とを対比すると、凍結乾燥した実施例１は、凍結乾燥しなかった比較例１よりも、凝集体の個数が少なく、かつ、高密度であった。
これは、実施例２と比較例２との対比、実施例３と比較例３との対比、実施例６と比較例９との対比、および、実施例７と比較例１０との対比においても、同様であった。
Specifically, for example, when comparing Example 1 and Comparative Example 1 in which only the drying method is different, the freeze-dried Example 1 has a smaller number of aggregates and is smaller than the freeze-dried Comparative Example 1. , High density.
This also applies to the comparison between Example 2 and Comparative Example 2, the comparison between Example 3 and Comparative Example 3, the comparison between Example 6 and Comparative Example 9, and the comparison between Example 7 and Comparative Example 10. , It was the same.
また、水スラリーの含水率のみ異なる実施例１と比較例４、比較例７および比較例８とを対比すると、含水率が３０質量％以下である実施例１は、含水率が３０質量％を超える比較例４、比較例７および比較例８よりも、凝集体の個数が少なく、かつ、高密度であった。
これは、実施例２と比較例５との対比、および、実施例３と比較例６との対比においても、同様であった。
Further, comparing Example 1 in which only the water content of the water slurry is different from Comparative Example 4, Comparative Example 7 and Comparative Example 8, Example 1 having a water content of 30% by mass or less has a water content of 30% by mass. The number of aggregates was smaller and the density was higher than that of Comparative Example 4, Comparative Example 7, and Comparative Example 8.
This was the same in the comparison between Example 2 and Comparative Example 5, and the comparison between Example 3 and Comparative Example 6.
《実施例どうしの対比》
原料金属微粒子の硫黄の含有量のみが異なる実施例１〜実施例３を対比すると、硫黄を含有しない実施例３よりも、硫黄の含有量が０．０５質量％以上である実施例１および実施例２の方が、凝集体の個数がより少なく、かつ、より高密度であった。
そして、実施例１と実施例２とを対比すると、硫黄の含有量が０．１質量％以上である実施例１の方が、硫黄の含有量が０．１質量％未満である実施例２よりも、凝集体の個数が更に少なく、かつ、更に高密度であった。
<< Comparison between Examples >>
Comparing Examples 1 to 3 in which only the sulfur content of the raw metal fine particles is different, Example 1 and Example 3 in which the sulfur content is 0.05% by mass or more as compared with Example 3 containing no sulfur. Example 2 had a smaller number of aggregates and a higher density.
When Example 1 and Example 2 are compared, Example 1 having a sulfur content of 0.1% by mass or more has a sulfur content of less than 0.1% by mass in Example 2. The number of aggregates was smaller and the density was higher than that.
また、水スラリーの含水率のみが異なる実施例１、実施例４および実施例５を対比すると、含水率の値が小さくなるに従い（すなわち、実施例５、実施例４、実施例１の順に）、凝集体の個数が少なくなり、かつ、密度が高くなる傾向が見られた。 Further, when comparing Examples 1, 4 and 5 in which only the water content of the water slurry is different, as the value of the water content becomes smaller (that is, in the order of Example 5, Example 4, and Example 1). , The number of aggregates tended to decrease and the density tended to increase.
〈静電容量の評価〉
実施例１および比較例１の金属微粒子を用いて、積層セラミックコンデンサを作製し、静電容量を評価した。
<Evaluation of capacitance>
Multilayer ceramic capacitors were prepared using the metal fine particles of Example 1 and Comparative Example 1, and the capacitance was evaluated.
