JP2000351631A - Granular iron oxide aggregated particle and powder containing the aggregated particle - Google Patents
Granular iron oxide aggregated particle and powder containing the aggregated particleInfo
- Publication number
- JP2000351631A JP2000351631A JP11164505A JP16450599A JP2000351631A JP 2000351631 A JP2000351631 A JP 2000351631A JP 11164505 A JP11164505 A JP 11164505A JP 16450599 A JP16450599 A JP 16450599A JP 2000351631 A JP2000351631 A JP 2000351631A
- Authority
- JP
- Japan
- Prior art keywords
- iron oxide
- particles
- aggregated
- powder
- 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.)
- Pending
Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、粒状酸化鉄凝集粒
子及び該凝集粒子を含む粉末に関し、詳しくは酸化鉄一
次粒子が凝集している特定の酸化鉄凝集粒子とすること
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
状酸化鉄凝集粒子及び該凝集粒子を含む粉末に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to granular iron oxide aggregated particles and powder containing the aggregated particles. More specifically, the present invention relates to specific iron oxide aggregated particles in which iron oxide primary particles are aggregated, thereby improving handling properties. Granular iron oxide aggregated particles having excellent fluidity and dispersibility, particularly used for applications such as material powder for electrostatic copying magnetic toner, carrier material powder for electrostatic latent image development, black pigment powder for paints, etc. And a powder comprising:
【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. H11-176, pp. 1 to 3 discloses that silica, alumina fine particles and the like are attached to the surface of silicon-containing magnetite particles. JP-A-9-59024 describes that each ridge line of magnetite particles containing silicon and other metal elements is formed into a curved surface. Further, Japanese Patent Application Laid-Open No. 9-241025 discloses that the shape of silicon-containing magnetite particles is rounded to a spinous shape. 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, causes the effect of magnetic aggregation in addition to the cohesiveness of the powder itself. 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
性に優れた酸化鉄凝集粒子及び該凝集粒子を含む粉末を
提供することにある。[0008] Accordingly, an object of the present invention is to provide excellent transportability,
Another object of the present invention is to provide iron oxide agglomerated particles having excellent handleability and fluidity, excellent dispersibility at the time of kneading with a resin by having appropriate strength while being agglomerated particles, and a powder containing the agglomerated particles. .
【０００９】[0009]
【課題を解決するための手段】本発明者らは、鋭意検討
の結果、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、凝集粒子の形状、大きさ、
強度等を制御することによって、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
た酸化鉄凝集粒子が得られ、このことにより本発明の目
的が達成し得ることを知見した。Means for Solving the Problems As a result of intensive studies, the present inventors have intentionally performed an aggregating operation using iron oxide particles manufactured by a conventional manufacturing method, and determined the shape, size,
By controlling the strength, etc., compared to the iron oxide particles of the starting material, dispersibility, handling properties, and fluidity can be obtained, so that iron oxide aggregated particles with remarkably excellent properties can be obtained, thereby achieving the object of the present invention. Was found.
【００１０】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
子が凝集しており、個数平均粒子径が３０〜３０００μ
ｍであり、かつ粒状酸化鉄凝集粒子の加熱減量値をＡ
（重量％）、酸化鉄一次粒子の比表面積をＢ（ｍ2 ／
ｇ）とした場合、式（1）の関係が成立することを特徴
とする粒状酸化鉄凝集粒子を提供するものである。０．
０２≦Ａ／Ｂ≦０．０８ ・・・ （1）The present invention has been made on the basis of the above-mentioned findings, in which iron oxide primary particles having a number average particle diameter of 0.05 to 1 μm are aggregated, and the number average particle diameter is 30 to 3000 μm.
m, and the heat loss value of the particulate iron oxide aggregated particles is A
(% By weight), the specific surface area of the iron oxide primary particles is represented by B (m 2 /
In the case of g), the present invention provides granular iron oxide aggregated particles characterized by satisfying the relationship of the formula (1). 0.
02 ≦ A / B ≦ 0.08 (1)
【００１１】また、本発明は、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
上であり、上記粒状酸化鉄凝集粒子を含むことを特徴と
する粒状酸化鉄凝集粉末を提供するものである。[0011] The present invention also provides a particulate iron oxide agglomerate characterized in that the weight ratio of the agglomerated particles having a particle size of 30 µm or more obtained by air classification is 80% by weight or more and contains the above-mentioned agglomerated iron oxide particles. It provides a powder.
【００１２】[0012]
【発明の実施の形態】以下、本発明の実施の形態を説明
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、なら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、顆粒化いずれの手段をも指す。Embodiments of the present invention will be described below. 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 agglomerates thereby, "intentional aggregation" in the present invention refers to any means of intentionally performing aggregation, granulation, and granulation.
