JP4854240B2 - Ultrafine particles by pressure vibration and spray granulation - Google Patents
Ultrafine particles by pressure vibration and spray granulation Download PDFInfo
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Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
Description
本発明は、ニッケル水素電池（Ｎｉ-ｍＨ）のような電池、セラミックコンデンサや電気二重層キャパシタのような電子部品用、医薬用、触媒用等の球状単体金属、球状活性炭、球状多孔質シリカ、プリンター用球状各種トナー等のような球状超微粒子原料を無粉砕で調製可能な微粒子の形状とその製法に関し、又、本発明の応用展開として、無粉砕で薄状、鱗片状の超微粒子の提供も可能にするものである。 The present invention relates to a battery such as a nickel metal hydride battery (Ni-mH), a spherical simple metal such as a ceramic capacitor or an electric double layer capacitor such as a ceramic capacitor or an electric double layer capacitor, a pharmaceutical or a catalyst, a spherical activated carbon, a spherical porous silica, Spherical ultrafine particle raw materials such as various toners for printers can be prepared without pulverization and the production method thereof, and as an application development of the present invention, provision of non-pulverized thin and scale-like ultrafine particles Is also possible.
従来の技術は、球状粒子を形成する原料の融点により製法が異なっている。半田等の金属球状粉末や多孔質シリカゲルの球状粒子は、半田では、２８０℃〜３３０℃の温度で、シリカゲルではアルカリリッチの低軟化点ガラスを７００℃〜９００℃の温度で、耐熱性のスプレーノズルを用いて、雰囲気制御を行い噴霧方式で生産されている。 The conventional technique differs in the production method depending on the melting point of the raw material for forming the spherical particles. Metal spherical powder such as solder and spherical particles of porous silica gel are heat resistant sprays at a temperature of 280 ° C. to 330 ° C. for solder, and an alkali-rich low softening point glass at a temperature of 700 ° C. to 900 ° C. for silica gel. The nozzle is used to control the atmosphere and is produced by a spray method.
また、フェノール樹脂の球状粒子は、カネボウ（株）製のベルパールＳや群栄化学工業（株）製のマリリンＨＦ−０５０Ｗが市販されている。これらの製法は、レゾール樹脂とホルマリンのようなアルデヒドを乳化重合する工程で高速回転させ微粒化重合している。しかし、特開２００３−２０３８２９号公報には、これらの粒状粒子の大きさは、３０μｍ〜５００μｍの大きな粒子のため３〜８μｍの実用粒径まで再粉砕してから、電子部品材料に用いられる。また、特開平１１−１３１４では、フェノール樹脂にセルロース誘導体と溶媒を混合させ、相互に層分離させ、フェノール樹脂を硬化させ、その後、溶媒、セルロースを除去する方法が提案されている。この方法は、工程が複雑で、かつ、樹脂の微粒化工程が記載されず、何故、微粒化粒子の形成が可能になるかが明確でない。
このように粒子径が９μｍ以下の超微粒子を無粉砕で、製造する方法は、現在迄に提案及び実用化されていないのが現状である。
As for the spherical particles of the phenol resin, Bell Pearl S manufactured by Kanebo Co., Ltd. and Marilyn HF-050W manufactured by Gunei Chemical Industry Co., Ltd. are commercially available. In these production methods, a resol resin and an aldehyde such as formalin are rotated and polymerized at a high speed in a step of emulsion polymerization. However, according to Japanese Patent Application Laid-Open No. 2003-203829, these granular particles are large particles of 30 μm to 500 μm, and are used for electronic component materials after being pulverized to a practical particle size of 3 to 8 μm. Japanese Patent Laid-Open No. 11-1314 proposes a method in which a phenol derivative is mixed with a cellulose derivative and a solvent, the layers are separated from each other, the phenol resin is cured, and then the solvent and cellulose are removed. In this method, the process is complicated, and the resin atomization process is not described, and it is not clear why the formation of atomized particles is possible.
Thus, the present method has not been proposed and put to practical use so far for producing ultrafine particles having a particle diameter of 9 μm or less without pulverization.
