JP2001002423A - Production of granular iron oxide agglomerate powder - Google Patents
Production of granular iron oxide agglomerate powderInfo
- Publication number
- JP2001002423A JP2001002423A JP11171646A JP17164699A JP2001002423A JP 2001002423 A JP2001002423 A JP 2001002423A JP 11171646 A JP11171646 A JP 11171646A JP 17164699 A JP17164699 A JP 17164699A JP 2001002423 A JP2001002423 A JP 2001002423A
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- JP
- Japan
- Prior art keywords
- particles
- iron oxide
- powder
- aggregated
- granular
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
Landscapes
- Developing Agents For Electrophotography (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Compounds Of Iron (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、粒状酸化鉄凝集粉
末の製造方法に関し、詳しくは酸化鉄一次粒子を乾式装
置で凝集させ特定の酸化鉄凝集粒子からなる粒状酸化鉄
凝集粉末とすることにより、ハンドリング性、流動性、
分散性に優れた、特に静電複写磁性トナー用材料粉、静
電潜像現像用キャリア用材料粉、塗料用黒色顔料粉等の
用途に用いられる粒状酸化鉄凝集粉末の製造方法に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing granular iron oxide agglomerated powder, and more particularly, to a method of aggregating primary iron oxide agglomerated particles in a dry apparatus to obtain a granular iron oxide agglomerated powder composed of specific iron oxide agglomerated particles. , Handling, fluidity,
The present invention relates to a method for producing a granular iron oxide agglomerated powder having excellent dispersibility, particularly used for applications such as a material powder for an electrostatic copying magnetic toner, a material powder for a carrier for developing an electrostatic latent image, and a black pigment powder for a paint.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】一般
に、静電複写磁性トナーや静電潜像現像用キャリア等
は、アクリル樹脂やポリエステル樹脂等の熱可塑性樹脂
を基材として、マグネタイト粒子に代表されるような磁
性と黒色顔料の性能を併せ持つ酸化鉄粒子が添加されて
製造される。この際、酸化鉄粒子に要求される特性とし
て、樹脂中へのより高い分散性が挙げられる。磁性トナ
ー製造において、この分散性が不良だとトナー中の酸化
鉄粒子の存在がばらつき、磁気特性を始めとする諸特性
に悪影響を与える。2. Description of the Related Art In general, a magnetic toner for electrostatic copying, a carrier for developing an electrostatic latent image, and the like are made of a thermoplastic resin such as an acrylic resin or a polyester resin, and are typically represented by magnetite particles. It is manufactured by adding iron oxide particles having both the magnetism and the performance of a black pigment. In this case, as a property required for the iron oxide particles, higher dispersibility in a resin can be cited. In the production of a magnetic toner, if the dispersibility is poor, the presence of iron oxide particles in the toner varies, which adversely affects various properties including magnetic properties.
【０００３】一方、磁性トナー製造においては、酸化鉄
粒子のハンドリング性、流動性も重要な特性である。例
えば、樹脂との混合、粉砕等の製造工程において、酸化
鉄粒子のハンドリング性や流動性が不良で供給が安定し
ない場合、より具体的には、ホッパー内や供給口での棚
つりや居付き、閉塞等が発生すると酸化鉄粒子と樹脂等
の混合品や粉砕品中において既に酸化鉄粒子の重量的な
分布不良が発生してしまうからである。On the other hand, in the production of magnetic toner, the handling properties and fluidity of iron oxide particles are also important characteristics. For example, in the manufacturing process such as mixing with resin and pulverization, when the handling and fluidity of iron oxide particles are poor and supply is not stable, more specifically, shelf hanging or staking in the hopper or at the supply port If blockage or the like occurs, a weight distribution defect of the iron oxide particles already occurs in a mixture or a pulverized product of the iron oxide particles and the resin.
【０００４】このような不都合を抑制するためには、使
用する酸化鉄粒子自体のハンドリング性、流動性、分散
性を改良する必要があり、これまでにも種々の提案がな
されている。例えば特開平６−１３０７１８号公報には
粒子表面にシリカ微粒子を付着させたものが提案されて
いる。特開平６−２３０６０３号公報には粒子表面にＳ
ｉ及び／又はＴｉ化合物及びカップリング剤層を有する
ことが開示されている。また、特開平７−２４０３０６
号公報にはケイ素含有マグネタイト粒子表面にシリカ及
びアルミナ微粒子その他を付着させることが示されてい
る。特開平９−５９０２４号公報にはケイ素その他の金
属元素含有マグネタイト粒子の各稜線を曲面状とするこ
とが記載されている。さらに特開平９−２４１０２５号
公報にはケイ素含有マグネタイト粒子の形状を角の丸い
金平糖状とすることが開示されている。しかし、これら
の従来技術を始めとして乾式、湿式を問わず公知の製造
工程により得られた酸化鉄粒子を用いたのでは、粉体そ
のものの凝集性に加え、磁気凝集の影響も相俟って酸化
鉄粒子自体のハンドリング性、流動性、分散性の改良効
果には限界があった。[0004] In order to suppress such inconveniences, it is necessary to improve the handleability, fluidity and dispersibility of the iron oxide particles used, and various proposals have been made so far. For example, Japanese Patent Application Laid-Open No. Hei 6-130718 proposes a method in which silica fine particles are adhered to the particle surface. JP-A-6-230603 discloses that S
It is disclosed to have an i and / or Ti compound and a coupling agent layer. Also, Japanese Patent Application Laid-Open No. 7-240306
Japanese Patent Application Laid-Open Publication No. H11-139, pp. 1 to 3 discloses that silica and alumina fine particles and the like are attached to the surface of silicon-containing magnetite particles. Japanese Patent Application Laid-Open No. 9-59024 describes that each ridge line of magnetite particles containing silicon and other metal elements has a curved surface. Further, Japanese Patent Application Laid-Open No. 9-241025 discloses that the shape of silicon-containing magnetite particles is rounded with spines. However, the use of iron oxide particles obtained by a known manufacturing process regardless of the dry type or wet type including these conventional techniques, in addition to the cohesiveness of the powder itself, combined with the influence of magnetic coagulation. There is a limit to the effect of improving the handling properties, fluidity, and dispersibility of the iron oxide particles themselves.
【０００５】また、特開平８−２５９２３８号公報に
は、個数平均粒子径が０．０５〜１μｍの酸化鉄粒状粒
子が凝集した粒子径２０μｍ以下の凝集粒子からなる着
色用顔料粉末が開示されており、該粉末は剪断作用が大
きい容器固定の水平複軸型の混練機を使用することによ
り得られるとしている。そして、同公報には、大きな凝
集粒子を粉砕して凝集粒子の粒子径を数十μｍ以下とす
る手段、例えば衝撃式粉砕機、ボールミル、振動ミル、
ロール圧縮成形機、ホイール型混練機を使用する手段に
ついても触れ、これらにより得られた凝集粒子に対する
上記粒子径２０μｍ以下の凝集粒子の優位性について記
載されている。Japanese Patent Application Laid-Open No. Hei 8-259238 discloses a pigment powder for coloring composed of aggregated particles having a particle diameter of 20 μm or less in which iron oxide granular particles having a number average particle diameter of 0.05 to 1 μm are aggregated. The powder is said to be obtained by using a horizontal double-shaft kneader fixed to a container having a large shearing action. The publication discloses means for pulverizing large agglomerated particles to reduce the particle diameter of the agglomerated particles to several tens μm or less, for example, an impact-type pulverizer, a ball mill, a vibration mill,
Means of using a roll compression molding machine and a wheel-type kneader are also mentioned, and the superiority of the aggregated particles having a particle diameter of 20 μm or less to the aggregated particles obtained by these methods is described.
【０００６】同公報に開示の技術によれば、確かに樹脂
成形物製造の際の分散性には優れているものの、凝集粒
子の大きいものは分散性が悪いという観点に立ってお
り、さらにハンドリング性、流動性の面で充分な性能を
有していない。According to the technology disclosed in the publication, although the dispersibility in the production of a resin molded product is excellent, the one having large aggregated particles is poor in dispersibility. It does not have sufficient performance in terms of fluidity and fluidity.
【０００７】以上のように、工程内での流動性に優れ、
かつ樹脂等との混練時の分散性に優れた酸化鉄凝集粒子
については未だ提案されていない。[0007] As described above, excellent fluidity in the process,
Iron oxide aggregated particles having excellent dispersibility at the time of kneading with a resin or the like have not yet been proposed.
