JPH0834617A - Black magnetic iron oxide particle-shaped powder - Google Patents
Black magnetic iron oxide particle-shaped powderInfo
- Publication number
- JPH0834617A JPH0834617A JP6192041A JP19204194A JPH0834617A JP H0834617 A JPH0834617 A JP H0834617A JP 6192041 A JP6192041 A JP 6192041A JP 19204194 A JP19204194 A JP 19204194A JP H0834617 A JPH0834617 A JP H0834617A
- Authority
- JP
- Japan
- Prior art keywords
- particle powder
- iron oxide
- magnetic
- magnetic iron
- particles
- 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.)
- Granted
Links
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、磁場１ｋＯｅにおける
磁化値σ1000（以下、単に「磁化値σ1000」という。）
が小さく、しかも、負の帯電量が大きく、黒色度に優れ
ている黒色磁性酸化鉄粒子粉末に関するものである。The present invention relates to a magnetization value σ 1000 in a magnetic field of 1 kOe (hereinafter, simply referred to as “magnetization value σ 1000 ”).
The present invention relates to a black magnetic iron oxide particle powder which has a small negative charge amount, a large negative charge amount, and an excellent blackness.
【０００２】本発明に係る黒色磁性酸化鉄粒子粉末の主
な用途は、磁性トナー用、磁性キャリア用材料粒子粉末
等である。The main uses of the black magnetic iron oxide particle powder according to the present invention are material particle powder for magnetic toner and magnetic carrier.
【０００３】[0003]
【従来の技術】黒色磁性酸化鉄粒子粉末は、黒色を呈し
ているため塗料用、印刷インキ用、ゴム・プラスチック
用の黒色着色顔料粉末として広く使用されている。2. Description of the Related Art Black magnetic iron oxide particle powder is widely used as a black color pigment powder for paints, printing inks, rubbers and plastics because it has a black color.
【０００４】また、黒色磁性酸化鉄粒子粉末のうちマグ
ネタイト粒子粉末は、強磁性粒子であることから、樹脂
中に混合分散させて複合体粒子とすることにより、静電
複写の為の磁性トナー用材料粒子粉末及び磁性キャリア
用材料粒子粉末として使用されている。Further, among the black magnetic iron oxide particle powders, the magnetite particle powder is a ferromagnetic particle. Therefore, by mixing and dispersing it in a resin to form a composite particle, a magnetic toner for electrostatic copying is used. It is used as a material particle powder and a material particle powder for magnetic carriers.
【０００５】上記いずれの分野においても高性能化、高
品質化の為の要求はとどまるところがなく、粒子粉末の
特性向上、特に、樹脂中への分散性がよいことが強く要
求されている。In any of the above-mentioned fields, there is no end to the demand for higher performance and higher quality, and there is a strong demand for improving the characteristics of the particle powder, in particular for its good dispersibility in the resin.
【０００６】磁性トナー用材料粒子粉末としてのマグネ
タイト粒子粉末に関しては、特開昭５５−６５４０６号
公報の「‥‥ＶＩＩ）樹脂との混合性がよいこと。通常
トナーの粒径は数１０μｍ以下であり、トナー中の微視
的混合度がトナーの特性にとって重要となる。‥‥」な
る記載の通りである。Regarding the magnetite particle powder as the material particle powder for magnetic toner, it should have good compatibility with "... VII) resin of JP-A-55-65406. Usually, the particle diameter of the toner is several tens of μm or less. Therefore, the degree of microscopic mixing in the toner is important for the characteristics of the toner.
【０００７】磁性キャリア用材料粒子粉末としてのマグ
ネタイト粒子粉末に関しては、特開昭６１−５３６６０
号公報の「‥‥本発明によれば、‥‥一次粒子の分散性
が向上し、磁性粉が均一に分散され、磁性現像剤粒子間
の帯電性、磁気特性の差が小さくなる。‥‥」なる記載
の通りである。Regarding the magnetite particle powder as the material particle powder for magnetic carrier, Japanese Patent Laid-Open No. 61-53660 is available.