【００１３】また、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を
含む粉末を指し、粒状酸化鉄凝集粉末とは粒状酸化鉄凝
集粒子を含む粉末を指す。[0013] The granular aggregated particles refer to an optical microscope 80
When observed at ×, no voids were observed in the aggregated particles,
The primary particles are densely aggregated, and the granular iron oxide aggregated particles are those formed of iron oxide particles. Further, the granular agglomerated powder refers to a powder containing granular agglomerated particles, and the granular iron oxide agglomerated powder refers to a powder containing granular iron oxide agglomerated particles.
【００１４】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.
【００１５】本発明の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、Ａ
ｌ、Ｍｎ、Ｎｉ、Ｚｎ、Ｃｕ、Ｍｇ、Ｔｉ、Ｃｏ、Ｚ
ｒ、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）が好ましい。The primary particles of iron oxide as a starting material of the present invention may be in the form of magnetite (Fe 3 O 4 ), maghemite (γ-Fe 2 O 3 ), or a beltlide compound having an intermediate composition (FeOx.Fe). 2 O 3 , 0 <X <1),
And Si or A other than Fe
1, Mn, Ni, Zn, Cu, Mg, Ti, Co, Z
Spinel ferrite particles containing at least one of r, W, Mo, P, etc. may be selected according to the required properties, and the shape thereof is not particularly limited as long as the properties suitable for toner can be imparted. General granular materials (spherical, octahedral, hexahedral) are preferable as the material powder for use.
【００１６】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。Furthermore, 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.
【００１７】一般に静電複写磁性トナーや静電潜像現像
用キャリアに用いられる酸化鉄粒子の一次粒子の個数平
均粒子径は０．０５〜１μｍ程度のものが汎用されてい
るが、本発明においては意図的な凝集操作を加えること
により、この一次粒子や一次粒子の微細な凝集粒子が凝
集してなる粒状酸化鉄凝集粒子であり、その個数平均粒
子径は３０〜３０００μｍであることが重要である。ま
た、本発明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。Generally, primary particles of iron oxide used in an electrostatic copying magnetic toner or a carrier for developing an electrostatic latent image have a primary particle having a number average particle size of about 0.05 to 1 μm. Is a particulate iron oxide aggregated particle obtained by aggregating the primary particles and fine aggregated particles of the primary particles by intentionally performing an aggregation operation, and it is important that the number average particle diameter thereof is 30 to 3000 μm. is there. The shape of the iron oxide aggregated particles of the present invention is not particularly limited as long as it is granular, but is preferably spherical from the viewpoint of fluidity.
【００１８】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 the 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.
【００１９】これに対し、本発明の粒状酸化鉄凝集粒子
は、基本的に水分や有機物等をバインダーとして意図的
に添加することなく、かつ強制的に粉体同士を圧着する
ような製造方法も用いず、粉体同士の凝集力を利用して
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 of the present invention can also be produced by a method in which powders are forcibly pressed together without intentionally adding moisture or an organic substance as a binder. Without using, the generation of free particles is suppressed by utilizing the cohesive force between powders,
It is excellent not only in fluidity but also in dispersibility in resin.
【００２０】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.
【００２１】つまり、本発明の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 granular iron oxide aggregated particles of the present invention, first, the aggregated particles are uniformly dispersed in the resin at a high dispersion speed. Then, at the time of kneading, since the aggregated particles are aggregated with an appropriately balanced strength, uniform stress is applied to each aggregated particle, and the secondary dispersion is completed.
【００２２】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 proceed 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.
【００２３】従って、凝集粒子を適度な大きさの粒径に
整えると共に、酸化鉄一次粒子の比表面積に応じて凝集
粒子の強度を加熱減量でバランスよく制御することは本
発明において重要な点である。Therefore, it is an important point in the present invention to adjust the aggregated particles to an appropriate size and to control the strength of the aggregated particles in a well-balanced manner by reducing the heating according to the specific surface area of the primary iron oxide particles. is there.
【００２４】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、本発明の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 of the present invention is less than 30 μm, the dispersibility is good. However, handling and fluidity are inferior. 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.
【００２５】また、本発明の粒状酸化鉄凝集粒子は、粒
状酸化鉄凝集粒子の加熱減量値をＡ（重量％）、酸化鉄
一次粒子の比表面積をＢ（ｍ2 ／ｇ）とした場合、式
（1）の関係が成立する。 ０．０２≦Ａ／Ｂ≦０．０８ ・・・ （1）The granular iron oxide agglomerated particles of the present invention are characterized in that the weight loss on heating of the agglomerated iron oxide particles is A (% by weight) and the specific surface area of the primary iron oxide particles is B (m 2 / g). Equation (1) holds. 0.02 ≦ A / B ≦ 0.08 (1)
【００２６】このＡ／Ｂが０．０２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、Ａ／Ｂが０．０８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が
強すぎ、分散性が不良となる。When the A / B is less than 0.02, 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. Property becomes poor. On the other hand, when A / B exceeds 0.08, the cohesion between the primary particles is too strong due to excessive water, and the dispersibility becomes poor.