【０００８】従って、本発明の目的は、搬送性に優れ、
またハンドリング性、流動性が良好で、凝集粒子であり
ながら適度な強度を有することで樹脂との混練時の分散
性に優れた粒状酸化鉄凝集粒子からなる粒状酸化鉄凝集
粉末の製造方法を提供することにある。[0008] Accordingly, an object of the present invention is to provide excellent transportability,
Also, the present invention provides a method for producing a granular iron oxide aggregate powder comprising granular iron oxide aggregate particles having good handling properties and fluidity, and having moderate strength while being agglomerated particles, and having excellent dispersibility during kneading with a resin. Is to do.
【０００９】[0009]
【課題を解決するための手段】一般的に、粉体そのもの
には少なからず凝集する性質があることが知られてお
り、その物理的、化学的な結合力としてのファンデルワ
ールスカ、静電的、磁気的、又は液架橋的な凝集作用以
外に、外部からの力学的又は熱的エネルギーを加えるこ
とによって、粉体を凝集、造粒、顆粒化することができ
る。In general, it is known that powder itself has a property of agglomeration to a certain extent, and its physical and chemical bonding force is van der Waalska, electrostatic Powder can be aggregated, granulated, and granulated by applying mechanical or thermal energy from the outside in addition to the magnetic or liquid crosslinking aggregation.
【００１０】しかしながら、本発明の場合には、得られ
た凝集粒子は、使用時にはその凝集形態がほぐれ、分散
性にも優れていることが要求される。この凝集粒子製造
の際に、外部から加えられるエネルギーが高いと、分散
時に必要となるエネルギーも大きくなり、結果としてか
かる凝集粒子の分散性は不良となることが容易に推定さ
れる。However, in the case of the present invention, the obtained agglomerated particles are required to be loose in agglomerated form and to be excellent in dispersibility when used. In the production of the aggregated particles, if the energy applied from the outside is high, the energy required at the time of dispersion is also increased, and as a result, it is easily presumed that the dispersibility of the aggregated particles becomes poor.
【００１１】本発明者等は、鋭意検討の結果、出発原料
である酸化鉄一次粒子に対してなるべくエネルギーを直
接的に加えることなく、分散時に少ないエネルギーでほ
ぐれる凝集粒子を製造できれば良いのではないかと考え
た。As a result of intensive studies, the present inventors have found that it is not sufficient to produce aggregated particles that can be loosened with a small amount of energy at the time of dispersion without directly applying energy to the primary particles of iron oxide as a starting material. I thought.
【００１２】そして、従来の製造方法で製造された酸化
鉄粒子を用いて意図的な凝集操作を加える製造方法にお
いて、粒子同士の接触機会を多くでき、その接触の際に
粒子同士が付着・凝集を繰り返す、いわゆる粒子の自己
凝集力及び／又は付着力を助長させる乾式装置を凝集操
作に使用することにより、凝集粒子の形状、大きさ、強
度等を制御することができ、出発原料の酸化鉄粒子に比
べ、分散性、ハンドリング性、流動性が格段に優れた粒
状酸化鉄凝集粒子が得られ、本発明の目的が達成し得る
ことを知見するに至った。[0012] In the production method in which the iron oxide particles produced by the conventional production method are subjected to an intentional aggregating operation, the chances of contact between the particles can be increased, and the particles adhere and aggregate during the contact. By using a dry apparatus that promotes the so-called self-cohesive force and / or adhesive force of the particles for the coagulation operation, the shape, size, strength, and the like of the coagulated particles can be controlled, and iron oxide as a starting material can be used. As a result, it has been found that granular iron oxide aggregated particles having remarkably excellent dispersibility, handling properties, and fluidity as compared with particles can be obtained, and that the object of the present invention can be achieved.
【００１３】本発明は、上記知見に基づきなされたもの
で、個数平均粒子径が０．０５〜１μｍの酸化鉄一次粒
子が凝集し、個数平均粒子径が３０〜３０００μｍであ
り、かつ加熱減量が０．０５〜２重量％である粒状酸化
鉄凝集粒子からなる粒状酸化鉄凝集粉末の製造方法であ
って、上記酸化鉄一次粒子の凝集操作を粒子の自己凝集
力及び／又は付着力を助長させる乾式装置により行うこ
とを特徴とする粒状酸化鉄凝集粉末の製造方法を提供す
るものである。The present invention has been made on the basis of the above findings, and primary iron oxide particles having a number average particle diameter of 0.05 to 1 μm are aggregated, the number average particle diameter is 30 to 3000 μm, and the heat loss is reduced. A method for producing a granular iron oxide agglomerated powder comprising 0.05 to 2% by weight of agglomerated iron oxide particles, wherein the aggregating operation of the iron oxide primary particles promotes self-agglomeration and / or adhesion of the particles. An object of the present invention is to provide a method for producing a granular iron oxide agglomerated powder, which is performed by a dry apparatus.
【００１４】[0014]
【発明の実施の形態】以下、本発明の実施の形態を説明
する。本発明の製造方法においては、出発原料である酸
化鉄一次粒子の形態は、マグネタイト（Ｆｅ3 Ｏ4 ）を
始めとして、マグヘマイト（γ−Ｆｅ2 Ｏ3 ）やその中
間組成のベルトライド化合物（ＦｅＯｘ・Ｆｅ2 Ｏ3 、
０＜Ｘ＜１）、及びこれらの単独又は複合化合物にＦｅ
以外のＳｉ、Ａｌ、Ｍｎ、Ｎｉ、Ｚｎ、Ｃｕ、Ｍｇ、Ｔ
ｉ、Ｃｏ、Ｚｒ、Ｗ、Ｍｏ、Ｐ等を少なくとも１種以上
含むスピネルフェライト粒子等を必要な特性に応じて選
択すればよく、その形状はトナー用に適した特性を付与
できるものなら特に限定されないが、トナー用材料粉と
して一般的な粒状品（球状、八面体状、六面体状）を用
いるのが好ましい。Embodiments of the present invention will be described below. In the production method of the present invention, the form of the iron oxide primary particles as the starting material includes magnetite (Fe 3 O 4 ), maghemite (γ-Fe 2 O 3 ), and a beltlide compound (FeOx) having an intermediate composition thereof. Fe 2 O 3 ,
0 <X <1), and these compounds alone or in combination with Fe
Other than Si, Al, Mn, Ni, Zn, Cu, Mg, T
Spinel ferrite particles containing at least one kind of i, Co, Zr, W, Mo, P, etc. may be selected according to the required characteristics, and the shape is not particularly limited as long as it can impart characteristics suitable for toner. However, it is preferable to use general granular products (spherical, octahedral, and hexahedral) as the toner material powder.
【００１５】さらに、分散性を向上させるために、Ｓｉ
やＡｌ、あるいは有機処理剤等による表面処理を施した
酸化鉄一次粒子を用いてもよい。Further, in order to improve dispersibility, Si
Iron oxide primary particles that have been subjected to a surface treatment with, for example, Al or an organic treating agent may be used.
【００１６】酸化鉄一次粒子としては、乾式、湿式を問
わず公知の製造工程により得られる個数平均粒子径０．
０５〜１μｍのものであればよく、乾燥工程を経たもの
であれば成形物でもよいが、予め一次粒子や一次粒子の
微細な凝集粒子レベルまでジェットミルやハンマーミル
等の粉砕装置やミックスマーラー等の圧密処理装置によ
る処理を加えて、大きな凝集粒子を少なくしておくほう
が好ましい。As the iron oxide primary particles, a number average particle diameter of 0.1 or less obtained by a known production process regardless of a dry type or a wet type.
It may be a molded product as long as it has a particle size of from 0.5 to 1 μm, and may be a molded product as long as it has passed through a drying step. It is more preferable to reduce the size of large aggregated particles by adding a treatment by a consolidation treatment device.
【００１７】本発明では、この酸化鉄一次粒子の凝集操
作を粒子の自己凝集力及び／又は付着力を助長させる乾
式装置により行い、粒状酸化鉄凝集粒子からなる粒状酸
化鉄凝集粉末とする。一般的に、意図的な凝集操作の中
には造粒、顆粒化という手段があり、この手段により得
られるものを造粒物、顆粒と呼んだりして、固有の粉体
特性等に起因する凝集、並びにそれによる凝集物と区別
されることが多いが、本発明でいう「意図的な凝集」は
意図的に行う凝集、造粒、顆粒化のいずれの手段をも指
す。In the present invention, the aggregating operation of the iron oxide primary particles is performed by a dry apparatus which promotes the self-aggregating force and / or the adhering force of the particles to obtain a granular iron oxide agglomerated powder composed of the granular iron oxide agglomerated particles. Generally, there are means of intentional agglomeration operations such as granulation and granulation, and what is obtained by this means is called granules or granules, and is caused by inherent powder characteristics and the like. Although it is often distinguished from agglomeration and the resulting aggregate, "intentional aggregation" in the present invention refers to any means of intentional aggregation, granulation, and granulation.
