JP2009064603A - Conductive paste for mlcc - Google Patents
Conductive paste for mlcc Download PDFInfo
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- JP2009064603A JP2009064603A JP2007229759A JP2007229759A JP2009064603A JP 2009064603 A JP2009064603 A JP 2009064603A JP 2007229759 A JP2007229759 A JP 2007229759A JP 2007229759 A JP2007229759 A JP 2007229759A JP 2009064603 A JP2009064603 A JP 2009064603A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/26—Folded capacitors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G5/00—Capacitors in which the capacitance is varied by mechanical means, e.g. by turning a shaft; Processes of their manufacture
- H01G5/01—Details
- H01G5/011—Electrodes
Abstract
Description
本発明は金属微粒子を用いた導電性ペーストに関し、特に積層セラミックコンデンサ(ＭＬＣＣ)用の導電性ペーストに関する。 The present invention relates to a conductive paste using metal fine particles, and more particularly to a conductive paste for a multilayer ceramic capacitor (MLCC).
導電性ペーストは、プリント基板における電極、配線などの回路形成や層間接合に使用する導電材料として広く知られ、用いられている。そして、近年、プリント基板が組み込まれる電子機器は、高性能化、小型化され、それに伴って、配線回路は狭ピッチ化されて、導電性ペースト内に分散される金属微粒子の粒子径もナノメートルサイズの大きさ(以下、単にナノサイズということもある)のものが求められている。 Conductive paste is widely known and used as a conductive material used for forming circuits such as electrodes and wiring on printed circuit boards and interlayer bonding. In recent years, electronic devices incorporating printed circuit boards have been improved in performance and reduced in size, and accordingly, the wiring circuit has been narrowed in pitch, and the particle size of the metal fine particles dispersed in the conductive paste is also nanometers. There is a demand for a size (hereinafter sometimes simply referred to as nano-size).
従来、金属微粒子を製造する方法として、気相法と液相法が知られている。気相法は金属粒子の形状及び不純物の制御が比較的容易なことから広く使用されてきたが、粒子の微細化と大量生産の面では不都合があった。一方、液相法は、大量生産に適しており、製造設備の初期投資費用及び製造工程費用が低いという長所がある。 Conventionally, a gas phase method and a liquid phase method are known as methods for producing metal fine particles. The vapor phase method has been widely used because it is relatively easy to control the shape and impurities of the metal particles, but has a disadvantage in terms of particle miniaturization and mass production. On the other hand, the liquid phase method is suitable for mass production and has an advantage that the initial investment cost and the manufacturing process cost of the manufacturing equipment are low.
最近の液相法によるナノサイズの粒径をもつ金属微粒子の製造方法として、特許文献１に示すものが知られている。この製造技術は、金属塩を溶解した溶液に所定時間マイクロ波を照射することによって、短時間の内にナノサイズの超微粒子を製造するようにしたものである。この方法では、数nm〜10数nmの粒径範囲の金属微粒子を精度よく製造可能であるが、数十nm〜数百nmの粒径範囲の金属粒子を精度よく製造することは困難であった。 As a method for producing metal fine particles having a nano-sized particle diameter by a recent liquid phase method, the one shown in Patent Document 1 is known. In this production technique, nano-sized ultrafine particles are produced within a short time by irradiating a solution in which a metal salt is dissolved with microwaves for a predetermined time. In this method, metal fine particles having a particle size range of several nanometers to several tens of nanometers can be accurately manufactured, but it is difficult to accurately manufacture metal particles having a particle diameter range of several tens of nanometers to several hundred nanometers. It was.
さらに、有機溶媒中に金属超微粒子を分散させた導電性ペーストとして、例えば特許文献２に示すものが提案されている。特許文献２に示すものは、有機溶媒に金属超微粒子を分散してなる導電性ペーストであって、脂肪酸金属塩またはアルキルスルホン酸金属塩に由来する金属成分から構成された金属コアと、金属コアの周囲を覆う表面修飾剤がその金属塩に由来する有機成分であり、有機溶媒中には、金属塩に由来し、金属超微粒子の合成後に残存する有機成分を含むようにしてある。この方法では、金属コアの周囲を覆う有機成分が金属塩に由来することから、金属コアの周囲を覆う有機成分の種類が制限されるという課題がある。
ＭＬＣＣ用導電性ペーストの内部電極に使用される金属微粒子は、層間剥離やクラック、ワレ等の発生を抑える為に適した粒径がある。例えば、電極膜厚が厚い場合には平均粒径が小さい方が望ましく、電極膜厚が薄い場合には平均粒径が大きい方が望ましい。ところが、従来の製法では、数nm〜数百nmの粒径範囲内において、所定の粒径に精度よく粒径を揃えた金属微粒子を製造することが困難であった。また、金属微粒子の凝縮を抑える表面修飾剤が制限されてしまう問題もあった。 The metal fine particles used for the internal electrode of the conductive paste for MLCC have a particle size suitable for suppressing the occurrence of delamination, cracks, cracks and the like. For example, when the electrode film thickness is large, it is desirable that the average particle diameter is small, and when the electrode film thickness is thin, it is desirable that the average particle diameter is large. However, in the conventional manufacturing method, it has been difficult to produce metal fine particles having a predetermined particle size and a uniform particle size within a range of several nm to several hundred nm. There is also a problem that the surface modifier that suppresses the condensation of the metal fine particles is limited.