【００２７】本発明の粒状酸化鉄凝集粒子は、圧縮度が
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。圧縮度が４０％を超える場合には、凝集強
度が不足を起こしやすく、衝撃による凝集粒子の破壊や
粒子の遊離が生じ、ひいてはハンドリング性や流動性の
悪化による設備内での付着、棚つり、閉塞の原因とな
る。また、凝集強度が強すぎても樹脂中での分散性、特
に混練時の一次粒子の分散性に影響がでやすいので、好
ましくは圧縮度は２０〜４０％である。The granular iron oxide aggregated particles of the present invention have a degree of compression of preferably 40% or less, more preferably 35% or less.
It is as follows. If the degree of compression exceeds 40%, the cohesive strength tends to be insufficient, and destruction of coagulated particles and liberation of particles due to impact occur, and as a result, adhesion in equipment due to deterioration of handling and fluidity, shelf hanging, May cause blockage. If the cohesive strength is too high, the dispersibility in the resin, particularly the dispersibility of the primary particles during kneading, is likely to be affected, so that the degree of compression is preferably 20 to 40%.
【００２８】本発明の酸化鉄凝集粒子は、安息角が好ま
しくは４０°以下であり、さらに好ましくは３８°以下
である。安息角が４０°を超える場合には、ハンドリン
グ性、流動性が不良となる。The iron oxide aggregate particles of the present invention have an angle of repose of preferably 40 ° or less, more preferably 38 ° or less. If the angle of repose exceeds 40 °, handling properties and fluidity will be poor.
【００２９】本発明の粒状酸化鉄凝集粒子は、見掛嵩密
度が好ましくは１ｇ／ｃｍ3 以上であり、さらに好まし
くは１．１ｇ／ｃｍ3以上である。見掛嵩密度が１ｇ／
ｃｍ3未満の場合には、樹脂中での粒状酸化鉄凝集粒子
の分散性が不良となる。The granular iron oxide aggregate particles of the present invention have an apparent bulk density of preferably 1 g / cm 3 or more, more preferably 1.1 g / cm 3 or more. Apparent bulk density is 1g /
If it is less than 3 cm 3, the dispersibility of the particulate iron oxide aggregated particles in the resin will be poor.
【００３０】本発明の粒状酸化鉄凝集粒子は、衝撃を加
えた後のスパチュラ角が好ましくは４５°以下であり、
さらに好ましくは４０°以下である。このスパチュラ角
が４５°を超える場合には、ハンドリング性、流動性が
不良となる。The granular iron oxide aggregated particles of the present invention preferably have a spatula angle of 45 ° or less after impact.
More preferably, it is 40 ° or less. If the spatula angle exceeds 45 °, handling properties and fluidity will be poor.
【００３１】本発明の粒状酸化鉄凝集粒子は、４５°傾
斜金属板上での重量付着率が１０重量％以下であること
が望ましい。この重量付着率が１０重量％を超える場合
には、流動性、特に設備内での粒子付着が多くなり好ま
しくない。The particulate iron oxide aggregated particles of the present invention desirably have a weight adhesion rate of 10% by weight or less on a 45 ° inclined metal plate. If the weight adhesion ratio exceeds 10% by weight, the fluidity, particularly the particle adhesion in the equipment increases, which is not preferable.
【００３２】次に、本発明の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９５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。Next, it is preferable that the granular iron oxide aggregate powder of the present invention is composed of only the granular iron oxide aggregate particles having the above-mentioned properties and properties. It is sufficient that the particulate iron oxide aggregated particles are contained so that the weight ratio of the aggregated particles having a particle size of 30 μm or more is 80% by weight or more, preferably 90% by weight or more, more preferably 95% by weight or more. . If the weight ratio is less than 80% by weight, the handling, fluidity and transportability of the aggregated powder will be extremely poor.
【００３３】次に、本発明の粒状酸化鉄凝集粒子及び粒
状酸化鉄凝集粉末の具体的な製造方法について述べる。
本発明の粒状酸化鉄凝集粒子の出発原料としては、乾
式、湿式を問わず公知の製造工程により得られる酸化鉄
粒子であればよく、乾燥工程を経たものであれば成形物
でもよいが、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機による常
法の粉砕を加えて、大きな凝集粒子を少なくしておく方
が好ましい。Next, a specific method for producing the granular iron oxide aggregated particles and the granular iron oxide aggregated powder of the present invention will be described.