【００１８】ここでいう粒状凝集粒子とは、光学顕微鏡
８０倍にて観察した際に、凝集粒子中に空隙が認められ
ず、かつ一次粒子が稠密に凝集しているものを指し、粒
状酸化鉄凝集粒子とは、粒状凝集粒子が酸化鉄粒子から
なるものを指す。さらに、粒状凝集粉末とは粒状凝集粒
子からなる粉末を指し、粒状酸化鉄凝集粉末とは粒状酸
化鉄凝集粒子からなる粉末を指す。この粒状酸化鉄凝集
粉末は、理想的には１００％粒状酸化鉄凝集粒子で構成
されていることが最も好ましいが、実用上は、８０重量
％以上の粒状酸化鉄凝集粒子が含まれていれば良い。The term "granular agglomerated particles" as used herein refers to particles in which no voids are observed in the agglomerated particles and primary particles are densely agglomerated when observed with an optical microscope at a magnification of x80. Aggregated particles refer to those in which granular aggregated particles are made of iron oxide particles. Further, the granular agglomerated powder refers to a powder composed of granular agglomerated particles, and the granular agglomerated iron oxide powder refers to a powder composed of agglomerated iron oxide particles. Ideally, the granular iron oxide aggregated powder is ideally composed of 100% granular iron oxide aggregated particles. However, in practice, if 80% by weight or more of the granular iron oxide aggregated particles are contained, good.
【００１９】また、一次粒子又は凝集粒子という場合に
は、その内容によって個々の粒子又はその集合のいずれ
も意味する。When referred to as primary particles or agglomerated particles, it means either individual particles or an aggregate thereof depending on the content.
【００２０】凝集を行う乾式装置としては、一次粒子の
面接触に基づく固い凝集を避け、点接触に基づく柔らか
でほぐれやすい凝集を実現し、かつ強度を加熱減量で調
整しながら凝集操作を加えられるものであればよい。具
体的には、ナウターミキサー、モルタルミキサーに代表
される混合装置、振動ふるい機、ロータップに代表され
るふるい装置、皿型、ドラム型に代表される転動式造粒
装置、振動フィーダーやスクリューフィーダーに代表さ
れる供給・搬送装置、サイクロンに代表される遠心力集
塵装置を凝集装置として利用することにより製造でき
る。上記装置に共通している点は、転動や振動等により
粒子同士の接触機会が多く、その接触の際に粒子同士が
付着、凝集を繰り返すことにある。As a dry apparatus for performing agglomeration, agglomeration operation can be added while avoiding hard agglomeration based on surface contact of primary particles, realizing soft and easy loosening based on point contact, and adjusting strength by heating loss. Anything should do. Concretely, mixing devices such as Nauta mixers and mortar mixers, vibrating sieves, sieve devices such as low taps, tumbling granulators such as plate type and drum type, vibrating feeders and screws It can be manufactured by using a feeding / conveying device represented by a feeder and a centrifugal dust collector represented by a cyclone as an aggregating device. What is common to the above-described devices is that there are many opportunities for particles to come into contact with each other due to rolling, vibration, and the like, and the particles repeatedly adhere and aggregate during the contact.
【００２１】これら装置は、粒子本来の有する凝集力及
び／又は付着力を利用し、その作用を助長する機能を有
しており、低速回転型、公転及び／又は自転機能のある
回転転動型、水平及び／又は垂直方向への振動移動型と
いった特徴を少なくとも一つ以上有するものである。These devices have a function of utilizing the cohesive force and / or adhesion force inherent in the particles and promoting the action thereof, and are provided with a low-speed rotation type, a revolving and / or a rotation rolling type having a rotation function. , And at least one feature such as a vibration-moving type in the horizontal and / or vertical directions.
【００２２】これに対し、酸化鉄一次粒子に大きなエネ
ルギーを直接的に加えるような装置の使用は好ましくな
い。個々の粒子を強力に相互圧縮したり、強固に成形さ
せるような装置、詳しくは短時間に衝撃を与える打錠機
やブリケッティングマシン等に代表される圧縮式造粒装
置、大きな圧縮応力により強制的に成形を行うスクリュ
ー型、ラム型、リング型等の各種押出し機に代表される
押出式造粒装置、高温度の雰囲気中でスラリー等を加熱
・乾燥・固結させるスプレードライヤーやディスクドラ
イヤーに代表される噴霧式造粒装置、粗大な塊状粒子を
粉砕する各種粉砕装置、あるいは圧縮応力の高いミック
スマーラーや圧縮ロールに代表される圧密処理装置等を
単独で用いたのでは、凝集粒子の流動性は改善されるも
のの、凝集粒子を構成する一次粒子や一次粒子の微細な
凝集粒子同士の凝集力が強すぎて分散性に劣るものであ
ったり、粗大な塊状の凝集粒子が破壊されただけの不定
形、かつ流動性、分散性が共に劣る凝集粒子しか得られ
ない。On the other hand, it is not preferable to use a device which directly applies a large energy to the primary iron oxide particles. A device that strongly compresses individual particles or forms them firmly, specifically a compression-type granulating device typified by a tableting machine or briquetting machine that gives an impact in a short time, and a large compressive stress Extrusion-type granulators represented by various types of extruders such as screw, ram, and ring types that forcibly mold, spray dryers and disk dryers that heat, dry, and consolidate slurries in a high-temperature atmosphere Spray granulation equipment, various types of pulverization equipment for pulverizing coarse agglomerated particles, or a consolidation processing equipment such as a mix muller or a compression roll with high compression stress are used alone. Although the fluidity is improved, the cohesive force between the primary particles constituting the aggregated particles and the fine aggregated particles of the primary particles is too strong and the dispersibility is inferior, or the coarse aggregate Amorphous just collecting particles are destroyed, and flowability, obtained only together poor aggregated particles dispersibility.
【００２３】次に、本発明の製造方法に使用できる好ま
しい製造装置について、具体的に説明する。Next, a preferred production apparatus that can be used in the production method of the present invention will be specifically described.
【００２４】ここで言う混合装置とは、粉体を乾式で機
械的な応力で混合する機械を指し、ナウターミキサー、
モルタルミキサー、フラッシュミキサー、ヘンシェルミ
キサー、リボン型混合機、Ｖ型混合機、スクリュー型混
合機、パドル型混合機、ニーダー等であり、好ましくは
ナウターミキサー、モルタルミキサー、Ｖ型混合機、ス
クリュー型混合機等であり、付着、凝集作用による機能
がより高い装置が好ましい。また、粉体同士が混合され
る過程でランダムに接触する機会があるものであればバ
ッチ式でも連続式のものでもよい。The term "mixing device" as used herein refers to a machine that mixes powder with dry mechanical stress, and includes a Nauta mixer,
Mortar mixer, flash mixer, Henschel mixer, ribbon type mixer, V type mixer, screw type mixer, paddle type mixer, kneader, etc., preferably Nauta mixer, mortar mixer, V type mixer, screw type A device such as a mixer, which has a higher function by the adhesion and coagulation actions, is preferable. Further, a batch type or a continuous type may be used as long as there is a chance that the powders come into contact with each other at random during the mixing process.
【００２５】また、ふるい装置とは、乾式で行うもの
で、振動ふるい機、ロータップ等であり、振動式、円運
動型、旋回型、３次元旋回運動型等の方式があるが、い
ずれも粉体同士がランダムに接触する機会があるもので
あれば使用できる。The sieving apparatus is of a dry type, and is a vibrating sieving machine, a low tap or the like, and includes a vibrating type, a circular motion type, a revolving type, a three-dimensional revolving type, and the like. Anything can be used as long as there is a chance that the bodies will come into contact randomly.
【００２６】供給・搬送装置とは、乾式で粉体を機械的
な応力により供給・搬送する装置を指し、振動フィーダ
ー又はコンベアー、空気コンベアー、スクリューフィー
ダー又はコンベアー等が代表として挙げられるが、粉体
が供給・搬送される際に系内での粒子の移動がランダム
にあるものであれば使用できる。The supply / transport apparatus refers to an apparatus for supplying / transporting powder in a dry manner by mechanical stress, and includes a vibration feeder or a conveyor, an air conveyor, a screw feeder, a conveyor and the like. Can be used as long as the particles move randomly in the system when is supplied and transported.
【００２７】転動式造粒装置とは、皿型又はドラム型に
代表される造粒装置を指し、ペレタイザーや媒体を用い
ない回転ドラム式の装置（ボールミル等）が代表として
挙げられる。The rolling type granulating apparatus refers to a granulating apparatus typified by a dish type or a drum type, and includes a rotary drum type apparatus (such as a ball mill) that does not use a pelletizer or a medium.