本発明はこのような点に鑑み、有機物の表面修飾剤で覆われた数nm〜数百nmの粒径範囲で粒径の揃った金属微粒子が有機溶媒に分散してなるＭＬＣＣ用導電性ペーストを提供することを目的とする。 In view of the above, the present invention is a conductive paste for MLCC in which metal fine particles having a uniform particle size in a particle size range of several nanometers to several hundred nanometers covered with an organic surface modifier are dispersed in an organic solvent. The purpose is to provide.
上述の目的を達成するために請求項１に記載した本発明は、マイクロ波を照射することによって生成したＮｉ微粒子であって、有機物の表面修飾剤により有機溶媒に高分散していることを特徴とするＮｉ微粒子を用いることを特徴とする。 In order to achieve the above object, the present invention described in claim 1 is characterized in that the Ni fine particles are produced by irradiating with microwaves and are highly dispersed in an organic solvent by an organic surface modifier. Ni fine particles to be used are used.
又、請求項２に記載した本発明は、請求項１に記載の発明での有機物の表面修飾剤で覆われたＮｉ微粒子の粒子径(ｒ)が２nm≦ｒ≦３００nmであることを特徴とし、請求項３に記載した発明は、請求項１又は２に記載の発明でのＮｉ微粒子の粒度分布が粒子径(ｒ)と標準偏差(σ)の比率で、０.０１≦σ／ｒ≦０.５の範囲内にあることを特徴としている。 The present invention described in claim 2 is characterized in that the particle diameter (r) of the Ni fine particles covered with the organic surface modifier in the invention described in claim 1 is 2 nm ≦ r ≦ 300 nm. In the invention described in claim 3, the particle size distribution of the Ni fine particles in the invention described in claim 1 or 2 is a ratio of the particle diameter (r) to the standard deviation (σ), and 0.01 ≦ σ / r ≦ It is characterized by being in the range of 0.5.
さらに、請求項４に記載した発明では、請求項１〜３のいずれかに記載の発明でのＮｉ微粒子が、Ｎｉ金属塩と還元剤と表面修飾剤とを有機溶媒に溶解させた溶液にマイクロ波照射を行い、Ｎｉ金属塩を還元することで均一な粒径を有するＮｉ微粒子を生成する加熱・還元工程と、前記加熱・還元工程にて生成したＮｉ微粒子を洗浄・分離することで有機溶媒からＮｉ微粒子を収集する収集工程と、前記収集工程で収集したＮｉ微粒子を有機溶媒に添加しＮｉ微粒子を混練し、導電性ペーストとする混練工程とからなる製造工程により生成されたことを特徴としている。 Furthermore, in the invention described in claim 4, the Ni fine particles in the invention of any one of claims 1 to 3 are added to a solution in which a Ni metal salt, a reducing agent, and a surface modifier are dissolved in an organic solvent. A heating / reduction process that generates Ni fine particles having a uniform particle size by reducing the Ni metal salt by performing wave irradiation, and an organic solvent by washing / separating the Ni fine particles generated in the heating / reduction process Produced by a manufacturing process consisting of a collecting step of collecting Ni fine particles from the mixture, and a kneading step of adding Ni fine particles collected in the collecting step to an organic solvent to knead Ni fine particles to form a conductive paste. Yes.
本発明では、有機物の表面修飾剤で表面が覆われた数nm〜数百nmの粒径範囲で粒径の揃ったＮｉ金属微粒子が有機溶媒に分散するＭＬＣＣ用導電性ペーストを得ることができる。 In the present invention, a conductive paste for MLCC in which Ni metal fine particles having a uniform particle size in a particle size range of several nanometers to several hundred nanometers covered with an organic surface modifier can be obtained in an organic solvent can be obtained. .