現在、市販の活性炭を例に挙げると平均粒径が５〜１０μm粒子で粉砕分級コストは３０％で、３〜５μｍの粒子サイズでは粉砕分級価格が活性炭価格の５０％を占めている。また、活性炭は、非常に活性を有するため粉砕分級工程で雰囲気中のガス成分を吸着したり、表面酸化を受け不活性に成る場合が少なくない。 In the case of commercially available activated carbon, for example, the average particle size is 5 to 10 μm and the pulverization classification cost is 30%. For the particle size of 3 to 5 μm, the pulverization classification price accounts for 50% of the activated carbon price. In addition, activated carbon is very active, and therefore, in many cases, the activated carbon adsorbs gas components in the atmosphere in the pulverization classification process or becomes inactive due to surface oxidation.
単体金属、合金、ガラス及び有機化合物のような融点を有する物質をその融点以上の温度で、スプレーノズルで微粒化する従来の方法は、物質の物性にも依存するが、通常、量産に成功している粒子径は数ｍｍのものが大部分で、１００μｍ〜５００μｍの粒子径は、実験室レベルが現状である。従って、１０μｍ以下の粒子を無粉砕で量産する方法は未開発であった。また、高温スプレーノズル方法は、ノズルの磨耗と腐食が激しく、製造した粒子径が大きく、粒度分布の分布幅が大きく、設定範囲内の粒度分布を有する粒子を製造することは、篩別機を使用しても、極めて困難であった。特に、１００〜１０００ｎｍオーダーの球状粉粒体は、工業的粉砕機、篩別機ともに未開発の状態である。
また、上記の従来例で、第２、第３物質を用いて、乳化重合時に高速回転し、微粒化粒子を得る方法も工程が複雑で、不純物の除去が困難で、また、粉砕工程を経ないと微粒化は、困難であった。
Conventional methods of atomizing substances with melting points such as single metals, alloys, glass and organic compounds at temperatures above the melting point with spray nozzles usually depend on the physical properties of the substances, but are usually successful in mass production. Most of the particle diameters are several millimeters, and the particle diameters of 100 μm to 500 μm are currently at the laboratory level. Therefore, a method for mass-producing particles of 10 μm or less without pulverization has not been developed. In addition, the high temperature spray nozzle method has severe nozzle wear and corrosion, the produced particle size is large, the particle size distribution width is large, and particles having a particle size distribution within the set range are produced by using a sieving machine. Even when used, it was extremely difficult. In particular, spherical powders of the order of 100 to 1000 nm are in an undeveloped state for both industrial pulverizers and sieving machines.
Further, in the above conventional example, the method of obtaining the atomized particles by using the second and third substances and rotating at high speed during the emulsion polymerization is complicated, and it is difficult to remove impurities. Otherwise, atomization was difficult.
本発明は、これらの従来の課題を解決し、以下の特性改善を目標とする。１）無粉砕で球状及び鱗片状の超微粒子を得る。２）篩別工程無しに、シャープな球形粒度分布を有する球状超微粒子を得る。３）極めて真円に近似した球状超微粒子を得る。粒子径が目的用途により、１００ｎｍ〜５００００ｎｍ、４）低コストでの工業的生産を可能にする。 The present invention solves these conventional problems and aims to improve the following characteristics. 1) Spherical and scale-like ultrafine particles are obtained without grinding. 2) Spherical ultrafine particles having a sharp spherical particle size distribution are obtained without a sieving step. 3) Spherical ultrafine particles very close to a perfect circle are obtained. Depending on the intended use, the particle size is 100 nm to 50000 nm, and 4) enables low-cost industrial production.
尚、本発明の超微粒子の真円度とは、電子顕微鏡画像上の粒子の投影断面積に等しい円の周長を粒子の投影輪郭長で除した値として定義される。また、真円度の精度上、１００〜１５０個の粒子の計測の平均値を示すものである。 The roundness of the ultrafine particles of the present invention is defined as a value obtained by dividing the circumference of a circle equal to the projected sectional area of the particle on the electron microscope image by the projected contour length of the particle. Moreover, the average value of the measurement of 100-150 particle | grains is shown on the precision of roundness.
本発明の課題解決の手段として、特殊な貫通孔と貫通孔密度を有する基盤をノズルに用いることを特徴としている。この基盤ノズルは、貫通孔の穴径が０．０５μｍ〜５０μｍで、貫通孔のアスペクト比（穴径と貫通孔の長さの比）が、５〜２００で有し、貫通孔の密度が１００〜７０００個／ｃｍ2の貫通孔密度を有する基盤をノズルに用いる。 As a means for solving the problems of the present invention, a substrate having a special through hole and a through hole density is used for the nozzle. This base nozzle has a through hole having a hole diameter of 0.05 μm to 50 μm, an aspect ratio of the through hole (ratio of the hole diameter to the length of the through hole) of 5 to 200, and the density of the through holes is 100. A substrate having a through hole density of ˜7000 / cm 2 is used for the nozzle.