【００２８】遠心力集塵装置とは、サイクロンを指し、
粉体が移動する際に粉体同士の接触機会がランダムにあ
るものなら使用できる。The centrifugal dust collector refers to a cyclone,
Any material can be used if there is a random chance of contact between the powders when they move.
【００２９】次に、本発明に用いられる上記乾式装置の
いずれかを利用する際の重要な操作条件を述べる。ま
ず、粒状酸化鉄凝集粉末を製造する環境条件は、温度０
〜５０℃、湿度１０〜９０％である。この範囲未満やこ
の範囲を超える環境条件では、得られる粒状酸化鉄凝集
粒子の加熱減量を容易に制御しにくいばかりか、コスト
的に不経済でもある。出発原料の加熱減量に応じて上記
の範囲内で環境条件の設定を行うのが好ましい。Next, important operating conditions when using any of the above-mentioned dry apparatuses used in the present invention will be described. First, the environmental conditions for producing the granular iron oxide aggregate powder are as follows.
５０50 ° C., humidity 10１０〜90%. Under environmental conditions below or above this range, it is not only difficult to easily control the loss on heating of the obtained particulate iron oxide aggregated particles, but it is also uneconomical in terms of cost. It is preferable to set the environmental conditions within the above range according to the heating loss of the starting material.
【００３０】この乾式装置を用いた酸化鉄一次粒子の凝
集においては、粒状酸化鉄凝集粒子の加熱減量を０．０
５〜２重量％に調整することが重要である。その手段と
して、原料となる加熱減量を調節した酸化鉄一次粒子を
使用する方法、凝集操作を行う装置の置かれた環境を調
節する方法、水噴霧等の方法により意図的に水分を供給
する方法等が挙げられるが、粒状凝集酸化鉄粒子の加熱
減量が０．０５〜２重量％となる条件であればどの方法
を用いてもよく、またこれらの方法を併用してもよい。In the agglomeration of primary iron oxide particles using this dry apparatus, the heat loss of the granular iron oxide agglomerated particles is reduced by 0.0%.
It is important to adjust to 5 to 2% by weight. As the means, a method of using iron oxide primary particles whose heating loss has been adjusted as a raw material, a method of adjusting an environment where a device for performing a coagulation operation is placed, and a method of intentionally supplying water by a method such as water spraying Any method may be used as long as the weight loss on heating of the particulate aggregated iron oxide particles is 0.05 to 2% by weight, and these methods may be used in combination.
【００３１】また、必要に応じて無機物や有機物等のバ
インダーを添加してもよい。しかし、バインダーの選定
には注意を要し、結着力の強すぎるバインダーを使用す
ると、樹脂との混練において一次粒子の分散性を阻害す
る恐れが生じる。Further, if necessary, a binder such as an inorganic substance or an organic substance may be added. However, care must be taken in selecting a binder. If a binder having too high a binding force is used, the dispersibility of the primary particles may be hindered in kneading with a resin.
【００３２】次に、本発明により得られる粒状酸化鉄凝
集粉末を構成する粒状酸化鉄凝集粒子の性状について述
べる。Next, the properties of the aggregated iron oxide particles constituting the aggregated iron oxide powder obtained by the present invention will be described.
【００３３】本発明により得られる粒状酸化鉄凝集粒子
は、一次粒子や一次粒子の微細な凝集粒子が凝集してな
るものであり、その個数平均粒子径は３０〜３０００μ
ｍである。また、この酸化鉄凝集粒子の形状は、粒状で
あれば特に限定されないが、流動性の面からすると好ま
しくは球状である。The granular iron oxide aggregated particles obtained by the present invention are obtained by aggregating primary particles or fine aggregates of primary particles, and have a number average particle diameter of 30 to 3000 μm.
m. The shape of the iron oxide aggregated particles is not particularly limited as long as it is granular, but is preferably spherical from the viewpoint of fluidity.
【００３４】上述した従来技術に示されるような、乾
式、湿式を問わず公知の製造工程により得られる凝集し
た酸化鉄粒子や、該凝集した酸化鉄粒子を粉砕して凝集
粒子の粒子径を数十μｍ以下とすることにより得られる
凝集粒子は、粉体自体の凝集や磁気凝集の影響が強かっ
たり、元の凝集粒子の形状に起因して不定形であるばか
りか、一次粒子が枝状に絡み合ったり、粒子中に空隙が
多く存在したりするため、分散性、ハンドリング性、流
動性に劣るものである。As described in the above-mentioned prior art, agglomerated iron oxide particles obtained by a known production process irrespective of a dry method or a wet method, or agglomerated iron oxide particles are pulverized to reduce the particle diameter of the agglomerated particles. The agglomerated particles obtained by setting the particle size to 10 μm or less are not only strongly affected by the agglomeration of the powder itself or the magnetic agglutination, but also have an irregular shape due to the shape of the original agglomerated particles, and the primary particles have a branch shape. They are inferior in dispersibility, handling, and fluidity because they are entangled or many voids are present in the particles.
【００３５】これに対し、本発明により得られる粒状酸
化鉄凝集粒子は、強制的に粉体同士を圧着するような製
造方法を用いず、粉体同士の凝集力及び／又は付着力を
利用して遊離粒子の発生を抑制しているため、ハンドリ
ング性、流動性に優れているのはもちろん、樹脂中での
分散性にも優れている。On the other hand, the granular iron oxide aggregated particles obtained according to the present invention utilize the cohesive force and / or adhesive force between the powders without using a production method in which the powders are pressed together. As a result, the generation of free particles is suppressed, so that it is excellent not only in handleability and fluidity but also in dispersibility in a resin.
【００３６】また、上記特開平８−２５９２３８号公報
に記載の粒子径２０μｍ以下の凝集粒子は、凝集粒子が
大きいと分散性が不良になるという観点から提案されて
いるのに対し、本発明では樹脂中で粒状酸化鉄凝集粒子
が均一な分散性を示した上で、凝集粒子を構成する一次
粒子や微細な凝集粒子がさらに分散してゆくという二段
分散が達成できることを前提として、凝集粒子を大きく
してハンドリング性、流動性をも向上させているのであ
る。The agglomerated particles having a particle diameter of 20 μm or less described in JP-A-8-259238 have been proposed from the viewpoint that large agglomerated particles cause poor dispersibility. Assuming that the two-stage dispersion in which the primary particles and fine aggregated particles constituting the aggregated particles are further dispersed can be achieved after the granular iron oxide aggregated particles show uniform dispersibility in the resin. To improve handling and fluidity.
【００３７】つまり、本発明によって得られる粒状酸化
鉄凝集粒子を用いることにより、まず樹脂中で凝集粒子
は速い分散速度で、かつ均一に分散していく。次いで、
混練の際、凝集粒子が適度にバランスされた強度で凝集
されているので個々の凝集粒子に均等な応力がかかり、
二次分散が完結するのである。That is, by using the particulate iron oxide aggregated particles obtained by the present invention, the aggregated particles are dispersed uniformly in the resin at a high dispersion speed. Then
At the time of kneading, since the aggregated particles are aggregated with appropriately balanced strength, an even stress is applied to each aggregated particle,
The secondary dispersion is complete.
【００３８】上述した従来技術による酸化鉄粒子におい
ては、流動性に劣るため、一次分散が進みにくく、その
結果一次分散と二次分散が同時に進行せざるを得ず、結
果として均等な混練応力が粒子にかからず一次粒子の分
散に不具合が生じるものと推測される。In the iron oxide particles according to the prior art described above, the primary dispersion is difficult to progress due to poor fluidity. As a result, the primary dispersion and the secondary dispersion have to proceed simultaneously, and as a result, the uniform kneading stress is reduced. It is presumed that a problem occurs in the dispersion of the primary particles regardless of the particles.
【００３９】従って、凝集粒子を適度な大きさの粒径に
整えると共に、その強度を加熱減量でバランスよく制御
した凝集粒子とすることが重要な点である。Therefore, it is important that the agglomerated particles be adjusted to an appropriate particle size and that the strength be controlled in a well-balanced manner by reducing the weight of the agglomerated particles.
【００４０】特に、凝集粒子径の大きさと凝集粒子の強
度のバランスは重要で、本発明により得られる粒状酸化
鉄凝集粒子の個数平均粒子径が３０μｍ未満の場合に
は、分散性の面では良好であっても、ハンドリング性、
流動性の面で劣ったものとなる。この個数平均粒子径が
３０００μｍを超える場合には、凝集粒子が大きすぎて
バインダーを用いない場合には強度が全く不足し、バイ
ンダーを使用すると強度が上がりすぎ、凝集粒子から一
次粒子レベルへの分散性の不良を免れない。In particular, the balance between the size of the aggregated particles and the strength of the aggregated particles is important. When the number average particle size of the granular iron oxide aggregated particles obtained according to the present invention is less than 30 μm, the dispersibility is good. Even, handling,
It is inferior in fluidity. When the number average particle size exceeds 3000 μm, the aggregated particles are too large and the strength is completely insufficient when no binder is used, and when the binder is used, the strength is too high, and the dispersion from the aggregated particles to the primary particle level occurs. Unavoidable sexual failure.