以下、本発明を発明の実施形態に基づき説明する。
本発明のＭＬＣＣ用導電性ペーストは、Ｎｉ金属塩と還元剤と表面修飾剤とを有機溶媒に溶解させた溶液にマイクロ波照射を行い、Ｎｉ金属塩を還元することでＮｉ微粒子を生成する加熱・還元工程と、前記加熱・還元工程にて生成したＮｉ微粒子を洗浄・分離することで有機溶媒からＮｉ収集する収集工程と、前記収集工程で収集したＮｉ微粒子を有機溶媒に添加しＮｉ微粒子が均一となるように混練し、導電性ペーストとする混練工程とからなる製造工程により生成される。
Hereinafter, the present invention will be described based on embodiments of the invention.
The conductive paste for MLCC of the present invention is a heating process in which a Ni metal salt, a reducing agent, and a surface modifier are dissolved in an organic solvent by irradiating them with microwaves to reduce the Ni metal salt to generate Ni fine particles. A collecting step for collecting Ni from an organic solvent by washing and separating the Ni fine particles generated in the heating and reducing step; and adding the Ni fine particles collected in the collecting step to the organic solvent to obtain Ni fine particles. It is produced by a production process comprising a kneading process in which the mixture is uniformly kneaded to form a conductive paste.
そして、加熱・還元工程で用いるＮｉ金属塩としては、有機溶媒に可溶な塩化ニッケル、硫酸ニッケル、硝酸ニッケル等が考えられる。 As the Ni metal salt used in the heating / reducing step, nickel chloride, nickel sulfate, nickel nitrate, etc. soluble in an organic solvent can be considered.
また、加熱・還元工程で用いる有機溶媒としては、プロパンジオール、ブタンジオール、ペンタンジオール、オクタノール、エチレングリコール、プロピレングリコール、ジエチレングリコール、トリエチレングリコール、ジプロピレグリコール、ヘキシレングリコールまたはブチレングリコール等のアルコール系溶媒やグリコール溶媒を用いることができる。 Moreover, as an organic solvent used in the heating / reduction step, alcoholic solvents such as propanediol, butanediol, pentanediol, octanol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, hexylene glycol or butylene glycol A solvent or a glycol solvent can be used.
加熱・還元工程で用いる還元剤としては、ヒドラジン、炭酸ヒドラジン、水素化ホウ素ナトリウム、水素化ホウ素リチウム、アミンボラン、亜ニチオン酸、ホルムアルデヒドスルホキシル酸ナトリウム、ホルムアルデヒドスルホキシル酸亜鉛、二酸化チオ尿素、次亜リン酸、次亜リン酸アルカリ、ハイドロサルファイト等から選択された1種又はこれらの2種以上を選択して用いることができる。 Examples of the reducing agent used in the heating / reduction process include hydrazine, hydrazine carbonate, sodium borohydride, lithium borohydride, amine borane, nitrous acid, sodium formaldehyde sulfoxylate, zinc formaldehyde sulfoxylate, thiourea, hypochlorous acid. One kind selected from phosphoric acid, alkali hypophosphite, hydrosulfite and the like, or two or more kinds thereof can be selected and used.
加熱・還元工程で用いる表面修飾剤としては、ＰＶＰ(ポリビニルピロリドン)、ポリエチレンイミン、ポリアクリルアミドなどの高分子樹脂、分子量としては２,０００から１０,０００が望ましく、ミリスチン酸、デカン酸、カプリル酸、パルミチン酸、リノール酸、リノレン酸、オレイン酸及びステアリン酸、コール酸 等などの長鎖カルボン酸またはステアリン酸ナトリウムなどの長鎖カルボン酸塩が望ましい。 The surface modifier used in the heating / reduction process is preferably a polymer resin such as PVP (polyvinylpyrrolidone), polyethyleneimine, or polyacrylamide. The molecular weight is preferably 2,000 to 10,000, and myristic acid, decanoic acid, caprylic acid. Long chain carboxylic acids such as palmitic acid, linoleic acid, linolenic acid, oleic acid and stearic acid, cholic acid and the like or long chain carboxylates such as sodium stearate are desirable.
加熱・還元工程でのマイクロ波による加熱は、その照射強度範囲として１０Ｗ〜２４５０Ｗ、照射時間が１分〜６０分の範囲で行うことが好ましい。 The heating by the microwave in the heating / reducing step is preferably performed in the irradiation intensity range of 10 W to 2450 W and the irradiation time of 1 minute to 60 minutes.