According to the present invention, the dispersibility of primary particles is improved, the magnetic powder is uniformly dispersed, and the difference in charging property and magnetic property between magnetic developer particles is reduced. ".
【０００８】通常、マグネタイト粒子粉末は、水溶液中
から直接生成させる、所謂、湿式法により製造されてい
る。Usually, the magnetite particle powder is produced by a so-called wet method in which it is directly produced from an aqueous solution.
【０００９】湿式法とは、硫酸第一鉄等の第一鉄塩水溶
液と水酸化ナトリウム、炭酸ナトリウム等のアルカリ性
水溶液とを混合して得られたＦｅ含有沈澱物を含む懸濁
液に、６０〜１００℃の温度範囲において酸素含有ガス
を通気する方法（特公昭４４−６６８号公報等）であ
る。The wet method is a suspension containing Fe-containing precipitate obtained by mixing an aqueous solution of ferrous salt such as ferrous sulfate with an alkaline aqueous solution such as sodium hydroxide and sodium carbonate. This is a method of ventilating an oxygen-containing gas in the temperature range of -100 ° C (Japanese Patent Publication No. 44-668).
【００１０】しかし、上記湿式法により得られるマグネ
タイト粒子粉末は、磁化値σ1000が５０〜７５ｅｍｕ／
ｇと大きく、磁気的な凝集が生じやすいものであり、分
散性改良の障害となっていた。However, the magnetite particle powder obtained by the above wet method has a magnetization value σ 1000 of 50 to 75 emu /
g, which is large and tends to cause magnetic aggregation, which is an obstacle to improving dispersibility.
【００１１】そこで、樹脂中への分散性をより向上させ
るために、磁化値σ1000が小さいマグネタイト粒子粉末
が強く要求されている。特に、マグネタイト粒子粉末を
磁性トナー用材料粉末として使用する場合、高画質を実
現する為に、磁化値σ1000が小さいマグネタイト粒子粉
末が強く要求されている。この事実について以下に説明
する。Therefore, in order to further improve the dispersibility in the resin, a magnetite particle powder having a small magnetization value σ 1000 is strongly required. In particular, when magnetite particle powder is used as a material powder for magnetic toner, a magnetite particle powder having a small magnetization value σ 1000 is strongly required in order to achieve high image quality. This fact will be explained below.
【００１２】静電複写機器の小型化や高速化等の高性能
化に伴い現像剤である磁性トナーの特性向上、即ち、高
濃度現像及び高解像度が可能な磁性トナーが強く要求さ
れている。As the electrostatic copying machine becomes smaller and faster and has higher performance, there is a strong demand for magnetic toner which is a developer and has improved characteristics, that is, high density development and high resolution.
【００１３】磁性トナーの特性は、樹脂中に含有される
磁性粒子粉末の諸特性と密接な関係にあり、高濃度現像
を可能にするためには、樹脂中に含まれる磁性粒子粉末
の含有量を多量にする必要があるが、磁性粒子粉末の含
有量を多量にすると磁性粒子粉末の磁気的な凝集により
現像した後の潜像上で磁性トナーが凝集塊として残存
し、細かい潜像を忠実に再現することが難しく、高解像
度が得られなくなる。The characteristics of the magnetic toner are closely related to the characteristics of the magnetic particle powder contained in the resin. In order to enable high density development, the content of the magnetic particle powder contained in the resin is required. However, if the content of the magnetic particle powder is increased, magnetic toner remains as agglomerates on the latent image after development due to magnetic agglomeration of the magnetic particle powder, and a fine latent image is faithfully reproduced. It is difficult to reproduce, and high resolution cannot be obtained.