まず、実施例１および比較例１の金属微粒子を用いて、導電ペーストを作製した。
具体的には、金属微粒子を４５質量％、樹脂（エチルセルロース、ダウ・ケミカル日本社製）を２．５質量％、共材（チタン酸バリウム、堺化学工業社製）を９．０質量％、溶剤（ジヒドロターピニルアセテート、日本テルペン社製）を４３．５質量％配合して、組成物を得た。得られた組成物を、３本ロールミル（ＳＤＹ３００、ビューラー社製）を用いて、８ｂａｒ、１０ｂａｒ、１２ｂａｒおよび１４ｂａｒの圧力でそれぞれ１パスずつ分散させた。こうして、導電ペーストを得た。
First, a conductive paste was prepared using the metal fine particles of Example 1 and Comparative Example 1.
Specifically, 45% by mass of metal fine particles, 2.5% by mass of resin (ethyl cellulose, manufactured by Dow Chemical Japan Co., Ltd.), 9.0% by mass of co-material (barium titanate, manufactured by Sakai Chemical Industry Co., Ltd.), A solvent (dihydroterpinyl acetate, manufactured by Nippon Terpen Co., Ltd.) was blended in an amount of 43.5% by mass to obtain a composition. The resulting composition was dispersed using a 3-roll mill (SDY300, manufactured by Buehler) at pressures of 8 bar, 10 bar, 12 bar and 14 bar, one pass each. In this way, a conductive paste was obtained.
次に、チタン酸バリウムを主成分とする誘電体セラミック粉末を用いて、ドクターブレード法により、厚さ２．５μｍの誘電体グリーンシートを形成した。形成した誘電体グリーンシート上に、スクリーン印刷によって、導電ペーストを、０．４ｍｇ／ｃｍ２となるように塗布した。導電ペーストと誘電体グリーンシートとを交互に積層させ、導電ペーストの層が５層である積層体を得た。 Next, a dielectric green sheet having a thickness of 2.5 μm was formed by a doctor blade method using a dielectric ceramic powder containing barium titanate as a main component. On the formed dielectric green sheet, a conductive paste was applied by screen printing to a concentration of 0.4 mg / cm 2 . The conductive paste and the dielectric green sheet were alternately laminated to obtain a laminated body having five layers of the conductive paste.
得られた積層体を切断して、３．２ｍｍ×２．５ｍｍのサイズの個片を分離した。分離した積層体の個片を加熱して樹脂などを除去した。その後、非酸化性雰囲気中で最高温度１２２０℃にて焼成し、次いで、窒素雰囲気中で９００℃にて焼付けを行なった。 The obtained laminate was cut to separate pieces having a size of 3.2 mm × 2.5 mm. The individual pieces of the separated laminate were heated to remove the resin and the like. Then, it was fired at a maximum temperature of 1220 ° C. in a non-oxidizing atmosphere, and then baked at 900 ° C. in a nitrogen atmosphere.
こうして、積層セラミックコンデンサを作製した。
作製した積層セラミックコンデンサの静電容量（単位：ｎＦ）を計測した。結果を下記表２に示す。
In this way, a monolithic ceramic capacitor was produced.
The capacitance (unit: nF) of the produced multilayer ceramic capacitor was measured. The results are shown in Table 2 below.
〈静電容量の評価結果のまとめ〉
上記表２に示すように、実施例１の静電容量の平均値は、比較例１と比べて約５％向上していた。
上述したように、実施例１の金属微粒子は、比較例１よりも、凝集体の個数が少なく、かつ、高密度であったことから、静電容量が向上したと考えられる。
<Summary of capacitance evaluation results>
As shown in Table 2 above, the average value of the capacitance of Example 1 was improved by about 5% as compared with Comparative Example 1.
As described above, it is considered that the metal fine particles of Example 1 had an improved capacitance because the number of aggregates was smaller and the density was higher than that of Comparative Example 1.
更に、実施例６および比較例９の金属微粒子（銅微粒子）を用いて、上記と同様にして、静電容量を評価したところ、実施例６の静電容量の平均値は、比較例９と比べて向上していた。
また、実施例７および比較例１０の金属微粒子（ニッケル銅合金微粒子）を用いて、上記と同様にして、静電容量を評価したところ、実施例７の静電容量の平均値は、比較例１０と比べて向上していた。
Further, when the capacitance was evaluated in the same manner as above using the metal fine particles (copper fine particles) of Example 6 and Comparative Example 9, the average value of the capacitance of Example 6 was the same as that of Comparative Example 9. It was improved compared to.