As a starting material of the granular iron oxide aggregated particles of the present invention, iron oxide particles obtained by a known production process regardless of a dry type or a wet type may be used, and a molded product may be used as long as it has passed through a drying process. It is preferable to reduce the size of large aggregated particles by adding conventional pulverization using a pulverizer such as a jet mill or a hammer mill to the level of fine aggregated particles of particles or primary particles.
【００３４】本発明における粒状酸化鉄凝集粒子及び粒
状酸化鉄凝集粉末は、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
加えられる方法としてナウターミキサーのように粒子同
士の接触機会の多い密閉式構造で、かつ二種類の混練動
作（公転混練と自転混練）を有する装置を使用して製造
できる。The granular iron oxide aggregated particles and the granular iron oxide aggregated powder according to the present invention avoid hard agglomeration based on surface contact of primary particles, realize soft and easily loosened agglomeration based on point contact, and reduce the strength by heating loss. As a method of adding a coagulation operation while adjusting, it can be manufactured using an apparatus having a closed type structure having many opportunities for contact between particles and having two types of kneading operations (revolution kneading and rotation kneading), such as a Nauta mixer. .
【００３５】この製造の際には、水分や有機物等をバイ
ンダーとして意図的に添加する必要はなく、出発原料の
比表面積と加熱減量に応じて、装置のおかれた温湿度環
境を調整した上で運転時間等の条件を調整することが好
ましい。より具体的には、温度０〜５０℃、湿度１０〜
９０％の範囲内で環境設定を行うのが好ましい。At the time of this production, it is not necessary to intentionally add moisture, organic substances, etc. as a binder, and the temperature and humidity environment in which the apparatus is placed is adjusted according to the specific surface area of the starting materials and the heat loss. It is preferable to adjust the conditions such as the operating time in the above. More specifically, a temperature of 0 to 50 ° C and a humidity of 10
It is preferable to set the environment within a range of 90%.
【００３６】なお、個々の粒子を強力に相互圧縮、又は
圧密させるような装置、詳しくは打錠機やブリケッティ
ングマシン等に代表される圧縮成形装置、スクリュー押
出し機やペレットミル等に代表される押出し成形装置、
シンプソン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、あるいはスプレードライヤーに代表され
る乾燥装置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
劣るものとなる。It should be noted that a device for strongly compressing or compacting the individual particles, specifically a compression molding device represented by a tableting machine or a briquetting machine, a screw extruder, a pellet mill and the like. Extrusion equipment,
If a consolidation treatment device such as a Simpson mix muller or a compression roll, or a drying device such as a spray dryer is used alone, the fluidity of the aggregated particles is improved, but the primary particles constituting the aggregated particles are The cohesive force between the fine agglomerated particles of the primary particles is too strong, resulting in poor dispersibility.
【００３７】本発明によれば、凝集粒子をある程度のあ
る程度の大きさにすることにより、工程での二次粒子の
均一な供給が行え、かつ酸化鉄一次粒子の比表面積に応
じて、凝集粒子の強度を加熱減量でバランスよく制御す
ることにより、適度の柔らかさを保ちつつも壊れにく
く、しかも樹脂との混合の際には一次粒子まで分散でき
る凝集粒子が得られるのである。According to the present invention, by making the agglomerated particles a certain size, the secondary particles can be uniformly supplied in the process, and the agglomerated particles can be supplied in accordance with the specific surface area of the iron oxide primary particles. By controlling the strength in a well-balanced manner by weight loss by heating, it is possible to obtain agglomerated particles that are hardly broken while maintaining appropriate softness and that can be dispersed to primary particles when mixed with a resin.
【００３８】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.
【００３９】また、本発明の粒状酸化鉄凝集粒子及び粒
状酸化鉄凝集粉末は、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、本発明の酸化鉄凝集粒子及び粒
状酸化鉄凝集粉末は優れている。The granular iron oxide aggregated particles and the granular iron oxide aggregated powder of the present invention can be stably and easily controlled when the powder is supplied in the process. 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 iron oxide aggregated particles and the granular iron oxide aggregated powder of the present invention are excellent.
【００４０】[0040]
【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。EXAMPLES Hereinafter, the present invention will be specifically described based on examples and the like.
【００４１】［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。[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.