【００４１】また、本発明により得られる粒状酸化鉄凝
集粒子は、加熱減量が０．０５〜２重量％である。加熱
減量が０．０５重量％未満の場合には、凝集粒子中の一
次粒子同士の凝集力が弱すぎ、一次粒子の一部が凝集粒
子から分離してしまい、特にハンドリング性、流動性が
不良となる。また、凝集粒子の加熱減量が２重量％を超
える場合には、水分過多により一次粒子同士の凝集力及
び／又は付着力が強すぎ、分散性が不良となる。The iron oxide aggregate particles obtained by the present invention have a heat loss of 0.05 to 2% by weight. When the weight loss on heating is less than 0.05% by weight, the cohesive force between the primary particles in the aggregated particles is too weak, and a part of the primary particles is separated from the aggregated particles, and particularly the handling property and the fluidity are poor. Becomes If the weight loss of the aggregated particles exceeds 2% by weight, the cohesive force and / or the adhesive force between the primary particles is too strong due to excessive moisture, resulting in poor dispersibility.
【００４２】この粒状酸化鉄凝集粒子は次の特性、性状
を有するものが好ましい。すなわち、圧縮度は好ましく
は４０％以下であり、さらに好ましくは３５％以下であ
る。安息角は好ましくは４０°以下であり、さらに好ま
しくは３８°以下である。見掛嵩密度は好ましくは１ｇ
／ｃｍ3 以上であり、さらに好ましくは１．１ｇ／ｃｍ
3 以上である。衝撃を加えた後のスパチュラ角は好まし
くは４５°以下であり、さらに好ましくは４０°以下で
ある。４５°傾斜金属板上での重量付着率は１０重量％
以下であることが望ましい。It is preferable that the granular iron oxide aggregated particles have the following properties and properties. That is, the degree of compression is preferably 40% or less, more preferably 35% or less. The angle of repose is preferably 40 ° or less, more preferably 38 ° or less. Apparent bulk density is preferably 1 g
/ Cm 3 or more, more preferably 1.1 g / cm 3
3 or more. The spatula angle after impact is preferably 45 ° or less, more preferably 40 ° or less. The weight adhesion rate on a 45 ° inclined metal plate is 10% by weight
It is desirable that:
【００４３】本発明により得られる粒状酸化鉄凝集粒子
からなる粒状酸化鉄凝集粉末は、上記特性、性状を有す
る粒状酸化鉄凝集粒子のみで構成されていることが好ま
しいが、実用面から考えて、風力分級により得られた粒
径３０μｍ以上の凝集粒子の重量比率が８０重量％以上
となるように、上記粒状酸化鉄凝集粒子を含有していれ
ばよく、好ましくは９０重量％以上、より好ましくは９
５重量％以上が望ましい。この重量比率が８０重量％未
満の場合には、凝集粉末のハンドリング性、流動性、搬
送性は著しく劣るものとなる。The particulate iron oxide aggregate powder comprising the particulate iron oxide aggregate particles obtained according to the present invention is preferably composed of only the particulate iron oxide aggregate particles having the above-described properties and properties. The particulate iron oxide aggregated particles may be contained so that the weight ratio of the aggregated particles having a particle size of 30 μm or more obtained by air classification is 80% by weight or more, preferably 90% by weight or more, more preferably 9
5% by weight or more is desirable. If the weight ratio is less than 80% by weight, the handling, fluidity and transportability of the aggregated powder will be extremely poor.
【００４４】上述した本発明の製造方法では、凝集物を
ある程度の大きさに調整することができ、それにより、
工程での二次粒子の均一な供給が行え、かつ、その凝集
粒子の硬さを柔らかく調整することもでき、それによ
り、凝集粒子を一次粒子まで分散させることができる。In the above-described production method of the present invention, the aggregate can be adjusted to a certain size, whereby
The secondary particles can be uniformly supplied in the process, and the hardness of the aggregated particles can be adjusted to be soft, whereby the aggregated particles can be dispersed to the primary particles.
【００４５】この凝集粒子の粒径や強度が維持できない
場合には、工程内での搬送中の衝撃や応力等により凝集
粒子がこわれ、その結果ハンドリング性や流動性に劣る
粒子が発生するので、装置内での付着や閉塞を起こすこ
ととなり、安定した供給が困難になる。If the particle size and strength of the aggregated particles cannot be maintained, the aggregated particles are broken by impact or stress during transportation in the process, and as a result, particles having poor handling properties and fluidity are generated. Adhesion and blockage in the device will occur, and stable supply will be difficult.
【００４６】また、本発明によって得られた粒状酸化鉄
凝集粒子からなる粒状酸化鉄凝集粉末は、樹脂と混練す
る等の工程で粉体を供給するときに、安定して、かつ容
易に投入のコントロールができる。特に、連続式で投入
され、全体の再混合、再混練が行われないときは、供給
時の複数物質のバランスが重要となり、いかに一定して
物質を供給し続けるかが重要になる。そういう観点か
ら、本発明によって得られた粒状酸化鉄凝集粉末は優れ
ている。The granular iron oxide aggregate powder comprising the granular iron oxide aggregate particles obtained according to the present invention can be stably and easily introduced when the powder is supplied in a process such as kneading with a resin. You have control. In particular, when the material is fed in a continuous manner and the whole is not remixed or kneaded, it is important to balance a plurality of substances at the time of supply, and it is important how to keep supplying the substances constantly. From such a viewpoint, the granular iron oxide aggregate powder obtained by the present invention is excellent.
【００４７】[0047]
【実施例】以下、実施例等に基づき本発明を具体的に説
明する。The present invention will be specifically described below based on examples and the like.
【００４８】［試験例］表１に出発原料となる酸化鉄粒
子Ａ〜Ｅについて、下記の方法によって測定した諸特性
を示す。この酸化鉄粒子は通常の湿式酸化法によって製
造され、通常の方法で洗浄、乾燥、粉砕されたものであ
る。なお、実施例及び比較例に記載の製造方法では、特
に記載のないものは通常の環境、詳しくは温度１５〜２
８℃、湿度４０〜７０％で行った。[Test Examples] Table 1 shows various properties of iron oxide particles A to E as starting materials measured by the following methods. The iron oxide particles are produced by a usual wet oxidation method, and are washed, dried and pulverized by a usual method. In the production methods described in Examples and Comparative Examples, those not particularly described are those in a normal environment, specifically, at a temperature of 15 to 2.
The test was performed at 8 ° C and a humidity of 40 to 70%.
【００４９】（１）一次粒子の個数平均粒子径；透過型
電子顕微鏡写真（倍率３０，０００倍）により、写真上
の粒径を計測し、その個数平均粒子径を求めた。 （２）安息角；ホソカワミクロン社製パウダーテスター
を用い、本体付属のマニュアルに従って測定した。 （３）見掛嵩密度；試料をふるい等を使用せず、そのま
ま内容量１００ｃｍ3の容器に投入し、重量を測定し単
位体積当たりの重量を求めた。 （４）加熱減量；窒素雰囲気下で、試料を９０℃、１時
間加熱し、変化した重量の元重量に対する割合を求め
た。 （５）衝撃後のスパチュラ角；ホソカワミクロン社製パ
ウダーテスターを用い、本体付属のマニュアルに従って
測定した。 （６）圧縮度；見掛嵩密度と、ホソカワミクロン社製パ
ウダーテスターを用い、本体付属のマニュアルに従って
測定したタップ密度に基づき、次式で計算して求めた。 圧縮度＝｛（タップ密度−見掛嵩密度）／（タップ密
度）｝×１００ （７）鏡面反射率；ＪＩＳ Ｋ ５１０１のフーバーマ
ーラー法に準じて調製した分散ペーストと硝化綿クリヤ
ーラッカーとの混練物を１ｍｉｌのフィルムアプリケー
ターを用いて白紙に展色した塗布膜面における２０°の
反射率を測定した。 （８）傾斜板上に付着する割合；厚さ０．５ｍｍ、縦３
０ｃｍ、横２０ｃｍの金属製板（材質ＳＵＳ３０４）を
４５°に傾け、試料１０ｇを高さ１０ｃｍのところから
一度に落下させ、金属板上を転がし、又は滑らせる。そ
の操作を１０回、計１００ｇの試料を落下させ、金属板
上に付着した重量を求め、投入した１００ｇに対する割
合で示した。(1) Number average particle diameter of primary particles: The particle diameter on the photograph was measured by a transmission electron microscope photograph (magnification: 30,000 times), and the number average particle diameter was determined. (2) Angle of repose: Measured using a powder tester manufactured by Hosokawa Micron Corp. according to the manual attached to the main body. (3) Apparent bulk density: The sample was put into a container having an internal volume of 100 cm 3 as it was without using a sieve or the like, and the weight was measured to determine the weight per unit volume. (4) Heating loss: The sample was heated in a nitrogen atmosphere at 90 ° C. for 1 hour, and the ratio of the changed weight to the original weight was determined. (5) Spatula angle after impact; measured using a powder tester manufactured by Hosokawa Micron Corp. according to the manual attached to the main body. (6) Degree of compression: Apparent bulk density and a tap density measured using a powder tester manufactured by Hosokawa Micron Co., Ltd. according to a manual attached to the main body, and calculated by the following formula. Compressibility = {(tap density−apparent bulk density) / (tap density)} × 100 (7) Specular reflectance; kneading of a dispersion paste prepared according to JIS K 5101 Hoover-Murler method and a nitrified cotton clear lacquer Using a 1 mil film applicator, the product was spread on white paper, and the reflectance at 20 ° on the coated film surface was measured. (8) Ratio of adhering on inclined plate; thickness 0.5 mm, length 3
A metal plate (material: SUS304) having a length of 0 cm and a width of 20 cm is tilted at 45 °, and 10 g of a sample is dropped at a time from a height of 10 cm, and rolled or slipped on the metal plate. The operation was repeated 10 times, and a total of 100 g of the sample was dropped, the weight attached to the metal plate was obtained, and the result was expressed as a percentage with respect to the input 100 g.