本発明では、この多数の貫通孔を有する基盤ノズルを圧電素子やモーター駆動により周期的に微振動させ、粉末原料からなる液状のスラリー状物質を多数の貫通孔を有するノズル開孔部で、定量的に、周期的にスラリーを切断し、球状の液滴とし、その後、乾燥、還元、酸化、熱処理、炭化、活性炭化等の工程を経る製造方法により、無粉砕で、目的の球状超微粒子を得ることができる。 In the present invention, the base nozzle having a large number of through holes is periodically vibrated by a piezoelectric element or a motor to quantitatively measure a liquid slurry-like substance made of a powder raw material at a nozzle opening portion having a large number of through holes. In addition, the slurry is periodically cut into spherical droplets, and then the desired spherical ultrafine particles are obtained without pulverization by a production method through processes such as drying, reduction, oxidation, heat treatment, carbonization, and activated carbonization. Obtainable.
なお、特に、本発明は、単位時間当たりの量産性を高め、品質の向上を図るため加圧下で振動を行い高粘度原料を高速度で噴射造粒を可能にする方法を提案するものである。さらに、本発明は、その工程中、必要に応じて、噴射造粒部に、外部電源を用いてコロナ放電により、印荷（直接または誘導荷電）させ、ノズルから噴出された霧化粒子には、荷電され、粒子相互が再結合しないように構成するのもその特徴の一つである。 In particular, the present invention proposes a method that enables high-speed injection granulation of a high-viscosity raw material by vibrating under pressure in order to increase mass productivity per unit time and improve quality. . Further, according to the present invention, during the process, if necessary, the spray granulation unit is subjected to imprinting (direct or induction charging) by corona discharge using an external power source, and the atomized particles ejected from the nozzle One of the features is that the particles are charged so that the particles do not recombine with each other.
本発明は、本文明細書に記載のように、高粘度原料溶液を用いて、加圧振動及び噴射造粒する製造することより、５０μｍ以下の超微粒子を無粉砕で高効率に工業的に生産可能な方法を提供し、なおかつ、目的用途により、真円度が低い粒子（ディンプル、表面凹凸、突起等）が求められたり、鱗片状の形状が求められる工業的用途にも柔軟に対応可能な工業的生産方法を提供するものである。さらに、本発明が開示する製造方法は、低コストでの工業生産が可能で、来るべき次世代のナノテク時代に最適の材料生産技術を提供可能な工業的価値、極めて大なるものである。 As described in this specification, the present invention industrially produces ultrafine particles of 50 μm or less without pulverization and high efficiency by producing a high-viscosity raw material solution using pressure vibration and spray granulation. Possible methods, and can be flexibly adapted to industrial applications where particles with low roundness (dimples, surface irregularities, protrusions, etc.) are required or scale-like shapes are required depending on the intended application An industrial production method is provided. Furthermore, the manufacturing method disclosed in the present invention is extremely large in industrial value that can provide industrial production at a low cost and can provide an optimum material production technique in the next generation nanotechnology era.
本発明の効果を更に高めるためにメッシュノズル部を弾性体を介して、貯液槽と接合させる。弾性体は、金属性箔体からなるダイヤフラムや耐熱耐薬品性の合成ゴム等で構成するのが好ましい。 In order to further enhance the effects of the present invention, the mesh nozzle portion is joined to the liquid storage tank via an elastic body. The elastic body is preferably composed of a diaphragm made of a metallic foil, a heat-resistant and chemical-resistant synthetic rubber, or the like.