【００４２】（１）比表面積；島津−マイクロメリティ
ックス製２２００型ＢＥＴ計にて測定した。 （２）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。 （３）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。 （４）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。 （５）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。 （６）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。 （７）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 （８）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。 （９）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) Specific surface area: Measured with a 2200 type BET meter manufactured by Shimadzu-Micromeritics. (2) 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. (3) Angle of repose: measured using a powder tester manufactured by Hosokawa Micron Corp. according to the manual attached to the main body. (4) Apparent bulk density: The sample was put into a container having an internal capacity of 100 cm3 without using a sieve or the like, and the weight was measured to determine the weight per unit volume. (5) Heating loss: The sample was heated under a nitrogen atmosphere at 90 ° C. for 1 hour, and the ratio of the changed weight to the original weight was determined. (6) Spatula angle after impact; measured using a powder tester manufactured by Hosokawa Micron Corp. according to the manual attached to the main body. (7) Compressibility: Calculated by the following formula based on apparent bulk density and tap density measured using a powder tester manufactured by Hosokawa Micron Co., Ltd. according to a manual attached to the main body. Compressibility = {(tap density−apparent bulk density) / (tap density)} × 100 (8) Specular reflectance; kneading of a dispersion paste prepared according to the 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. (9) Ratio of adhering on inclined plate; thickness 0.5 mm, length 3
A metal plate (material: SUS304) having a width of 0 cm and a width of 20 cm is tilted at 45 °, and 10 g of a sample is dropped at once from a height of 10 cm, and the sample is rolled or slid 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.
【００４３】[0043]
【表１】 [Table 1]
【００４４】［実施例１］上記酸化鉄粒子Ａ３０ｋｇ
を、温度１０℃、湿度１０％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 10 ° C. and a humidity of 10%, 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.
【００４５】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.
【００４６】（１０）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
３０μｍ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。 （１１）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。 （１２）粒状酸化鉄凝集粉末と樹脂との混練物中のム
ラ；試料と樹脂（三洋化成社製ＴＢ−１０００Ｆ）を用
いて重量比１：１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、冷却した。
この板状の成型物を切断し、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。 （１３）粒状酸化鉄凝集粉末と樹脂との混練物中の分
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。(10) Weight ratio of agglomerated particles of 30 μm or more by air classification: Aggregated particles of 30 μm or more are classified using an air classifier (Turbo Classifier TC-15M, manufactured by Nisshin Engineering Co., Ltd.) The weight ratio of aggregated particles of 30 μm or more was determined based on the weight of the granular iron oxide aggregate powder subjected to the classification. (11) 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. (12) Unevenness in the kneaded product of the granular iron oxide agglomerated powder and the resin; the sample and the resin (TB-1000F, manufactured by Sanyo Chemical Co., Ltd.) were mixed at a weight ratio of 1: 1 using a Henschel mixer, and mixed into two axes. After melt-kneading at 180 ° C. for 1 minute in a kneader, the kneaded material was molded into a plate using a roller and cooled.
The plate-shaped molded product was cut, and the cut surface was observed using a scanning electron microscope (magnification: 5,000 times). Were evaluated as Δ, and those with remarkably uneven distribution were evaluated as x. (13) Dispersion in the kneaded product of granular iron oxide aggregated powder and resin; Δ, markedly aggregated ×.
【００４７】［実施例２］製造する環境を、温度３５
℃、湿度８５％で維持し、ナウターミキサーの処理時間
を１２０分間とした以外は、実施例１と同様に粒状酸化
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] The manufacturing environment was set to a temperature of 35.
A granular iron oxide agglomerated powder was obtained in the same manner as in Example 1 except that the temperature and the humidity were maintained at 85 ° C and the processing time of the Nauter mixer was changed to 120 minutes. About this granular iron oxide aggregate powder,
Various characteristics were evaluated in accordance with Example 1. Table 2 shows the results.
【００４８】［実施例３］出発原料を上記酸化鉄粒子Ｂ
とした以外は、実施例１と同様に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 starting material was iron oxide particles B
A granular iron oxide aggregated powder was obtained in the same manner as in Example 1, except that Various properties of this granular iron oxide aggregated powder were evaluated in accordance with Example 1. Table 2 shows the results.
【００４９】［実施例４］製造する環境を、温度３５
℃、湿度８５％で維持した以外は、実施例３と同様に粒
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。[Embodiment 4] The manufacturing environment was set to a temperature of 35.
A granular iron oxide aggregate powder was obtained in the same manner as in Example 3, except that the temperature was maintained at 85 ° C and a temperature of 85 ° C. Various properties of this granular iron oxide aggregated powder were evaluated in accordance with Example 1. Table 2 shows the results.
【００５０】［実施例５］出発原料を上記酸化鉄粒子Ｃ
とし、製造する環境を、温度２３℃、湿度５５％で維持
した以外は、実施例１と同様に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 5 The starting material was iron oxide particles C
A granular iron oxide aggregated powder was obtained in the same manner as in Example 1, except that the production environment was maintained at a temperature of 23 ° C. and a humidity of 55%. Various properties of this granular iron oxide aggregated powder were evaluated in accordance with Example 1. Table 2 shows the results.