収集工程では、加熱・還元工程で生成したＮｉ微粒子を遠心分離機により有機溶媒から分離し、その後メタノール等を用いてＮｉ微粒子に付着している不純物を洗い流す。 In the collecting step, the Ni fine particles generated in the heating / reducing step are separated from the organic solvent by a centrifuge, and then impurities adhering to the Ni fine particles are washed away using methanol or the like.
さらに、混練工程で用いる有機溶媒としては、テルピネオール、デカノール、ヘキサノール、メタノール、エタノール、エチルカルビトール、ブチルカルビトール、ジオール類、グリコール類、ポリオール類などのアルコール類、ジメチルホルムアミド(ＤＭＦ)、Ｎ−メチル−２−ピロリドン(ＮＭＰ)などのアミン類、ヘキサン、トルエン、キシレン、オクタン、デカン、ウンデカン、テトラデカンなどの炭化水素類、メチルエチルケトン(ＭＥＫ)、メチルイソブチルケトンなどのケトン類、ジプロピレングリコールモノメチルエーテルなどのエーテル類、酢酸エチル、エチルカルビトールアセテート、ブチルカルビトールアセテートなどのエステル類を用いることができる。 Furthermore, as the organic solvent used in the kneading step, terpineol, decanol, hexanol, methanol, ethanol, ethyl carbitol, butyl carbitol, diols, glycols, polyols and other alcohols, dimethylformamide (DMF), N- Amines such as methyl-2-pyrrolidone (NMP), hydrocarbons such as hexane, toluene, xylene, octane, decane, undecane and tetradecane, ketones such as methyl ethyl ketone (MEK) and methyl isobutyl ketone, dipropylene glycol monomethyl ether And ethers such as ethyl acetate, ethyl carbitol acetate, and butyl carbitol acetate can be used.
本発明の導電性ペーストにおいて、混練するＮｉ微粒子と有機溶媒との重量比率は１：１〜１.１程度である。また、導電性ペーストの物性安定化や品質向上のために、有機バインダーや添加剤を加えることもできる。有機バインダーとしては、例えばエチルセルロースが挙げられる。また、添加剤としては、可塑剤、増粘防止剤、分散剤等が挙げられる。 In the conductive paste of the present invention, the weight ratio of the Ni fine particles to be kneaded and the organic solvent is about 1: 1 to 1.1. Moreover, an organic binder and an additive can also be added in order to stabilize the physical properties and improve the quality of the conductive paste. Examples of the organic binder include ethyl cellulose. Examples of the additive include a plasticizer, a thickening inhibitor, and a dispersant.
核発生粒子成長過程を通して生成する金属微粒子において、通常の加熱合成では熱伝導ならびに対流による影響により熱勾配が生じ、反応容器壁面と中心とでは粒子の生成・成長に差があるが、マイクロ波加熱では、電磁波の一種であるマイクロ波が被加熱物内に浸透し、誘電損失により発熱する内部加熱により急速な昇温且つ均一に加熱されることから、粒子の生成・成長の差が小さく粒径制御された単分散な金属微粒子が合成できる。 In the fine metal particles generated through the nucleation particle growth process, thermal gradients occur due to the effects of heat conduction and convection in normal heating synthesis, and there is a difference in the generation and growth of particles between the reaction vessel wall and the center. In this case, microwaves, which are a type of electromagnetic wave, penetrate into the object to be heated and are heated rapidly and uniformly by internal heating that generates heat due to dielectric loss, so the difference in particle generation and growth is small. Controlled monodisperse metal fine particles can be synthesized.
そして、本発明が適用しようとするＭＬＣＣ用の導電性ペーストに使用するＮｉ微粒子では、その粒子径としては平均粒子径が２nm〜３００nmの粒径範囲内であることが望ましい。 The Ni fine particles used in the MLCC conductive paste to be applied by the present invention preferably have an average particle size in the range of 2 nm to 300 nm.
本発明で製造するＮｉ微粒子の粒径は数nm〜数百nmにわたるが、平均粒子径が数nm程度と小さいときは標準偏差の値が小さく、平均粒子径が数百nm程度まで大きくなると標準偏差の値も大きくなり、標準偏差(σ)のみでは粒子径に即した評価ができない。そこで異なる平均粒子径においても粒径分布の評価ができるようにする為に、単位平均粒径に対する標準偏差(σ)を平均粒子径(ｒ)で除するσ／ｒを使用することとした。 The particle size of the Ni fine particles produced in the present invention ranges from several nm to several hundreds of nm. When the average particle size is as small as several nm, the standard deviation value is small, and when the average particle size is large up to several hundred nm, it is standard. The value of the deviation also increases, and evaluation based on the particle diameter cannot be performed only with the standard deviation (σ). Therefore, in order to be able to evaluate the particle size distribution even at different average particle sizes, σ / r, which is obtained by dividing the standard deviation (σ) with respect to the unit average particle size by the average particle size (r), was used.