本発明で使用する多数の貫通孔を有するノズルの製法は、基本的には電鋳法で生産される。貫通孔の穴径は、０．０５μｍ〜５０μｍが好ましい。０．０５μｍ以下は、量産性が悪く、５μｍ以上では、強度が必要になる。アスペクト比は、５〜２００が好ましい。
アスペクト比が５以下では、真円度が低下する。アスペクト比が２００以上は、ノズルの加工が困難でコスト高となる。工業的量産を配慮するとアスペクト比は、５〜２００が好ましい。また、ノズルの穴密度は、量産効果を勘案すると１００〜７０００個／ｃｍ2が好ましい。
The method for producing a nozzle having a large number of through holes used in the present invention is basically produced by electroforming. The diameter of the through hole is preferably 0.05 μm to 50 μm. If it is 0.05 μm or less, mass productivity is poor, and if it is 5 μm or more, strength is required. The aspect ratio is preferably 5 to 200.
When the aspect ratio is 5 or less, the roundness decreases. When the aspect ratio is 200 or more, it is difficult to process the nozzle and the cost becomes high. In consideration of industrial mass production, the aspect ratio is preferably 5 to 200. Further, the hole density of the nozzle is preferably 100 to 7000 / cm 2 considering the mass production effect.
ノズルの基盤の材質は、ニッケル、ニッケル基合金、チタン、タンタルのような弁作用金属及びその合金及び白金族、白金族基合金、炭素材料、ＳｉＣ等で構成することが好ましい。量産性とコストを考慮するとニッケル、ニッケル基合金、チタン、タンタルのような弁作用金属及びその合金及び白金族、白金族基合金、炭素材料等が経済的である。 The material of the nozzle base is preferably made of a valve action metal such as nickel, nickel-base alloy, titanium or tantalum and alloys thereof, platinum group, platinum group base alloy, carbon material, SiC, or the like. Considering mass productivity and cost, valve action metals such as nickel, nickel-base alloys, titanium, and tantalum and alloys thereof, and platinum groups, platinum group alloys, carbon materials, and the like are economical.
本発明が応用可能な材料は、有機物、無機物、セラミックス及びこれらのスラリー状の液状物が本発明の原料材料である。これらの諸材料を多数の貫通孔を有するノズルを通過させ、その後、所定の粒子に無粉砕で加工する。 The materials to which the present invention can be applied are organic materials, inorganic materials, ceramics, and these slurry-like liquid materials. These materials are passed through a nozzle having a large number of through holes, and then processed into predetermined particles without pulverization.
本発明では、これらのスラリー状の液状物をチタン酸バリウムやＰＺＴ等を使用した超音波振動子やモーター駆動で、定速度で、加圧下で圧送されたスラリー状液状物を一定間隔で切断し、超微粒子を形成させる。この工程の高効率化を図る目的で、すなわち、定速度振動の効率化を図るため、弾性体を介して、多孔体からなるノズルを接合することを特徴としている。この弾性体として、金属から成るダイヤフラムを用いることが好ましい。 In the present invention, these slurry-like liquid materials are cut at regular intervals by slurry-like liquid materials fed under pressure at a constant speed by an ultrasonic vibrator or motor drive using barium titanate, PZT or the like. To form ultrafine particles. For the purpose of improving the efficiency of this process, that is, in order to improve the efficiency of constant speed vibration, a nozzle made of a porous body is joined through an elastic body. It is preferable to use a metal diaphragm as the elastic body.
本発明で、上記のノズルは、外部電源で、４００〜５０００Ｖの電圧でコロナ放電により印荷され、ノズルから定量的に切断された球状粒子は、荷電されているために相互に再結合することなく次の工程である乾燥、焼成、還元、炭化、賦活等の工程に進行する。 In the present invention, the above-mentioned nozzle is externally powered and charged by corona discharge at a voltage of 400 to 5000 V, and the spherical particles quantitatively cut from the nozzle are recharged because they are charged. Without proceeding to the next step such as drying, firing, reduction, carbonization, activation and the like.
本発明で使用する熱硬化性樹脂は、フェノール樹脂、フリフラール樹脂、メラミン樹脂、尿素樹脂、エポキシ樹脂、アルキド樹脂、不飽和ポリエステル樹脂、シリコーン樹脂、キシレン樹脂、ウレタン樹脂等の単体または複合化された樹脂を使用する。超微粒子状の炭素を必要とする場合には、フェノール樹脂、フリフラール樹脂等の炭化収率の高いものを選択する。また、抵抗の低い炭素系超微粒子が必要な場合は、石油系タール、石炭系タール、ナフタレンピッチ、アンスラセンピツチを原料に用いる。 The thermosetting resin used in the present invention is a simple substance or a composite of phenol resin, furfural resin, melamine resin, urea resin, epoxy resin, alkyd resin, unsaturated polyester resin, silicone resin, xylene resin, urethane resin, etc. Use resin. When ultrafine carbon is required, one having a high carbonization yield such as phenol resin or furfural resin is selected. When carbon-based ultrafine particles with low resistance are required, petroleum-based tar, coal-based tar, naphthalene pitch, and anthracene pitch are used as raw materials.