【００５０】[0050]
【表１】 [Table 1]
【００５１】［実施例１］上記酸化鉄粒子Ａ３０ｋｇ
を、温度２３℃、湿度３５％の環境を維持しながら、ナ
ウターミキサー（ホソカワミクロン（株）社製、ＮＸ−
１）を用い、スクリューの自転９０ｒｐｍ、公転３ｒｐ
ｍの回転で、６０分間処理することにより粒状酸化鉄凝
集粉末を得た。Example 1 30 kg of the above iron oxide particles A
While maintaining an environment of a temperature of 23 ° C. and a humidity of 35%, a Nauter mixer (manufactured by Hosokawa Micron Corporation, NX-
Using 1), screw rotation 90 rpm, revolution 3 rpm
By treating with a rotation of m for 60 minutes, a granular iron oxide aggregated powder was obtained.
【００５２】この粒状酸化鉄凝集粉末について、上記試
験例の酸化鉄粒子の測定に準拠して諸特性を評価した。
また、風力分級による３０μｍ以上の凝集粒子の重量比
率、凝集粒子の個数平均粒子径、粒状酸化鉄凝集粉末と
樹脂との混練物中のムラ、粒状酸化鉄凝集粉末と樹脂と
の混練物中の分散については下記の方法によって測定し
た。結果を表２に示す。Various properties of the granular iron oxide aggregate powder were evaluated based on the measurement of the iron oxide particles in the above test examples.
In addition, the weight ratio of the aggregated particles of 30 μm or more by air classification, the number average particle diameter of the aggregated particles, unevenness in the kneaded product of the granular iron oxide agglomerated powder and the resin, the kneaded material of the granular iron oxide agglomerated powder and the resin The dispersion was measured by the following method. Table 2 shows the results.
【００５３】（９）風力分級による３０μｍ以上の凝集
粒子の重量比率；風力分級機（日清エンジニアリング社
製、ターボクラシファイアＴＣ−１５Ｍ型）を用いて３
０μｍ以上の凝集粒子を分級し、その重量と分級に供し
た粒状酸化鉄凝集粉末重量により３０μｍ以上の凝集粒
子重量比率を求めた。 （１０）凝集粒子の個数平均粒子径；光学顕微鏡（倍率
８０倍）により、写真上の粒径を計測し、その個数平均
粒子径を求めた。 （１１）粒状酸化鉄凝集粉末と樹脂、負帯電制御剤、剥
離剤との混練物中のムラ；試料と樹脂（三洋化成社製Ｔ
Ｂ−１０００Ｆ）、負帯電制御剤（オリエント化学社製
ポントロンＳ−３４）及び剥離剤（三洋化成社製ビスコ
ール５５０Ｐ）を用いて重量比１００：１００：１：２
でヘンシェルミキサーを用いて混合し、２軸のニーダー
で１８０℃、１分間溶融混練した後、混練物をローラー
を用いて板状に成型、冷却の後、粗粉砕、微粉砕（ファ
インミル）し、得られたものを風力分級して磁性トナー
を得た。この磁性トナーを常温硬化型エポキシ樹脂にて
固定し、この試料を切断、研磨した後、切断面を走査型
電子顕微鏡を用いて観察し（倍率５，０００倍）、切断
面中の酸化鉄粒子が均一に分布しているものを○、少し
分布に偏りがあるものを△、分布の偏りが著しいものを
×として評価した。 （１２）粒状酸化鉄凝集粉末と樹脂、負帯電制御剤、剥
離剤との混練物中の分散；上記（１１）の観察におい
て、切断面中の酸化鉄一次粒子が凝集していないものを
○、やや凝集しているものを△、著しく凝集しているも
の×として評価した。(9) Weight ratio of agglomerated particles having a size of 30 μm or more by air classification: 3 using an air classifier (Turbo Classifier TC-15M, manufactured by Nisshin Engineering Co., Ltd.)
The agglomerated particles of 0 μm or more were classified, and the weight ratio of the agglomerated particles of 30 μm or more was determined from the weight and the weight of the granular iron oxide agglomerated powder used for the classification. (10) Number average particle diameter of aggregated particles: The particle diameter on the photograph was measured with an optical microscope (magnification: 80 times), and the number average particle diameter was determined. (11) Unevenness in a kneaded product of the granular iron oxide aggregated powder and a resin, a negative charge control agent, and a release agent; a sample and a resin (manufactured by Sanyo Chemical Co., Ltd.)
B-1000F), a negative charge control agent (Pontron S-34 manufactured by Orient Chemical Co., Ltd.) and a release agent (Viscol 550P manufactured by Sanyo Chemical Co., Ltd.) in a weight ratio of 100: 100: 1: 2.
After mixing with a Henschel mixer and melting and kneading at 180 ° C. for 1 minute with a biaxial kneader, the kneaded material is molded into a plate shape using a roller, cooled, coarsely crushed and finely crushed (fine mill). The obtained product was subjected to air classification to obtain a magnetic toner. The magnetic toner was fixed with a cold-setting epoxy resin, the sample was cut and polished, and the cut surface was observed using a scanning electron microscope (magnification: 5,000 times). Were evaluated as △ when the distribution was uniform, Δ when the distribution was slightly uneven, and X when the distribution was significantly uneven. (12) Dispersion in a kneaded product of the granular iron oxide aggregate powder and a resin, a negative charge control agent, and a release agent; in the observation of the above (11), a particle in which the primary iron oxide particles in the cut surface are not aggregated was evaluated as ○. And those that were slightly aggregated were evaluated as Δ, and those that were significantly aggregated were evaluated as x.
【００５４】［実施例２］上記酸化鉄粒子Ｂ５００ｋｇ
を、ロータップ型振動ふるい機（（株）平工製作所社
製、ロータップ型振動ふるい機）を用い、使用するふる
いのメッシュを３段とし、上側から４２５μｍ、２５０
μｍ、１２５μｍとし、振動回転数２９０ｒｐｍ、タッ
プ頻度１５６ｔｐｍの条件で、３０分間処理し、各メッ
シュ上の凝集粒子をひとまとめに混合し、粒状酸化鉄凝
集粉末を得た。この粒状酸化鉄凝集粉末について、実施
例１に準拠して諸特性を評価した。結果を表２に示す。Example 2 500 kg of the above iron oxide particles B
Using a low-tap vibrating sieve (a low-tap vibrating sieve manufactured by Heiko Seisakusho Co., Ltd.), using a three-stage sieve mesh, 425 μm from the upper side, 250
μm, 125 μm, a vibration frequency of 290 rpm and a tap frequency of 156 tpm for 30 minutes, and agglomerated particles on each mesh were mixed together to obtain a granular iron oxide agglomerated powder. Various properties of this granular iron oxide aggregated powder were evaluated in accordance with Example 1. Table 2 shows the results.