【００１４】この事実は、特開平４−１８４３５４号公
報の「‥‥このように信号に忠実、原稿に忠実、すなわ
ち、潜像に忠実でしかも高濃度で現像をするトナーが必
要になってきている。しかしながら、磁性体を含有する
トナーを用いて以上のような高度な要求を満足すること
は難しい。たとえば、磁性トナーの着色力を上げて高濃
度をだそうとして単に磁性体の含有量を上げれば、画像
性が悪くなり高解像度を満足することができなくなる。
なぜなら、‥‥穂の大きさはそのトナーのもつ磁気力に
関係している。磁性体を増すと穂も大きくなる。このよ
うな穂はトナーが現像した後の潜像上でも凝集力のため
凝集塊として残る傾向であり、細かい潜像を忠実に再現
することが難しくなってくる。逆に高解像度を満足する
ために、磁性体の含有量を減らし磁気凝集力を小さくさ
せることも考えられるが、着色力の減少の他に帯電量の
増加による現像性の低下、トナーの製造効率の低下など
が生じる。ならばカーボンブラックなどの着色剤の併用
により改善することが考えられるが、さらに、特に環境
依存性の悪化を招く場合があり実用化はむずかしい。‥
‥そこで、磁気力を調整して高性能のトナーを得ること
がいくつか提案されている。‥‥」及び「‥‥磁気力が
適当に小さい磁性体を適当量含有させることで、細線再
現性が向上し、潜像あるいは信号に高忠実な現像による
画質が得られる。‥‥」なる記載の通りである。This fact is described in Japanese Unexamined Patent Publication No. 4-184354, "... In this way, a toner faithful to a signal, an original, that is, a latent image and a high density developing toner is required. However, it is difficult to satisfy the above high requirements by using a toner containing a magnetic substance, for example, by increasing the coloring power of the magnetic toner to obtain a high density, the content of the magnetic substance is simply increased. If it is increased, the image quality becomes poor and the high resolution cannot be satisfied.
Because the size of the ears is related to the magnetic force of the toner. As the amount of magnetic material increases, the ears grow larger. Such ears tend to remain as agglomerates due to the aggregating force even on the latent image after the toner is developed, and it becomes difficult to faithfully reproduce a fine latent image. On the contrary, in order to satisfy high resolution, it may be possible to reduce the magnetic substance content to reduce the magnetic cohesive force, but in addition to the decrease in coloring power, the decrease in developability due to the increase in the charge amount and the toner production efficiency. Decrease. In that case, it may be improved by using a colorant such as carbon black in combination, but it may be difficult to put it into practical use because it may cause deterioration of environmental dependency. ...
Therefore, it has been proposed to adjust the magnetic force to obtain high-performance toner. "..." and "..." By containing an appropriate amount of a magnetic material having an appropriately small magnetic force, fine line reproducibility is improved, and an image quality can be obtained by developing a latent image or a signal with high fidelity. Is the street.
【００１５】そこで、高濃度現像及び高解像度が可能な
磁性トナーを得るためには、樹脂中に含まれる磁性粒子
粉末の含有量を多量にしても磁気的な凝集力が生じない
ように、磁性粒子粉末の磁化値σ1000ができるだけ小さ
く、しかも、黒色を呈していることが要求される。Therefore, in order to obtain a magnetic toner capable of high-concentration development and high resolution, even if the content of the magnetic particle powder contained in the resin is increased, magnetic cohesive force does not occur, so that the magnetic property is improved. It is required that the magnetization value σ 1000 of the particle powder be as small as possible and that it be black.