以下、研究室段階での実施例により本発明を具体的に説明するが、本発明はこれら実施例のみに限定されるものではない。 Hereinafter, the present invention will be specifically described by examples in the laboratory stage, but the present invention is not limited to these examples.
１００ml石英製丸底フラスコに塩化ニッケル６水和物２.３３ｇ(１８mmol)とポリビリルピロリドン(PVP)(Ｍｗ＝１０,０００)０.４ｇをエチレングリコール５０mlに加えて攪拌・溶解した後、水素化ホウ素ナトリウム１.３６ｇ(３６mmol)を添加し４００rpmで攪拌した。それを電子レンジ型マイクロ波反応装置(四国計測工業社製、ＭＩＣＲＯ ＲＡＮＧＥ−ＰＲＯ)にてマイクロ波照射により室温から１２０℃まで４５secで急速に加熱したのち、その温度で１０min保持した。なお温度の制御は、光ファイバー温度計(安立計器(株)社製「AMOTHTM-5886」)を用いて温度を測定しながらマイクロ波照射出力を制御しながら、反応を行った。得られた反応溶液を冷却した後、久保田製作所社製遠心機(ＫＵＢＯＴＡ６９３０)を用いて１５,０００ＧによりＮｉ微粒子粉体とエチレングリコール溶媒を分離した。同様に５０mlメタノールを用いて洗浄を２回実施し、Ｎｉ微粒子粉体と不純物を除去した。得られた黒色粉体を真空乾燥装置で４０℃に加熱乾燥して、Ｎｉ微粒子粉体を取り出した。 In a 100 ml quartz round bottom flask, 2.33 g (18 mmol) of nickel chloride hexahydrate and 0.4 g of polybilylpyrrolidone (PVP) (Mw = 10,000) were added to 50 ml of ethylene glycol and stirred and dissolved. 1.36 g (36 mmol) of sodium borohydride was added and stirred at 400 rpm. This was rapidly heated from room temperature to 120 ° C. in 45 seconds by microwave irradiation in a microwave oven type microwave reactor (MICRO RANGE-PRO, manufactured by Shikoku Keiki Kogyo Co., Ltd.), and held at that temperature for 10 minutes. The temperature was controlled by measuring the temperature using an optical fiber thermometer (“AMOTHTM-5886” manufactured by Anritsu Keiki Co., Ltd.) while controlling the microwave irradiation output. After cooling the obtained reaction solution, the Ni fine particle powder and the ethylene glycol solvent were separated by 15,000 G using a centrifuge (KUBOTA 6930) manufactured by Kubota Corporation. Similarly, washing was performed twice using 50 ml of methanol to remove Ni fine particle powder and impurities. The obtained black powder was dried by heating at 40 ° C. with a vacuum dryer, and the Ni fine particle powder was taken out.
（評価結果）
（Ｎｉ微粒子の同定）
得られたＮｉ微粒子の同定をＸ線回折(ＸＲＤ)(理学電気(株)社製、MultiFlex)により評価した。
Ｘ線解析の回折角度(２θ)＝４４.７°、５２.５°、７６.６°にそれぞれニッケルの(１１１)、(２００)、(２２０)面のピークを有することより、得られた粉体が面心立方構造(face-centered cubic(fcc))を有するＮｉ微粒子であることが確認され、ニッケル酸化物は確認されなかった。このＸ線回折図を図１に表す。
(Evaluation results)
(Identification of Ni fine particles)
Identification of the obtained Ni fine particles was evaluated by X-ray diffraction (XRD) (manufactured by Rigaku Corporation, MultiFlex).
X-ray analysis diffraction angle (2θ) = 44.7 °, 52.5 °, and 76.6 °, respectively having nickel (111), (200), (220) plane peaks. The powder was confirmed to be Ni fine particles having a face-centered cubic (fcc), and nickel oxide was not confirmed. This X-ray diffraction diagram is shown in FIG.