これらの液状スラリーの粘度は、１５０〜３０００ｃｐが好ましいが、量産性を勘案すると１５０〜１０００ｃｐが大量生産に適合している。 The viscosity of these liquid slurries is preferably 150 to 3000 cp, but 150 to 1000 cp is suitable for mass production considering mass productivity.
本発明の主な目的は、球状超微粒子であるが、本発明で、霧化球状粒子を反応させる液層に界面活性剤を添加させる濃度により、球状〜卵状〜鱗片状に任意に形状を変化させることが可能である。この場合の界面活性剤は、非イオン及び両イオン界面活性剤、フッ素系界面活性剤を用いる。 The main object of the present invention is spherical ultrafine particles, but in the present invention, the shape can be arbitrarily formed into a spherical shape, an egg shape, or a scale shape depending on the concentration at which the surfactant is added to the liquid layer for reacting the atomized spherical particles. It is possible to change. As the surfactant in this case, nonionic and amphoteric surfactants and fluorosurfactants are used.
以下、本発明の実施の形態を下記の工程構成図により詳述する。 Hereinafter, embodiments of the present invention will be described in detail with reference to the following process configuration diagrams.
（実施例１ 本発明の主要工程図）
図１は本発明の加圧振動噴射造粒装置の概念図である。貯液タンク１は、加圧原料導入口２から加圧原料溶液（原料液Ａ）が加圧原料貯液槽３に貯液される。この加圧原料溶液は貯液タンク３に接合された弾性体ダイヤフラム４を通過して、貫通孔メッシュ６で、圧電振動体７の振動エネルギーにより、球状微粒化粒子１０となる。なお、弾性体４は、弾性体接合部５にて、貯液タンク１に固定されている。
(Example 1 main process diagram of the present invention)
FIG. 1 is a conceptual diagram of a pressurized vibration injection granulator of the present invention. In the liquid storage tank 1, the pressurized raw material solution (raw material liquid A) is stored in the pressurized raw material storage tank 3 from the pressurized raw material inlet 2. The pressurized raw material solution passes through the elastic diaphragm 4 joined to the liquid storage tank 3, and becomes spherical atomized particles 10 by the vibration energy of the piezoelectric vibrator 7 through the through-hole mesh 6. The elastic body 4 is fixed to the liquid storage tank 1 at the elastic body joint portion 5.
圧電振動部７は、電源８から原料溶液の濃度、粘度に応じて、数１００ＫＨｚの電圧が供給される。霧化粒子荷電部９（図２）で、コロナ放電により帯電粒子１１となり、霧化粒子１０が相互に凝集しないように帯電させる。 The piezoelectric vibration unit 7 is supplied with a voltage of several hundreds KHz from the power source 8 according to the concentration and viscosity of the raw material solution. In the atomized particle charging unit 9 (FIG. 2), charged particles 11 are formed by corona discharge and charged so that the atomized particles 10 do not aggregate with each other.
霧化粒子荷電部９を通過した帯電霧化粒子１１は、反応槽１２に導入され、反応溶液（Ｂ）は反応溶液導入口１３から反応槽１２に導入され、サイクロン式反応槽１４で反応し、反応貯液槽１５に貯液される。この反応液は、パイプ１６と、移送ポンプ１７及び移送パイプ１８で、次の工程に移送される。
The charged atomized particles 11 that have passed through the atomized particle charging unit 9 are introduced into the reaction vessel 12, and the reaction solution (B) is introduced into the reaction vessel 12 through the reaction solution inlet 13 and reacted in the cyclone reaction vessel 14. The liquid is stored in the reaction liquid storage tank 15. This reaction liquid is transferred to the next step by the pipe 16, the
反応槽１４はサイクロンの形状でなくても良いがこのような形状は、微粒子の均一化に効果的であつた。その理由は、原料液Ａの微粒子と反応液Ｂとの薄層の膜反応が均一反応を容易にさせるものと考えられる。図１には示されていないが、この後の工程は、先願の工程図のように固体と液体を分離し、固体球状粒子は、濾過工程、乾燥工程を経て、目的の球状超微粒子を得る。 The reaction vessel 14 does not have to be in the shape of a cyclone, but such a shape was effective for homogenizing fine particles. The reason is considered that the thin film reaction between the fine particles of the raw material liquid A and the reaction liquid B facilitates the uniform reaction. Although not shown in FIG. 1, in the subsequent process, the solid and liquid are separated as in the process chart of the prior application, and the solid spherical particles are subjected to a filtration process and a drying process to obtain the desired spherical ultrafine particles. obtain.