【００１６】また、磁性トナー用材料粒子粉末としての
帯電性については、特開昭６０−１１７２５９号公報の
「‥‥トナーは、感光体の種類に応じ正又は負に帯電す
るよう調整する必要があり、かかる観点からマグネタイ
ト等の磁性体粒子を考えた場合負に帯電する特性を有す
る。かかる磁性体粒子の特性は、正帯電性を付与した磁
性トナーに用いた場合、トナー表面に露出した磁性体粒
子の存在によって一つのトナー粒子表面に正帯電部分と
負帯電部分が共存したり、トナー粒子毎に帯電特性を異
にするといった現象が推定され、磁性トナーを使用する
一成分現像方式では、環境条件によって複写画像特性が
著しく異常を生じることの一つの原因と想定され、トナ
ー中の磁性体粒子を正帯電性にすることが望まれる。‥
‥」なる記載の通り、正帯電性トナーに用いる磁性粒子
は正に帯電し、負帯電性トナーに用いる磁性粒子は負に
帯電するものが好ましく、更に、各トナーの帯電量を現
像装置に適合するように、適切な範囲に調整することが
必要である。Regarding the charging property of the magnetic toner material particle powder, "... Toner of Japanese Patent Application Laid-Open No. 60-117259 needs to be adjusted so as to be charged positively or negatively depending on the type of the photoreceptor. From this point of view, when magnetic particles such as magnetite are considered, they have the property of being negatively charged.The characteristics of such magnetic particles are that when they are used in a magnetic toner having a positive charging property, the magnetic particles exposed on the toner surface are Due to the presence of body particles, a phenomenon in which positively charged portions and negatively charged portions coexist on the surface of one toner particle, or different charging characteristics for each toner particle is presumed, and in the one-component development method using magnetic toner, It is assumed that this is one of the causes of remarkably abnormal copy image characteristics due to environmental conditions, and it is desired to make the magnetic particles in the toner positively charged.
As described above, it is preferable that the magnetic particles used for the positively charged toner are positively charged and the magnetic particles used for the negatively charged toner are negatively charged. Furthermore, the charge amount of each toner is adapted to the developing device. Therefore, it is necessary to adjust to an appropriate range.
【００１７】トナーの帯電量については、前出特開平４
−１８４３５４号公報の「‥‥トナーの帯電量も適正で
ないと良好な画像が得られない。トナーの帯電量は、‥
‥絶対値が５〜５０μｃ／ｇが良い。好ましくは、５〜
４０μｃ／ｇ、さらに好ましくは５〜３０μｃ／ｇであ
る。５μｃ／ｇ未満であると、画像の鮮鋭さが悪くな
り、バックグラウンドの汚れを生じる。さらに、高温高
湿環境下では、画像濃度の低下などが問題となってく
る。５０μｃ／ｇより大きいと、静電凝集力が大きくな
り画質が低下し細線再現性などが不十分となる。特に、
低温低湿環境下ではトナー担持体との鏡映力が必要以上
に大きくなるため、画像濃度の低下などが生じる。‥
‥」なる記載の通り、トナーの帯電量を５〜４０μｃ／
ｇとすることが求められている。Regarding the charge amount of the toner, the above-mentioned Japanese Patent Laid-Open No.
No. 184354, “... A good image cannot be obtained unless the toner charge amount is appropriate.
An absolute value of 5 to 50 μc / g is good. Preferably 5 to
It is 40 μc / g, and more preferably 5 to 30 μc / g. When it is less than 5 μc / g, the sharpness of the image is deteriorated and the background is stained. Further, in a high temperature and high humidity environment, a decrease in image density becomes a problem. If it is larger than 50 μc / g, the electrostatic cohesive force becomes large, the image quality is deteriorated, and the fine line reproducibility becomes insufficient. In particular,
In a low-temperature and low-humidity environment, the mirroring power with respect to the toner carrying member becomes larger than necessary, so that the image density is lowered. ...
... ", the charge amount of the toner is 5 to 40 μc /
g is required.
【００１８】そして、同公報中の「‥‥表面を疎水化処
理された磁性体を用いることにより、トナーの帯電性を
安定化させ、‥‥」なる記載の通り、粒子表面を疎水化
処理された磁性体、即ち、粒子表面が疎水化処理された
亜鉛フェライトや亜鉛−マンガンフェライト粒子を用い
るとともに、同公報の各実施例に示されるように負帯電
性コロイダルシリカや正帯電性コロイダルシリカを外添
してトナーの帯電量を調整している。Then, as described in the above publication, "... Stabilize the chargeability of the toner by using a magnetic material whose surface is hydrophobized, ...", the particle surface is hydrophobized. In addition to using a magnetic material, that is, zinc ferrite or zinc-manganese ferrite particles whose surface is hydrophobized, negatively chargeable colloidal silica or positively chargeable colloidal silica is used as shown in each Example of the publication. In addition, the charge amount of the toner is adjusted.