（表面修飾剤の量及びＮｉ微粒子の収率）
Ｎｉ微粒子に修飾されている表面修飾剤の量は、熱重量測定(島津社製ＴＧＡ−５０)により評価を行った。１０ｍｇのＮｉ微粒子を窒素雰囲気下(５０ml/min)、昇温速度１０℃／minで２０℃から６００℃まで、操作し、熱重量変化を調べたところ、約２４％の重量減少が確認された。
この熱重量測定図を図２に表す。
(Amount of surface modifier and yield of Ni fine particles)
The amount of the surface modifier modified with the Ni fine particles was evaluated by thermogravimetry (TGA-50 manufactured by Shimadzu Corporation). When 10 mg of Ni fine particles were operated from 20 ° C. to 600 ° C. under a nitrogen atmosphere (50 ml / min) at a rate of temperature increase of 10 ° C./min, and the thermogravimetric change was examined, a weight loss of about 24% was confirmed. .
This thermogravimetric diagram is shown in FIG.
（Ｎｉ微粒子形状）
得られたＮｉ微粒子粉体の形状をヘキサン・メタノール溶媒に分散した後、エラスティックカーボン支持体を貼った銅グリッドに滴下し、減圧乾燥したものを透過型電子顕微鏡((株)日立ハイテクノロジーズ社製、日立透過型電子顕微鏡H-9000)にて観察した。
観察試料のＴＥＭ像を図３に示す。
尚、図３のＴＥＭ像より見積もられたＮｉ微粒子の粒径を表１に示す。
(Ni fine particle shape)
After the shape of the obtained Ni fine particle powder was dispersed in a hexane / methanol solvent, it was dropped on a copper grid with an elastic carbon support and dried under reduced pressure to obtain a transmission electron microscope (Hitachi High-Technologies Corporation). Manufactured by Hitachi Transmission Electron Microscope H-9000).
A TEM image of the observation sample is shown in FIG.
Table 1 shows the particle diameter of the Ni fine particles estimated from the TEM image of FIG.
又、図３のＴＥＭ画像より７６８個カウントし粒径を計測した。粒子径に対する出現頻度を図４に示す。
この結果、平均粒子径(ｒ)が５.６nm、標準偏差(σ)が１.８７nmで粒子径に対する標準偏差(σ／r)は０.３３であった。
Further, 768 particles were counted from the TEM image in FIG. The appearance frequency with respect to the particle diameter is shown in FIG.
As a result, the average particle size (r) was 5.6 nm, the standard deviation (σ) was 1.87 nm, and the standard deviation (σ / r) with respect to the particle size was 0.33.
５００ml石英製丸底フラスコに硫酸ニッケル六水和物２.３７ｇ(９mmol)をエチレングリコール１２０mlに加えて攪拌・溶解した後、ヒドラジン一水和物２.８８ｇ(９０mmol)を添加し室温で３０min、４００rpmで攪拌した。得られた桃色溶液に１０mlのイオン交換水に溶解させた水酸化ナトリウム１.５ｇ(３７.５mmol)水溶液を滴下したのち１０分間室温で攪拌した。それを電子レンジ型マイクロ波反応装置(四国計測工業社製、ＭＩＣＲＯ ＲＡＮＧＥ−ＰＲＯ)にてマイクロ波照射により室温から１２０℃まで４５secで急速に加熱したのち、その温度で３０min保持した。得られたＮｉ微粒子粉体は実施例１と同様に洗浄したのち評価を行った。評価結果、Ｘ線回折図およびＴＥＭ像をそれぞれ表１、図５、図６に示す。 To a 500 ml quartz round bottom flask, 2.37 g (9 mmol) of nickel sulfate hexahydrate was added to 120 ml of ethylene glycol, stirred and dissolved, then 2.88 g (90 mmol) of hydrazine monohydrate was added, and 30 minutes at room temperature. Stir at 400 rpm. An aqueous solution of 1.5 g (37.5 mmol) of sodium hydroxide dissolved in 10 ml of ion-exchanged water was added dropwise to the resulting pink solution, and the mixture was stirred for 10 minutes at room temperature. It was rapidly heated from room temperature to 120 ° C. by microwave irradiation in a microwave oven type microwave reactor (MICRO RANGE-PRO, manufactured by Shikoku Keiki Kogyo Co., Ltd.) in 45 seconds, and held at that temperature for 30 minutes. The obtained Ni fine particle powder was washed and evaluated in the same manner as in Example 1. The evaluation results, X-ray diffraction patterns and TEM images are shown in Table 1, FIG. 5 and FIG. 6, respectively.