【００５１】［実施例６］製造する環境を、温度３５
℃、湿度８５％で維持した以外は、実施例５と同様に粒
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。[Embodiment 6] The manufacturing environment was set to a temperature of 35.
A granular iron oxide aggregated powder was obtained in the same manner as in Example 5, except that the temperature and the humidity were maintained at 85%. Various properties of this granular iron oxide aggregated powder were evaluated in accordance with Example 1. Table 2 shows the results.
【００５２】［実施例７］製造する環境を、温度１０
℃、湿度１０％で維持した以外は、実施例５と同様に粒
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。[Embodiment 7] The manufacturing environment was set to a temperature of 10
A granular iron oxide aggregate powder was obtained in the same manner as in Example 5, except that the temperature was maintained at 10 ° C. and the humidity was 10%. Various properties of this granular iron oxide aggregated powder were evaluated in accordance with Example 1. Table 2 shows the results.
【００５３】［実施例８］出発原料を上記酸化鉄粒子Ｄ
とた以外は、実施例５と同様に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 8 The starting material was the above iron oxide particles D
A granular iron oxide agglomerated powder was obtained in the same manner as in Example 5, except that the powder was not melted. Various properties of this granular iron oxide aggregated powder were evaluated in accordance with Example 1. Table 2 shows the results.
【００５４】［実施例９］出発原料を上記酸化鉄粒子Ｅ
とた以外は、実施例５と同様に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 9 The starting material was iron oxide particles E
A granular iron oxide agglomerated powder was obtained in the same manner as in Example 5, except that the powder was not melted. Various properties of this granular iron oxide aggregated powder were evaluated in accordance with Example 1. Table 2 shows the results.
【００５５】［比較例１］上記酸化鉄粒子Ｃについて何
ら処理を施さなかった。この酸化鉄粒子について、実施
例１に準拠して諸特性を評価した。結果を表３に示す。Comparative Example 1 No treatment was performed on the iron oxide particles C. Various characteristics of the iron oxide particles were evaluated in accordance with Example 1. Table 3 shows the results.
【００５６】［比較例２］製造する環境を、温度４５
℃、湿度９５％で維持し、ナウターミキサーの処理時間
を１２０分間とした以外は、実施例５と同様に粒状酸化
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３に示
す。[Comparative Example 2] The manufacturing environment was set to a temperature of 45.
A granular iron oxide aggregate powder was obtained in the same manner as in Example 5, except that the temperature and the humidity were maintained at 95 ° C and the processing time of the Nauter mixer was changed to 120 minutes. About this granular iron oxide aggregate powder,
Various characteristics were evaluated in accordance with Example 1. Table 3 shows the results.
【００５７】［比較例３］製造する環境を、温度２℃、
湿度１０％で維持した以外は、実施例５と同様に粒状酸
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３
に示す。[Comparative Example 3] The manufacturing environment was set at a temperature of 2 ° C.
A granular iron oxide aggregate powder was obtained in the same manner as in Example 5, except that the humidity was maintained at 10%. Various properties of this granular iron oxide aggregated powder were evaluated in accordance with Example 1. Table 3 shows the results
Shown in
【００５８】［比較例４］製造する環境を、温度４５
℃、湿度９５％で維持した以外は、実施例２と同様に粒
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
３に示す。[Comparative Example 4] The manufacturing environment was set to a temperature of 45.
A granular iron oxide aggregated powder was obtained in the same manner as in Example 2 except that the temperature and the temperature were maintained at 95 ° C and 95%, respectively. Various properties of this granular iron oxide aggregated powder were evaluated in accordance with Example 1. Table 3 shows the results.
【００５９】［比較例５］製造する環境を、温度２℃、
湿度１０％で維持し、ナウターミキサーを運転しながら
酸化鉄粒子を定量的に６０分間で供給し、供給終了後も
引き続き１０分間処理を行った以外は、実施例３と同様
に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３に示す。[Comparative Example 5] The manufacturing environment was set at a temperature of 2 ° C.
Except that the humidity was maintained at 10%, the iron oxide particles were quantitatively supplied for 60 minutes while operating the Nauter mixer, and the treatment was continued for 10 minutes after the supply was completed, except that the granular iron oxide was treated in the same manner as in Example 3. An agglomerated powder was obtained. Various properties of this granular iron oxide aggregated powder were evaluated in accordance with Example 1. Table 3 shows the results.
【００６０】［比較例６］製造する環境を、温度２３
℃、湿度３５％で維持し、ナウターミキサーの処理時間
を１５分間とした以外は、実施例５と同様に粒状酸化鉄
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３に示
す。[Comparative Example 6] The manufacturing environment was set to a temperature of 23.