【００１９】前述した湿式法により得られるマグネタイ
ト粒子の帯電量は０〜−１０μＣ／ｇ程度であり、前述
の通り、該マグネタイト粒子を樹脂中へ分散させて高濃
度現像、高解像度が可能な磁性トナーを実現することが
困難である。従って、樹脂中に含まれる磁性粒子粉末の
含有量を多量にしたり、また、カーボンブラックなどの
着色剤の併用をすることなく、高濃度現像、高解像度が
可能な磁性トナーを得るためには、磁性粒子粉末の帯電
量が大きく、しかも、黒色であることが要求される。The amount of charge of the magnetite particles obtained by the above-mentioned wet method is about 0 to -10 μC / g, and as described above, the magnetite particles are dispersed in a resin to achieve high density development and high resolution magnetic properties. It is difficult to realize the toner. Therefore, in order to obtain a magnetic toner capable of high-concentration development and high resolution without increasing the content of the magnetic particle powder contained in the resin or using a colorant such as carbon black in combination, It is required that the magnetic particle powder has a large charge amount and that it be black.
【００２０】従来、磁化値σ1000の小さい磁性粒子粉末
としては、前出特開平４−１８４３５４号公報に記載の
スピネル型結晶構造である亜鉛フェライト粒子や亜鉛−
マンガンフェライト粒子が挙げられる。また、磁化値σ
1000が非常に小さく、黒色を呈した粒子粉末としては、
特開平３−２２７６号公報に記載の黒色顔料粒子粉末が
挙げられる。Conventionally, as magnetic particle powders having a small magnetization value σ 1000 , zinc ferrite particles or zinc-containing spinel type crystal structure described in the above-mentioned JP-A-4-184354 can be used.
Examples include manganese ferrite particles. Also, the magnetization value σ
1000 is very small, as a black particle powder,
The black pigment particle powder described in JP-A-3-2276 can be used.
【００２１】[0021]
【発明が解決しようとする課題】しかし、磁化値σ1000
が小さく、しかも、負の帯電量が大きい黒色磁性酸化鉄
粒子粉末はまだ得られていない。[Problems to be Solved by the Invention] However, the magnetization value σ 1000
Of black magnetic iron oxide particles having a large negative charge amount and a large negative charge amount have not yet been obtained.
【００２２】即ち、汎用マグネタイト粒子粉末について
言えば、八面体や六面体の形状を呈する所謂粒状マグネ
タイト粒子粉末は、磁化値σ1000が５０〜７０ｅｍｕ／
ｇ程度で帯電量が−５〜−１０μＣ／ｇ程度であり、球
状マグネタイト粒子粉末は、磁化値σ1000が６０〜７５
ｅｍｕ／ｇ程度で帯電量が０〜−７μＣ／ｇ程度であ
る。That is, as for general-purpose magnetite particles, so-called granular magnetite particles having an octahedral or hexahedral shape have a magnetization value σ 1000 of 50 to 70 emu /
The charge amount is about −5 to −10 μC / g at about g, and the magnetic value σ 1000 of the spherical magnetite particles is 60 to 75.
The charge amount is about 0 to −7 μC / g at about emu / g.