【００５５】［実施例３］上記酸化鉄粒子Ｃを振動コン
ベアー（幅３０ｃｍ、高さ１０ｃｍ、長さ２ｍ）を用
い、振幅１ｍｍ、振動数６０Ｈｚの振動を加え、３ｋｇ
／ｍｉｎの速度で原料酸化鉄粒子を投入することで処理
を行い、粒状酸化鉄凝集粉末を得た。この粒状酸化鉄凝
集粉末について、実施例１に準拠して諸特性を評価し
た。結果を表２に示す。Example 3 The above iron oxide particles C were subjected to vibration of 1 mm in amplitude and 60 Hz in frequency of 3 kg using a vibration conveyor (30 cm in width, 10 cm in height and 2 m in length).
The treatment was carried out by charging the raw iron oxide particles at a rate of / min to obtain a granular iron oxide aggregate powder. Various properties of this granular iron oxide aggregated powder were evaluated in accordance with Example 1. Table 2 shows the results.
【００５６】［実施例４］上記酸化鉄粒子Ｄ１０ｋｇ
を、パン型造粒機（パンの内径１．２ｍ、深さ１５ｃ
ｍ）を用い、パンの傾斜を４５度、回転数２０ｒｐｍで
３０分間処理し、粒状酸化鉄凝集粉末を得た。この粒状
酸化鉄凝集粉末について、実施例１に準拠して諸特性を
評価した。結果を表２に示す。Example 4 10 kg of the above iron oxide particles D
Using a pan-type granulator (inner diameter of bread 1.2 m, depth 15c)
m), the pan was tilted at 45 ° and the rotation speed at 20 rpm for 30 minutes to obtain a granular iron oxide aggregated powder. Various properties of this granular iron oxide aggregated powder were evaluated in accordance with Example 1. Table 2 shows the results.
【００５７】［実施例５］上記酸化鉄粒子Ｅ１ｋｇを、
サイクロン（ＯＳＡＷＡ社製ＭＰ−３８）を用い、凝集
されていない粒子は循環し、凝集された物は順次サイク
ロンの系から排出し、排出された物を粒状酸化鉄凝集粉
末として得た。この粒状酸化鉄凝集粉末について、実施
例１に準拠して諸特性を評価した。結果を表２に示す。Example 5 1 kg of the above iron oxide particles E was
Using a cyclone (MP-38 manufactured by OSAWA), non-agglomerated particles were circulated, and the agglomerated matter was sequentially discharged from the cyclone system, and the discharged matter was obtained as a granular iron oxide agglomerated powder. Various properties of this granular iron oxide aggregated powder were evaluated in accordance with Example 1. Table 2 shows the results.
【００５８】［比較例１］上記酸化鉄粒子Ａを何も処理
しないで、実施例１に準拠して諸特性を評価した。結果
を表２に示す。Comparative Example 1 Various characteristics were evaluated according to Example 1 without any treatment of the iron oxide particles A. Table 2 shows the results.
【００５９】［比較例２］上記酸化鉄粒子Ｅを何も処理
しないで、実施例１に準拠して諸特性を評価した。結果
を表２に示す。Comparative Example 2 Various characteristics were evaluated according to Example 1 without any treatment of the iron oxide particles E. Table 2 shows the results.
【００６０】［比較例３］上記酸化鉄粒子Ａの未粉砕品
である塊をショックレスハンマーで砕き、３ｍｍの篩を
通して粗粒子を取り除き、酸化鉄凝集粉末を得た。この
酸化鉄凝集粉末について、実施例１に準拠して諸特性を
評価した。結果を表２に示す。[Comparative Example 3] A lump as an unground product of the iron oxide particles A was crushed with a shockless hammer, and coarse particles were removed through a 3 mm sieve to obtain an iron oxide aggregate powder. Various characteristics of this iron oxide aggregated powder were evaluated in accordance with Example 1. Table 2 shows the results.
【００６１】［比較例４］上記酸化鉄粒子Ｄの未粉砕品
である塊をショックレスハンマーで砕き、３ｍｍの篩を
通して粗粒子を取り除き、酸化鉄凝集粉末を得た。この
酸化鉄凝集粉末について、実施例１に準拠して諸特性を
評価した。結果を表２に示す。[Comparative Example 4] An unmilled lump of the iron oxide particles D was crushed with a shockless hammer, and coarse particles were removed through a 3 mm sieve to obtain an iron oxide aggregate powder. Various characteristics of this iron oxide aggregated powder were evaluated in accordance with Example 1. Table 2 shows the results.
【００６２】［比較例５］上記酸化鉄粒子Ａを１０ｇ／
Ｌとなるように水で希釈し、スプレードライヤー（三井
三池化工機（株）社製、ＳＤ−１０型）を用い、１２０
℃の条件下で給液量を２００ｍＬ／ｍｉｎで処理し、粒
状酸化鉄凝集粉末を得た。この粒状酸化鉄凝集粉末につ
いて、実施例１に準拠して諸特性を評価した。結果を表
２に示す。[Comparative Example 5] The above-mentioned iron oxide particles A were added in an amount of 10 g /
L and diluted with water using a spray dryer (SD-10, manufactured by Mitsui Miike Kakoki Co., Ltd.).
The solution was treated at a rate of 200 mL / min at a temperature of ° C. to obtain a granular iron oxide aggregate powder. Various properties of this granular iron oxide aggregated powder were evaluated in accordance with Example 1. Table 2 shows the results.
【００６３】［比較例６］上記酸化鉄粒子Ｃを１０ｇ／
Ｌとなるように水で希釈し、スプレードライヤー（三井
三池化工機（株）社製、ＳＤ−１０型）を用い、１２０
℃の条件下で給液量を２００ｍＬ／ｍｉｎで処理し、粒
状酸化鉄凝集粉末を得た。この粒状酸化鉄凝集粉末につ
いて、実施例１に準拠して諸特性を評価した。結果を表
２に示す。[Comparative Example 6] The iron oxide particles C were added in an amount of 10 g /
L and diluted with water using a spray dryer (SD-10, manufactured by Mitsui Miike Kakoki Co., Ltd.).
The solution was treated at a rate of 200 mL / min at a temperature of ° C. to obtain a granular iron oxide aggregate powder. Various properties of this granular iron oxide aggregated powder were evaluated in accordance with Example 1. Table 2 shows the results.
【００６４】［比較例７］上記酸化鉄粒子Ｂを製造する
工程で洗浄工程が完了し、乾燥を行う前の水分２０ｗｔ
％を含んだ粘土状の塊を直径１ｍｍの穴から押し出し、
ひも状に成形した物を１ｍｍ間隔で切断し、５０℃の乾
燥機中で６時間乾燥し、酸化鉄凝集粉末を得た。この酸
化鉄凝集粉末について、実施例１に準拠して諸特性を評
価した。結果を表２に示す。[Comparative Example 7] The washing step was completed in the step of producing the iron oxide particles B, and the water content before drying was 20 wt%.
% Extruded through a 1 mm diameter hole,
The string-shaped product was cut at intervals of 1 mm, and dried in a dryer at 50 ° C. for 6 hours to obtain an iron oxide aggregate powder. Various characteristics of this iron oxide aggregated powder were evaluated in accordance with Example 1. Table 2 shows the results.
【００６５】[0065]
【表２】 [Table 2]
【００６６】表２から明らかな通り、実施例１〜５の粒
状酸化鉄凝集粉末は、いずれも安息角が４０°以下、見
掛嵩密度が１ｇ／ｃｍ3 以上、加熱減量が０．０５〜２
重量％、衝撃を加えた後のスパチュラ角が４５°以下、
圧縮度が４０％以下、傾斜板上に付着する割合が１０重
量％以下であり、かつ鏡面反射率が４０°以下のものが
得られ、樹脂との混練の製造工程において、二次粒子の
均一な供給と一次粒子の良好な分散とを兼ね備えてい
た。また、混練物中のムラや一次粒子の分散性の評価に
おいても良好な結果が得られた。なお、樹脂との混合粉
末を混練する際の供給も安定していた。As is clear from Table 2, the granular iron oxide aggregated powders of Examples 1 to 5 all have an angle of repose of 40 ° or less, an apparent bulk density of 1 g / cm 3 or more, and a heating loss of 0.05 to 0.05. 2
Weight%, spatula angle after impact is 45 ° or less,
The degree of compression is 40% or less, the rate of adhering on the inclined plate is 10% by weight or less, and the specular reflectivity is 40 ° or less. Supply and good dispersion of the primary particles. Good results were also obtained in evaluation of unevenness in the kneaded material and dispersibility of the primary particles. In addition, the supply at the time of kneading the mixed powder with the resin was also stable.