硫酸ニッケル六水和物をステアリン酸ニッケルとして用いた以外は実施例２と同様な方法で行った。評価結果及びＴＥＭ像をそれぞれ表１、図７に示す。 The same procedure as in Example 2 was performed except that nickel sulfate hexahydrate was used as nickel stearate. The evaluation results and TEM images are shown in Table 1 and FIG. 7, respectively.
５００ml石英製丸底フラスコに硫酸ニッケル六水和物２.３７ｇ(９mmol)とポリビリルピロリドン(PVP)(Ｍｗ＝１０,０００)０.８ｇをエチレングリコール１２０mlに加えて攪拌・溶解した後、ヒドラジン一水和物２.８８ｇ(９０mmol)を添加し室温で３０min、４００rpmで攪拌した。その後の操作は実施例３と同様な方法で行った。評価結果及びＴＥＭ像をそれぞれ表１、図８に示す。 In a 500 ml quartz round bottom flask, 2.37 g (9 mmol) of nickel sulfate hexahydrate and 0.8 g of polybilylpyrrolidone (PVP) (Mw = 10,000) were added to 120 ml of ethylene glycol, stirred and dissolved, and then hydrazine. 2.88 g (90 mmol) of monohydrate was added and stirred at room temperature for 30 min and 400 rpm. Subsequent operations were performed in the same manner as in Example 3. The evaluation results and TEM images are shown in Table 1 and FIG.
５００ml石英製丸底フラスコに硫酸ニッケル六水和物２.３７ｇ(９mmol)とコール酸７.３５ｇ(１８mmol)をエチレングリコール１２０mlに加えて攪拌・溶解した後、ヒドラジン一水和物２.８８ｇ(９０mmol)を添加し室温で３０min、４００rpmで攪拌した。その後の操作は実施例３と同様な方法で行った。評価結果及びＴＥＭ像をそれぞれ表１、図９に示す。 In a 500 ml quartz round bottom flask, 2.37 g (9 mmol) of nickel sulfate hexahydrate and 7.35 g (18 mmol) of cholic acid were added to 120 ml of ethylene glycol, stirred and dissolved, and then 2.88 g of hydrazine monohydrate ( 90 mmol) was added and stirred at room temperature for 30 min and 400 rpm. Subsequent operations were performed in the same manner as in Example 3. The evaluation results and TEM images are shown in Table 1 and FIG.
又、図３のＴＥＭ画像より３３サンプルを抽出しその粒子径を計測した。粒子径に対する出現頻度を図１０に示す。
この結果、平均粒子径(ｒ)が２６０nm、標準偏差(σ)が３３.４nmで粒子径に対する標準偏差(σ／ｒ)は０.１３であった。
Moreover, 33 samples were extracted from the TEM image of FIG. 3 and the particle diameter was measured. The appearance frequency with respect to the particle diameter is shown in FIG.
As a result, the average particle size (r) was 260 nm, the standard deviation (σ) was 33.4 nm, and the standard deviation (σ / r) with respect to the particle size was 0.13.
実施例１及び５の粒度分布から、平均粒子径が５nm程度と小さい時には、標準偏差の値は小さいが、平均粒子径が２６０nm程度まで大きくなると、標準偏差の値も大きくなる。
そこで、単位平均粒径に対する標準偏差を求めると、前記したように、０.３３と０.１３となる。平均粒子径が２６０nmで単位平均粒径に対する標準偏差が０.４とすると、２６０±１００nm程度の分布となることから、Ｎｉ微粒子の粒度分布が粒子径(ｒ)と標準偏差(σ)の比率で、０.０１≦σ／ｒ≦０.５の範囲内にあることが望ましい。
[比較例１]
From the particle size distributions of Examples 1 and 5, when the average particle size is as small as about 5 nm, the standard deviation value is small, but when the average particle size is increased up to about 260 nm, the standard deviation value becomes large.
Therefore, when the standard deviation with respect to the unit average particle diameter is obtained, as described above, they are 0.33 and 0.13. If the average particle size is 260 nm and the standard deviation with respect to the unit average particle size is 0.4, the distribution is about 260 ± 100 nm, so the Ni particle size distribution is the ratio of the particle size (r) to the standard deviation (σ). Therefore, it is desirable to be within the range of 0.01 ≦ σ / r ≦ 0.5.