【００２３】また、前掲特開平４−１８４３５４号公報
に記載の亜鉛フェライト粒子や亜鉛−マンガンフェライ
ト粒子は、磁化値σ1000が１０〜４０ｅｍｕ／ｇと小さ
く、帯電量も０〜−１５μＣ／ｇ程度であるが、後出比
較例１に示す通り、色相が黒色ではなく茶褐色である
為、磁性トナー用の材料としては黒色度が不十分であ
る。The zinc ferrite particles and zinc-manganese ferrite particles described in JP-A-4-184354 have a small magnetization value σ 1000 of 10 to 40 emu / g and a charge amount of about 0 to -15 μC / g. However, as shown in Comparative Example 1 below, since the hue is not black but dark brown, the blackness is insufficient as a material for the magnetic toner.
【００２４】また、前掲特開平３−２２７６号公報に記
載の黒色顔料粒子粉末は、チタン化合物がマグネタイト
粒子中の全Ｆｅに対してＴｉ換算で１５．０〜５０．０
原子％含まれたものであり、磁化値σ1000も０．５〜
５．０ｅｍｕ／ｇであるから、ほとんど磁性を有してお
らず、磁性トナー用や磁性キャリア用材料粒子粉末とし
ては適さない。尚、同公報には、帯電量について示唆・
教示する如き記載はない。In the black pigment particle powder described in JP-A-3-2276, the titanium compound is 15.0 to 50.0 in terms of Ti based on the total Fe in the magnetite particles.
Atomic% is included, and the magnetization value σ 1000 is 0.5-
Since it is 5.0 emu / g, it has almost no magnetism and is not suitable as a material particle powder for a magnetic toner or a magnetic carrier. In this publication, the charge amount is suggested.
There is no description to teach.
【００２５】そこで、本発明は、磁化値σ1000が小さ
く、しかも、負の帯電量が大きく、黒色度に優れている
黒色磁性酸化鉄粒子粉末を得ることを技術的課題とす
る。Therefore, a technical object of the present invention is to obtain a black magnetic iron oxide particle powder having a small magnetization value σ 1000 , a large negative charge amount, and an excellent blackness.
【００２６】[0026]
【課題を解決する為の手段】前記技術的課題は、次の通
りの本発明により達成できる。The above technical problems can be achieved by the present invention as follows.
【００２７】即ち、本発明は、磁化値σ1000が２０〜５
０ｅｍｕ／ｇであって、黒色磁性酸化鉄粒子粉末中の全
Ｆｅに対してＴｉ換算で０．５〜１０．０原子％のチタ
ン化合物を含有する黒色磁性酸化鉄粒子粉末である。That is, in the present invention, the magnetization value σ 1000 is 20 to 5
It is 0 emu / g, and is a black magnetic iron oxide particle powder containing a titanium compound in an amount of 0.5 to 10.0 atomic% in terms of Ti based on the total Fe in the black magnetic iron oxide particle powder.
【００２８】また、本発明は、帯電量が−１０〜−７０
μＣ／ｇである前記黒色磁性酸化鉄粒子粉末である。In the present invention, the charge amount is -10 to -70.
The black magnetic iron oxide particle powder is μC / g.
【００２９】本発明の構成をより詳しく説明すれば、次
の通りである。The structure of the present invention will be described in more detail as follows.
【００３０】本発明における黒色磁性酸化鉄粒子粉末の
チタン化合物の含有量は、黒色磁性酸化鉄粒子粉末中の
全Ｆｅに対してＴｉ換算で０．５〜１０．０原子％であ
る。チタン化合物の含有量が０．５原子％未満の場合に
は、磁化値σ1000が５０ｅｍｕ／ｇ以下とはならず、負
の帯電量も小さい。１０．０原子％を越える場合には、
磁化値σ1000が２０ｅｍｕ／ｇ未満となるため、磁性ト
ナー用材料粉末として好ましくない。好ましい含有量は
０．５〜８．０原子％であり、より好ましくは１．０〜
８．０原子％である。The content of the titanium compound in the black magnetic iron oxide particle powder in the present invention is 0.5 to 10.0 atom% in terms of Ti based on the total Fe in the black magnetic iron oxide particle powder. When the content of the titanium compound is less than 0.5 atom%, the magnetization value σ 1000 does not become 50 emu / g or less and the negative charge amount is small. If it exceeds 10.0 atomic%,
The magnetization value σ 1000 is less than 20 emu / g, which is not preferable as a magnetic toner material powder. The preferred content is 0.5 to 8.0 atomic%, more preferably 1.0 to
It is 8.0 atomic%.