【００６７】一方、比較例１及び２の酸化鉄粒子は見掛
嵩密度が低く、かつ衝撃を加えた後のスハ゜チュラ 角、安息
角、圧縮度が実施例１〜５に比べて大きく、流動性や凝
集強度において劣るものであった。また、傾斜板上に付
着する粒子も多く、混練物中のムラや一次粒子の分散性
の評価においても劣るものであった。なお、樹脂等との
混合粉末を粉体供給フィーダーやホッパーに供給する
際、付着や閉塞を度々起こし、強制的に粉体を押し込む
操作が必要であた。On the other hand, the iron oxide particles of Comparative Examples 1 and 2 have a low apparent bulk density, and have a larger sputter angle, angle of repose, and degree of compression after impact than those of Examples 1 to 5, and have fluidity. And poor cohesive strength. In addition, many particles adhered to the inclined plate, and were poor in evaluation of unevenness in the kneaded material and dispersibility of primary particles. In addition, when the mixed powder with the resin or the like is supplied to the powder supply feeder or the hopper, the powder often adheres or is blocked, and an operation of forcibly pushing the powder is required.
【００６８】比較例３及び４の酸化鉄凝集粉末は、見掛
嵩密度、安息角、及び衝撃を加えた後のスパチュラ角は
良好なため、流動性に優れ安定して粉体を供給できる
が、その凝集過程で湿式で行われ、かつ、目的とする凝
集粒子の大きさまでの粉砕しか行っていないため、粒子
同士の凝集力が強すぎ、鏡面反射率も低く、一次粒子の
分散性に劣るものであった。The iron oxide agglomerated powders of Comparative Examples 3 and 4 have good bulk density, angle of repose, and spatula angle after impact, and therefore have excellent fluidity and can supply powder stably. In the coagulation process, the coagulation process is performed in a wet manner, and since the pulverization is performed only up to the size of the target coagulated particles, the cohesive force between the particles is too strong, the mirror reflectance is low, and the dispersibility of the primary particles is poor. Was something.
【００６９】比較例５及び６の粒状酸化鉄凝集粉末は、
見掛嵩密度、安息角、及び衝撃を加えた後のスパチュラ
角は良好なため、流動性に優れ安定して粉体を供給でき
るが、高温での強力な加熱、乾燥、固結により、実施例
１〜５に比べて凝集粒子の一次粒子への分散が悪く、従
って鏡面反射率が低く、かつ樹脂との混練時には混合ム
ラはないものの、一次粒子の分散不良を起こしていた。The granular iron oxide aggregate powders of Comparative Examples 5 and 6
Since the apparent bulk density, angle of repose, and spatula angle after impact are good, it can supply powder stably with excellent fluidity, but it is implemented by strong heating, drying and consolidation at high temperature As compared with Examples 1 to 5, the dispersion of the aggregated particles in the primary particles was poor, and thus the specular reflectance was low, and there was no mixing unevenness during kneading with the resin, but poor dispersion of the primary particles occurred.
【００７０】比較例７の酸化鉄凝集粉末は、見掛嵩密
度、安息角、及び衝撃を加えた後のスパチュラ角は良好
なため、流動性に優れ安定して粉体を供給できるが、湿
式で得られた凝集粒子を乾燥しているものであり、その
乾燥過程で凝集粒子がより強く凝集するため、実施例１
〜５に比べて凝集粒子の一次粒子への分散が悪く、従っ
て鏡面反射率が低く、かつ樹脂との混練時には混合ムラ
はないものの、一次粒子の分散不良を起こしていた。The iron oxide agglomerated powder of Comparative Example 7 has good apparent bulk density, angle of repose, and spatula angle after impact, so that it has excellent fluidity and can supply powder stably. The aggregated particles obtained in Example 1 are dried, and the aggregated particles aggregate more strongly during the drying process.
The dispersion of the agglomerated particles in the primary particles was poorer than that of Nos. 5 to 5, so the specular reflectance was low, and there was no mixing unevenness during kneading with the resin, but poor dispersion of the primary particles occurred.
【００７１】[0071]
【発明の効果】以上説明したように、本発明の製造方法
によって、凝集粒子でありながら適度な強度を有するこ
とで樹脂との混合時の分散性に優れ、かつハンドリング
性、流動性にも優れた粒状酸化鉄凝集粒子からなる粒状
酸化鉄凝集粉末が得られる。そして、この粒状酸化鉄凝
集粉末は、静電複写磁性トナー用材料粉、静電潜像現像
用キャリア用材料粉、塗料用黒色顔料粉等の用途に好適
に用いられる。As described above, according to the production method of the present invention, even though the particles are agglomerated particles, they have an appropriate strength, so that they are excellent in dispersibility when mixed with a resin, and also excellent in handling properties and fluidity. Thus, a granular iron oxide aggregate powder comprising the granular iron oxide aggregate particles is obtained. The granular iron oxide aggregated powder is suitably used for applications such as material powder for electrostatic copying magnetic toner, material powder for electrostatic latent image developing carrier, and black pigment powder for paint.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 2H005 AA02 AB02 CB03 EA03 EA05 EA07 4F201 AC04 AR12 BA02 BC01 BC12 BL01 BL03 BL21 BL23 BL42 BL47 BN30 BN32 BQ11 4G002 AB01 AD04 AE01 AE03 AF01 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H005 AA02 AB02 CB03 EA03 EA05 EA07 4F201 AC04 AR12 BA02 BC01 BC12 BL01 BL03 BL21 BL23 BL42 BL47 BN30 BN32 BQ11 4G002 AB01 AD04 AE01 AE03 AF01
Claims (6)
化鉄一次粒子が凝集し、個数平均粒子径が３０〜３００
０μｍであり、かつ加熱減量が０．０５〜２重量％であ
る粒状酸化鉄凝集粒子からなる粒状酸化鉄凝集粉末の製
造方法であって、 上記酸化鉄一次粒子の凝集操作を粒子の自己凝集力及び
／又は付着力を助長させる乾式装置により行うことを特
徴とする粒状酸化鉄凝集粉末の製造方法。1. An iron oxide primary particle having a number average particle size of 0.05 to 1 μm is aggregated, and a number average particle size of 30 to 300
A method for producing a granular iron oxide aggregate powder comprising granular iron oxide aggregate particles having a particle size of 0 μm and a heat loss of 0.05 to 2% by weight, wherein the operation of aggregating the primary iron oxide particles is performed by the self-aggregation force of the particles. And / or a dry apparatus that promotes adhesion.
に記載の粒状酸化鉄凝集粉末の製造方法。2. The dry apparatus according to claim 1, wherein said dry apparatus is a mixing apparatus.
3. The method for producing a granular iron oxide aggregate powder according to item 1.
１に記載の粒状酸化鉄凝集粉末の製造方法。3. The method according to claim 1, wherein the dry apparatus is a sieving apparatus.
求項１に記載の粒状酸化鉄凝集粉末の製造方法。4. The method according to claim 1, wherein the dry apparatus is a tumbling granulator.
求項１に記載の粒状酸化鉄凝集粉末の製造方法。5. The method according to claim 1, wherein the dry apparatus is a supply / transport apparatus.
求項１に記載の粒状酸化鉄凝集粉末の製造方法。6. The method according to claim 1, wherein the dry apparatus is a centrifugal dust collector.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17164699A JP3662778B2 (en) | 1999-06-17 | 1999-06-17 | Method for producing granular iron oxide agglomerated powder |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17164699A JP3662778B2 (en) | 1999-06-17 | 1999-06-17 | Method for producing granular iron oxide agglomerated powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001002423A true JP2001002423A (en) | 2001-01-09 |
| JP3662778B2 JP3662778B2 (en) | 2005-06-22 |
Family
ID=15927082
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17164699A Expired - Fee Related JP3662778B2 (en) | 1999-06-17 | 1999-06-17 | Method for producing granular iron oxide agglomerated powder |
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| JP (1) | JP3662778B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006160579A (en) * | 2004-12-09 | 2006-06-22 | Toyota Central Res & Dev Lab Inc | Fine iron oxide powder and its producing method |
| JP2013211351A (en) * | 2012-03-30 | 2013-10-10 | Toda Kogyo Corp | Ferrite particle powder for bond magnet, resin composition for bond magnet, and molding using them |
-
1999
- 1999-06-17 JP JP17164699A patent/JP3662778B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006160579A (en) * | 2004-12-09 | 2006-06-22 | Toyota Central Res & Dev Lab Inc | Fine iron oxide powder and its producing method |
| JP4729914B2 (en) * | 2004-12-09 | 2011-07-20 | 株式会社豊田中央研究所 | Fine iron oxide powder and method for producing the same |
| JP2013211351A (en) * | 2012-03-30 | 2013-10-10 | Toda Kogyo Corp | Ferrite particle powder for bond magnet, resin composition for bond magnet, and molding using them |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3662778B2 (en) | 2005-06-22 |
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