（実施例２）
本発明の荷電部（図１における荷電部９）を図２で荷電方法（絶縁槽の概念図）を詳細に説明する。絶縁体で構成された帯電層２１には電源２２から供給された高圧電源を帯電槽２１に部分埋設された対極２３と、絶縁シールド２４ａで周囲と絶縁され、且つ霧化粒子２５の中央部に設置されたコロナ放電先端部電極２４との間でコロナ放電を行い、霧化粒子２５をマイナスに帯電させる。電源は、原料の種類と粘度により変化するが、通常数１００ＫＶの荷電でコロナ放電を行うのが本発明では安全で、効果的である。
(Example 2)
The charging method (charging unit 9 in FIG. 1) of the present invention will be described in detail with reference to FIG. The charging layer 21 made of an insulator is insulated from the surroundings by a
（実施例３）
本発明の主要部のその他の概念図を図３に示す。圧送された原料溶液を、弾性体３５を介して接合された貫通孔を有するメッシュ３４を圧電素子３６の動力で加圧下で振動を与え、霧化し、微粒化を行う。圧電素子３６として、例えば、圧電セラミックス素子を使用することができる。この微粒子に電極２３及び２４によりコロナ放電により霧化粒子２５に帯電させる。尚、電極２３及び２４は、絶縁シールド２３ａ、２４ａで周囲に対してそれぞれ絶縁状態が保たれている。電極２４の先端部は、針状であることが好ましく、針状電極は、コロナ放電を効率的に行い霧化粒子２５の凝集を防止させる。尚、弾性体３５として、有機溶媒耐性を有するゴム及び／或いは金属から構成されるダイヤフラムを使用することができる。
(Example 3)
FIG. 3 shows another conceptual diagram of the main part of the present invention. A mesh 34 having a through hole joined with the raw material solution fed through the
（実施例４）
実施例４では、図１及び図２で示した加圧振動噴射造粒装置を用いて、フェノール樹脂の球状粒子とカーボントナーの球状粒子を製造した。
Example 4
In Example 4, spherical particles of phenol resin and spherical particles of carbon toner were produced using the pressure vibration jet granulator shown in FIGS. 1 and 2.
表１のＮｏ．１〜Ｎｏ．４は、フェノール樹脂原料のレゾール樹脂（Ａ液）の粘度を６０〜５００ｃｐに変化させ、加圧振動噴射造粒による製造試験を行った。ノズルの条件は、５μｍの貫通孔で、穴密度が６０００個/ｃｍ2で、ホルマリン（Ｂ液）で反応させた。常圧（１ｋｇ/ｃｍ2）の条件では、生産量が０〜１５ｇ／１５ｍｉｎであつたが、圧力を２〜５ｋｇ/ｃｍ2に変化させるとほぼ、圧力に比例して、フェノールの球状粒子が３０〜５５０ｇ/１５ｍｉｎの生産量が得られた。得られた球状粒子は、真円度も優れたものであつた。 No. in Table 1 1-No. No. 4 changed the viscosity of the resole resin (liquid A), which is a phenol resin raw material, to 60 to 500 cp, and performed a production test by pressure vibration jet granulation. The nozzle conditions were 5 μm through holes, a hole density of 6000 holes / cm 2 , and a reaction with formalin (liquid B). Under normal pressure (1 kg / cm 2 ) conditions, the production amount was 0 to 15 g / 15 min. However, when the pressure was changed to 2 to 5 kg / cm 2 , the spherical particles of phenol were almost proportional to the pressure. A yield of 30-550 g / 15 min was obtained. The obtained spherical particles had excellent roundness.