Further, when the capacitance was evaluated in the same manner as above using the metal fine particles (nickel-copper alloy fine particles) of Example 7 and Comparative Example 10, the average value of the capacitance of Example 7 was found in Comparative Example. It was improved compared to 10.
Claims (6)
前記水スラリーを、凍結乾燥することにより、金属微粒子を得る、金属微粒子の製造方法。 A water slurry containing raw metal fine particles having a particle size of 1 μm or less and having a water content of 30% by mass or less was prepared.
A method for producing metal fine particles, which obtains metal fine particles by freeze-drying the water slurry.
条件１：下記条件２で作製されるペーストを、厚さ１０μｍで塗布し、１００℃で１分間乾燥して乾燥膜を得る。得られた乾燥膜を、光学顕微鏡を用いて、倍率２００倍で観察する。視野面積が２８．３ｍｍ２である１視野あたりの最小径５μｍ以上である凝集体の個数を測定する。
条件２：前記金属微粒子を５０質量％、樹脂としてダウ・ケミカル日本社製のエチルセルロースを０．３質量％、溶剤として日本テルペン社製のジヒドロターピニルアセテートを４８．８質量％、分散剤として日油社製のエスリーム２２１Ｐを０．９質量％配合して、組成物を得る。得られた組成物を、３本ロールミルとしてビューラー社製のＳＤＹ３００を用いて、８ｂａｒ、１０ｂａｒ、１２ｂａｒおよび１４ｂａｒの圧力でそれぞれ１パスずつ分散させて、ペーストを作製する。 Metal fine particles in which the number of aggregates having a minimum diameter of 5 μm or more measured under the following condition 1 is 20 or less on average in five fields of view.
Condition 1: The paste prepared under the following condition 2 is applied to a thickness of 10 μm and dried at 100 ° C. for 1 minute to obtain a dry film. The obtained dry film is observed at a magnification of 200 times using an optical microscope. The number of aggregates having a minimum diameter of 5 μm or more per visual field having a visual field area of 28.3 mm 2 is measured.
Condition 2: 50% by mass of the metal fine particles, 0.3% by mass of ethyl cellulose manufactured by Dow Chemical Japan as a resin, 48.8% by mass of dihydroterpinyl acetate manufactured by Nippon Terpen as a solvent, and 48.8% by mass as a dispersant. A composition is obtained by blending 0.9% by mass of Eslim 221P manufactured by Nichiyu Co., Ltd. The obtained composition is dispersed in 1 pass each at pressures of 8 bar, 10 bar, 12 bar and 14 bar using SDY300 manufactured by Buehler as a 3-roll mill to prepare a paste.
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| JP2007284715A (en) * | 2006-04-13 | 2007-11-01 | Sumitomo Osaka Cement Co Ltd | Method for producing nickel nanoparticle, and nickel nanoparticle |
| JP2011089147A (en) * | 2009-10-20 | 2011-05-06 | Mitsubishi Materials Corp | Silver fine particle and method for producing the same |
| JP2015190043A (en) * | 2014-03-28 | 2015-11-02 | 住友金属鉱山株式会社 | Wet manufacturing process of nickel powder |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2007284715A (en) * | 2006-04-13 | 2007-11-01 | Sumitomo Osaka Cement Co Ltd | Method for producing nickel nanoparticle, and nickel nanoparticle |
| JP2011089147A (en) * | 2009-10-20 | 2011-05-06 | Mitsubishi Materials Corp | Silver fine particle and method for producing the same |
| JP2015190043A (en) * | 2014-03-28 | 2015-11-02 | 住友金属鉱山株式会社 | Wet manufacturing process of nickel powder |
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