A granular iron oxide aggregated powder was obtained in the same manner as in Example 5, except that the temperature and the humidity were maintained at 35 ° C. and the processing time of the Nauter mixer was changed to 15 minutes. Various properties of this granular iron oxide aggregated powder were evaluated in accordance with Example 1. Table 3 shows the results.
【００６１】［比較例７］製造する環境を、温度４５
℃、湿度９５％で維持した以外は、実施例８と同様に粒
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
３に示す。[Comparative Example 7] The manufacturing environment was set to a temperature of 45.
A granular iron oxide aggregate powder was obtained in the same manner as in Example 8, except that the temperature was kept at 95 ° C and the humidity was 95%. Various properties of this granular iron oxide aggregated powder were evaluated in accordance with Example 1. Table 3 shows the results.
【００６２】［比較例８］製造する環境を、温度２℃、
湿度１０％で維持した以外は、実施例８と同様に粒状酸
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３
に示す。[Comparative Example 8] The manufacturing environment was set at a temperature of 2 ° C.
A granular iron oxide aggregate powder was obtained in the same manner as in Example 8, except that the humidity was maintained at 10%. Various properties of this granular iron oxide aggregated powder were evaluated in accordance with Example 1. Table 3 shows the results
Shown in
【００６３】［比較例９］製造する環境を、温度４５
℃、湿度９５％で維持した以外は、実施例９と同様に粒
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
３に示す。[Comparative Example 9] The manufacturing environment was set to a temperature of 45.
A granular iron oxide aggregated powder was obtained in the same manner as in Example 9 except that the temperature was kept at 95 ° C. and the humidity was 95%. Various properties of this granular iron oxide aggregated powder were evaluated in accordance with Example 1. Table 3 shows the results.
【００６４】［比較例１０］製造する環境を、温度２
℃、湿度１０％で維持した以外は、実施例９と同様に粒
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
３に示す。[Comparative Example 10] The manufacturing environment was set to a temperature of 2
A granular iron oxide aggregate powder was obtained in the same manner as in Example 9 except that the temperature was maintained at 10 ° C. and the humidity was 10%. Various properties of this granular iron oxide aggregated powder were evaluated in accordance with Example 1. Table 3 shows the results.
【００６５】[0065]
【表２】 [Table 2]
【００６６】[0066]
【表３】 [Table 3]
【００６７】表２から明らかな通り、実施例１〜９で得
られた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、かつ鏡面反射率が出発原料と
比較しても良好な結果が得られ、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 obtained in Examples 1 to 9 all have a repose angle of 40 °.
Hereinafter, the apparent bulk density is 1 g / cm 3 or more, and the weight loss on heating is 0.1 g / cm 3 .
0.5 to 2% by weight, spatula angle after impact is 45
° or less, the degree of compression is 40% or less, the ratio of adhering on the inclined plate is 10% by weight or less, and a good result is obtained even when the specular reflectance is compared with the starting material. In the process, both uniform supply of the secondary particles and good dispersion of the primary particles were provided. 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.
【００６８】一方、表３に示されるように、比較例１の
酸化鉄粒子は、見掛嵩密度が低く、かつ衝撃を加えた後
のスパチュラ角、安息角、圧縮度が実施例１〜９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った。On the other hand, as shown in Table 3, the iron oxide particles of Comparative Example 1 had a low apparent bulk density, and exhibited a spatula angle, a repose angle and a compression degree after impact, which were obtained in Examples 1 to 9. And inferior in fluidity and 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 is supplied to the powder supply feeder or the hopper, adhesion or blockage often occurs, and an operation of forcibly pushing the powder is required.
【００６９】また、比較例２、４、７及び９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、一次粒子の比表面積に対して加熱
減量（水分）が多いため粒子同士の凝集力が強すぎ、圧
縮度が低めで、混練物中のムラはないものの、一次粒子
の分散性に劣るものであった。The granular iron oxide agglomerates of Comparative Examples 2, 4, 7 and 9 have good apparent bulk density, angle of repose, and spatula angle after impact, and therefore have excellent fluidity and stability. Although the powder can be supplied by heating, the heat loss (moisture) is large relative to the specific surface area of the primary particles, so the cohesive force between the particles is too strong, the compression degree is low, and there is no unevenness in the kneaded material. Was inferior in dispersibility.