表１のＮｏ．５〜Ｎｏ．８は、黒色のカーボントナーの製造を行った。前記のフェノールの球状粒子を６５０℃で焼成し、炭化収率５０％で、カーボントナー原料を得て、公知のワックス、接着剤、分散剤、溶剤を用いて、トナー原料スラリーを作成し、ノズル条件として、７μｍの貫通孔で、穴密度５０００個/ｃｍ2で製造を行った。粘度は、３００〜１５００ｃｐに変化させ、スラリーの圧力は、１〜５ｋｇ/ｃｍ2の条件で製造した。その結果、常圧では粘度が高く、殆ど、製造出来なかったが、圧力を２〜５ｋｇに昇圧することにより、圧力とスラリー粘度に比例して、１３〜３６５ｇ/１５ｍｉｎの球状トナーを無粉砕で、無分級で得られた。 No. in Table 1 5-No. No. 8 produced black carbon toner. The above spherical spherical particles of phenol are fired at 650 ° C. to obtain a carbon toner raw material with a carbonization yield of 50%, and a toner raw material slurry is prepared using a known wax, adhesive, dispersant, and solvent, and a nozzle As a condition, a 7 μm through hole was manufactured at a hole density of 5000 holes / cm 2 . The viscosity was changed to 300-1500 cp, and the slurry pressure was 1-5 kg / cm 2 . As a result, the viscosity was high at normal pressure and could hardly be produced. Obtained without classification.
（実施例５ 銀の球状超微粒子の製造）
原料液Ａとして１５重量％濃度の硝酸銀アンモニア溶液を用い、反応溶液Ｂとして濃度７．５ｇ／ｌが溶液グリオキザール液を用いて、図１の加圧振動噴射造粒装置により、銀の球状超微粒子を製造した。得られた銀粒子は、平均粒径が５０μｍ以下であり、真円度も優れたものであった。
Example 5 Production of Silver Ultrafine Particles
A spherical ultrafine particle of silver is produced by using a pressure-vibration jet granulator of FIG. 1 using a 15 wt% silver nitrate ammonia solution as the raw material liquid A and a solution glyoxal liquid having a concentration of 7.5 g / l as the reaction solution B. Manufactured. The obtained silver particles had an average particle diameter of 50 μm or less and excellent roundness.
本発明は、本文明細書に記載のように加圧振動噴射造粒装置を用いて、５０μ以下の超微粒子を無粉砕、無分級で高効率に工業的に生産可能な方法を提供し、なおかつ、目的用途により、真円度が低い粒子が求められたり、鱗片状の形状が求められる工業的用途にも柔軟に対応可能な工業的生産方法を提供するものである。さらに、本発明方法は、低コストでの工業生産が可能で、極めて優れた省エネルギー化、炭酸ガスの削減を可能で、来るべき次世代のナノテク時代に最適に材料生産技術を提供可能な工業的価値、極めて大なるものである。 The present invention provides a method capable of industrially producing ultrafine particles of 50 μm or less without pulverization, non-classification and high efficiency using a pressure vibration injection granulator as described in the present specification, and The present invention provides an industrial production method that can flexibly cope with an industrial application in which particles having low roundness are required or a scaly shape is required depending on the intended application. Furthermore, the method of the present invention enables industrial production at a low cost, enables extremely excellent energy saving and reduction of carbon dioxide gas, and can provide material production technology optimally in the coming next generation nanotechnology era. Value is tremendous.