[Comparative Example 1]
１００ml石英製丸底フラスコに塩化ニッケル６水和物２.３３ｇ(１８mmol)をエチレングリコール５０mlに加えて攪拌・溶解した後、水素化ホウ素ナトリウム１.３６ｇ(３６mmol)を添加し、７０℃のオイルバスにおいて４００rpmで３０min攪拌した。得られたＮｉ微粒子粉体は実施例１と同様に洗浄したのち評価を行った。評価結果、Ｘ線回折図及びＴＥＭ像をそれぞれ表１、図１１、図１２に示す。 To a 100 ml quartz round bottom flask, 2.33 g (18 mmol) of nickel chloride hexahydrate was added to 50 ml of ethylene glycol, stirred and dissolved, then 1.36 g (36 mmol) of sodium borohydride was added, and an oil at 70 ° C. The mixture was stirred for 30 minutes at 400 rpm in a bath. The obtained Ni fine particle powder was washed and evaluated in the same manner as in Example 1. The evaluation results, X-ray diffraction diagrams and TEM images are shown in Table 1, FIG. 11 and FIG. 12, respectively.
本発明は、積層セラミックコンデンサに使用することができる。 The present invention can be used for multilayer ceramic capacitors.
Claims (4)
ａ．Ｎｉ金属塩と還元剤と表面修飾剤とを有機溶媒に溶解させた溶液にマイクロ波照射を行い、Ｎｉ金属塩を還元することで均一な粒径を有するＮｉ微粒子を生成する加熱・還元工程。、
ｂ．前記加熱・還元工程にて生成したＮｉ微粒子を洗浄・分離することで有機溶媒からＮｉ微粒子を収集する収集工程。
ｃ．前記収集工程で収集したＮｉ微粒子を有機溶媒に添加しＮｉ微粒子を混練し、導電性ペーストとする混練工程。 4. The MLCC conductive paste according to claim 1, wherein the Ni fine particles are generated by the following three steps.
a. A heating / reduction process in which a Ni metal salt, a reducing agent and a surface modifier dissolved in an organic solvent are irradiated with microwaves to reduce the Ni metal salt to produce Ni fine particles having a uniform particle size. ,
b. A collecting step of collecting Ni fine particles from the organic solvent by washing and separating the Ni fine particles generated in the heating / reducing step.
c. A kneading step in which the Ni fine particles collected in the collecting step are added to an organic solvent to knead the Ni fine particles to obtain a conductive paste.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2011137226A (en) * | 2009-12-05 | 2011-07-14 | National Institute Of Advanced Industrial Science & Technology | Method for producing metal particulate |
| JP2013184830A (en) * | 2012-03-06 | 2013-09-19 | Nippon Steel & Sumikin Chemical Co Ltd | Surface-modified metal oxide nanoparticle and method for producing the same |
| WO2016129686A1 (en) * | 2015-02-13 | 2016-08-18 | 株式会社カネカ | Solar cell, method for manufacturing same, and solar cell module |
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|---|---|---|---|---|
| JP2000256707A (en) * | 1999-03-05 | 2000-09-19 | Univ Osaka | Production of hyperfine particle and hyperfine particle |
| JP2001167631A (en) * | 1999-12-07 | 2001-06-22 | Sumitomo Metal Mining Co Ltd | Ultra-fine particle conductor paste, method of preparing the same, and conductor film and laminated ceramic electronic parts using the same |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000256707A (en) * | 1999-03-05 | 2000-09-19 | Univ Osaka | Production of hyperfine particle and hyperfine particle |
| JP2001167631A (en) * | 1999-12-07 | 2001-06-22 | Sumitomo Metal Mining Co Ltd | Ultra-fine particle conductor paste, method of preparing the same, and conductor film and laminated ceramic electronic parts using the same |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011137226A (en) * | 2009-12-05 | 2011-07-14 | National Institute Of Advanced Industrial Science & Technology | Method for producing metal particulate |
| JP2013184830A (en) * | 2012-03-06 | 2013-09-19 | Nippon Steel & Sumikin Chemical Co Ltd | Surface-modified metal oxide nanoparticle and method for producing the same |
| WO2016129686A1 (en) * | 2015-02-13 | 2016-08-18 | 株式会社カネカ | Solar cell, method for manufacturing same, and solar cell module |
| JPWO2016129686A1 (en) * | 2015-02-13 | 2017-11-24 | 株式会社カネカ | SOLAR CELL, MANUFACTURING METHOD THEREOF, AND SOLAR CELL MODULE |
| CN107408583A (en) * | 2015-02-13 | 2017-11-28 | 株式会社钟化 | Solar cell and its manufacture method and solar cell module |
| CN107408583B (en) * | 2015-02-13 | 2019-09-03 | 株式会社钟化 | Solar battery and its manufacturing method and solar cell module |
| US10522704B2 (en) | 2015-02-13 | 2019-12-31 | Kaneka Corporation | Solar cell, method for manufacturing same |
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