【００７０】比較例３、５、８及び１０の粒状酸化鉄凝
集粉末は、一次粒子の比表面積に対して加熱減量（水
分）が少ないため、圧縮度が大きいことからも明らかな
ように、粒子同士の凝集力が弱かった。また、見掛嵩密
度が低く、かつ衝撃を加えた後のスパチュラ角、安息角
がいずれも大きく、流動性に劣るものであった。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だった。As apparent from the fact that the granular iron oxide aggregate powders of Comparative Examples 3, 5, 8 and 10 have a small heat loss (moisture) with respect to the specific surface area of the primary particles, and thus have a high degree of compression. The cohesion between them was weak. In addition, the apparent bulk density was low, the spatula angle and the angle of repose after impact were both large, and the fluidity was poor. Also,
Many of the particles adhered to the inclined plate, and the evaluation was uneven in the kneaded material and poor in the dispersibility of the primary particles. When the mixed powder with the resin was supplied to the powder supply feeder or the hopper, the powder often adhered or clogged, and it was necessary to forcibly push the powder.
【００７１】比較例６の粒状酸化鉄凝集粉末は、凝集操
作の不足により、小粒径の微粒凝集粒子もしくは凝集さ
れていない粒子が多いため、見掛嵩密度が低く、かつ衝
撃を加えた後のスパチュラ角、安息角がいずれも大き
く、流動性に劣るものであった。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、樹脂との混合
粉末を粉体供給フィーダーやホッパに供給する際、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
要だった。The granular iron oxide agglomerated powder of Comparative Example 6 has a small apparent bulk density and a large amount of unagglomerated particles due to lack of aggregating operation. Had a large spatula angle and a large angle of repose, and were poor in fluidity. 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. When the mixed powder with the resin was supplied to the powder supply feeder or the hopper, the powder often adhered or clogged, and an operation of forcibly pushing the powder was required.
【００７２】[0072]
【発明の効果】以上説明したように、本発明の粒状酸化
鉄凝集粒子及び該凝集粒子を含む粉末は、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、流動性にも優れるの
で、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であ
る。As described above, the granular iron oxide aggregated particles and the powder containing the aggregated particles of the present invention are excellent in dispersibility at the time of mixing with a resin by having moderate strength while being aggregated particles. Also, since it is excellent in handling properties and fluidity, it is suitable for applications such as material powder for magnetic toner for electrostatic copying, carrier material powder for electrostatic latent image development, and black pigment powder for paints.
フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｇ０３Ｇ 9/107 Ｇ０３Ｇ 9/10 ３１１ ３３１ Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat II (reference) G03G 9/107 G03G 9/10 311 331
Claims (6)
化鉄一次粒子が凝集しており、個数平均粒子径が３０〜
３０００μｍであり、かつ粒状酸化鉄凝集粒子の加熱減
量値をＡ（重量％）、酸化鉄一次粒子の比表面積をＢ
（ｍ2 ／ｇ）とした場合、式 （1）の関係が成立するこ
とを特徴とする粒状酸化鉄凝集粒子。 ０．０２≦Ａ／Ｂ≦０．０８ ・・・ （1）An iron oxide primary particle having a number average particle diameter of 0.05 to 1 μm is aggregated, and a number average particle diameter of 30 to 1 μm.
A (weight%) is the heat loss value of the particulate iron oxide aggregated particles, and the specific surface area of the iron oxide primary particles is B
When (m 2 / g), the particulate iron oxide agglomerated particles are characterized by satisfying the relationship of the formula (1). 0.02 ≦ A / B ≦ 0.08 (1)
載の粒状酸化鉄凝集粒子。2. The granular iron oxide aggregated particles according to claim 1, which has a degree of compression of 40% or less.
２に記載の粒状酸化鉄凝集粒子。3. The particulate iron oxide aggregate particles according to claim 1, wherein the angle of repose is 40 ° or less.
求項１、２又は３に記載の粒状酸化鉄凝集粒子。4. The granular iron oxide aggregated particles according to claim 1, wherein the apparent bulk density is 1 g / cm 3 or more.
以下である請求項１〜４のいずれかに記載の粒状酸化鉄
凝集粒子。5. A spatula angle of 45 ° after applying an impact.
The granular iron oxide aggregated particles according to any one of claims 1 to 4, which are:
上の凝集粒子の重量比率が８０重量％以上であり、請求
項１〜５のいずれかに記載の粒状酸化鉄凝集粒子を含む
ことを特徴とする粒状酸化鉄凝集粉末。6. A weight ratio of agglomerated particles having a particle size of 30 μm or more obtained by air classification is 80% by weight or more, and comprises the granular iron oxide agglomerated particles according to any one of claims 1 to 5. Agglomerated iron oxide powder.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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|---|---|
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Family
ID=15794447
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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 |
| JP2008503428A (en) * | 2004-06-24 | 2008-02-07 | ケルントナー・モンタンインドゥストリー・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング | Lamellar iron oxide (III) |
-
1999
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008503428A (en) * | 2004-06-24 | 2008-02-07 | ケルントナー・モンタンインドゥストリー・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング | Lamellar iron oxide (III) |
| 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 |
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