１ 貯液タンク
２ 加圧原料（Ａ液）導入口
３ 加圧原料液タンク
４ 弾性体
５ 弾性体接合部
６ 貫通孔を有する本発明の金属メッシュ
７ 圧電振動体
８ 電源
９ 霧化粒子荷電部
１０ 霧化粒子
１１ 帯電粒子
１２ 反応槽
１３ 反応溶液導入口
１４ サイクロン式反応槽
１５ 反応貯液槽
１６ パイプ
１７ 移送ポンプ
１８ 移送パイプ
２１ 帯電槽
２２ 電源部
２３ 電極２４の対電極（正極）
２３ａ 絶縁シールド
２４ コロナ放電電極（負極）
２４ａ 絶縁シールド
２５ 霧化粒子
３４ 金属メッシュ
３５ 弾性体
３６ 圧電素子
DESCRIPTION OF SYMBOLS 1 Liquid storage tank 2 Pressurized raw material (A liquid) inlet 3 Pressurized raw material liquid tank 4 Elastic body 5 Elastic body joint part 6 Metal mesh of this invention which has a through-hole 7 Piezoelectric vibrator 8 Power supply 9 Atomized particle charge part DESCRIPTION OF SYMBOLS 10 Atomization particle 11 Charged particle 12 Reaction tank 13 Reaction solution inlet 14 Cyclone type reaction tank 15 Reaction storage tank 16
Claims (3)
前記貯液タンクと筒状の弾性体を介して接合され、前記弾性体内を通過した前記液状物が通過される多数の貫通孔を有する基盤ノズルと、
前記液状物の濃度、粘度に応じて電源から電圧が供給され、前記基盤ノズルを定速度振動させることで前記液状物を前記貫通孔に通過させて球状微粒子化粒子を形成する圧電振動部と、
コロナ放電により前記球状微粒子化粒子を帯電させて帯電霧化粒子にする霧化粒子荷電部と、
を備えた加圧振動噴射造粒装置。 A liquid storage tank in which a slurry-like liquid material pumped under pressure is stored ;
A base nozzle having a number of through-holes that are joined to the liquid storage tank via a cylindrical elastic body and through which the liquid material that has passed through the elastic body passes ;
The concentration of the liquid material is supplied voltage from the power source depending on the viscosity, and the piezoelectric vibrating portion for forming said base nozzle the liquid was passed through the through hole by causing the constant velocity vibration spherical fine particles,
An atomized particle charging unit that charges the spherical micronized particles by corona discharge to form charged atomized particles ;
A pressure vibration jet granulation apparatus comprising:
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| US20100009191A1 (en) * | 2006-07-28 | 2010-01-14 | Mitsubishi Materials Corporation | Fine silver particles, production method thereof, and production apparatus therefor |
| JP5224022B2 (en) * | 2006-07-28 | 2013-07-03 | 三菱マテリアル株式会社 | Method and apparatus for producing silver fine particles |
| JP2009020349A (en) * | 2007-07-12 | 2009-01-29 | Ricoh Co Ltd | Method for producing toner, toner and developer |
| JP5033590B2 (en) * | 2007-11-12 | 2012-09-26 | 株式会社リコー | Toner production method and toner |
| JP5434061B2 (en) * | 2007-12-19 | 2014-03-05 | 株式会社リコー | Electrophotographic developer carrier manufacturing method, electrophotographic developer carrier, electrophotographic developer, electrophotographic developing method, process cartridge |
| JP5224104B2 (en) * | 2008-04-16 | 2013-07-03 | 株式会社リコー | Toner manufacturing method and toner |
| KR101502867B1 (en) | 2008-10-30 | 2015-03-18 | 주식회사 탑 엔지니어링 | Head apparatus and liqiud crystal dispenser having the same |
| KR101645347B1 (en) * | 2014-11-17 | 2016-08-04 | 재단법인 포항산업과학연구원 | DEVICE FOR producing anisotropic micro carbon spheres, AND THE Method |
| JP6443774B2 (en) * | 2017-07-03 | 2018-12-26 | 株式会社リコー | Particle production method |
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| JPH0243943A (en) * | 1988-04-12 | 1990-02-14 | Mitsuboshi:Kk | Preparation of ultrafine powder |
| JP3201818B2 (en) * | 1992-03-10 | 2001-08-27 | 大川原化工機株式会社 | Spray pyrolysis method and apparatus |
| JP3363938B2 (en) * | 1993-03-29 | 2003-01-08 | 日鉄鉱業株式会社 | Method for producing spherical iron nitride fine particles by sintering method |
| DE19928392A1 (en) * | 1999-06-22 | 2000-12-28 | Merck Patent Gmbh | Spray pyrolysis or spray drying apparatus used in the production of inorganic oxides and mixed oxides or powder material comprises a reaction tube located in an outer tube, an atomizing system, gas inlet supports, and gas inlet slits |
| DE60140625D1 (en) * | 2000-08-15 | 2010-01-07 | Univ Illinois | PROCESS FOR PRODUCING MICROPARTICLES |
| JP5113308B2 (en) * | 2001-08-29 | 2013-01-09 | 智彦 羽柴 | Ultrafine particle production equipment |
| JP3957581B2 (en) * | 2002-07-19 | 2007-08-15 | 電気化学工業株式会社 | Method for producing spherical silica powder |
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