【００３１】本発明における黒色磁性酸化鉄粒子粉末の
磁化値σ1000は、２０〜５０ｅｍｕ／ｇである。磁化値
σ1000が２０ｅｍｕ／ｇ未満の場合には、磁化値が小さ
くなりすぎるため、磁性トナー用材料粉末として好まし
くない。５０ｅｍｕ／ｇを越える場合には、磁気による
凝集力が大きくなるため、樹脂中への分散性が低下す
る。好ましくは２５〜５０ｅｍｕ／ｇであり、より好ま
しくは２５〜４８ｅｍｕ／ｇである。The magnetization value σ 1000 of the black magnetic iron oxide particle powder according to the present invention is 20 to 50 emu / g. When the magnetization value σ 1000 is less than 20 emu / g, the magnetization value becomes too small, which is not preferable as the magnetic toner material powder. When it exceeds 50 emu / g, the cohesive force by magnetism becomes large, and the dispersibility in the resin decreases. It is preferably 25 to 50 emu / g, more preferably 25 to 48 emu / g.
【００３２】本発明における黒色磁性酸化鉄粒子粉末の
用途が磁性トナーや磁性キャリア用であるときには、当
該粒子粉末の帯電量は、−１０〜−７０μＣ／ｇであ
る。帯電量が−１０μＣ／ｇ未満の場合には、通常の磁
性トナー中に含まれる磁性酸化鉄粒子粉末の含有量を３
０〜５０ｗｔ％としたときの磁性トナーは、帯電量が適
正範囲よりも低くなるので好ましくない。−７０μＣ／
ｇを越える場合には、磁性トナーとした場合の帯電量が
高くなって静電凝集が生ずることがある。好ましくは−
１０〜−６０μＣ／ｇであり、より好ましくは−１５〜
−６０μＣ／ｇである。When the use of the black magnetic iron oxide particle powder in the present invention is for a magnetic toner or magnetic carrier, the charge amount of the particle powder is -10 to -70 μC / g. When the charge amount is less than −10 μC / g, the content of the magnetic iron oxide particle powder contained in a normal magnetic toner is 3 or less.
When the magnetic toner is set to 0 to 50 wt%, the charge amount becomes lower than the proper range, which is not preferable. -70 μC /
If it exceeds g, the amount of charge of the magnetic toner becomes high and electrostatic aggregation may occur. Preferably-
10 to -60 μC / g, more preferably -15 to
-60 μC / g.
【００３３】本発明における黒色磁性酸化鉄粒子粉末の
黒色度は、明度Ｌ* 値が０〜２５であり、ａ* 値が−
１．０〜＋１．０である（Ｌ* 値及びａ* 値は、ＣＩＥ
１９７６（Ｌ* 、ａ* 、ｂ* ) 均等知覚色空間で表示し
た値である。) 。明度Ｌ* 値が２５を越える場合には、
黒色度が不足する。好ましくは０〜２０である。ａ* 値
が−１．０より負に大きい場合には、緑味が強くなって
黒色度が低下する。＋１．０を越える場合には、赤味が
強くなって黒色度が低下する。好ましくは−１．０〜＋
０．８である。The blackness of the black magnetic iron oxide particles according to the present invention has a lightness L * value of 0 to 25 and an a * value of −.
1.0 to +1.0 (L * value and a * value are CIE
1976 (L * , a * , b * ) is a value displayed in the uniform perceptual color space. ). If the lightness L * value exceeds 25,
Blackness is insufficient. It is preferably 0 to 20. When the a * value is negatively larger than -1.0, the greenness is increased and the blackness is lowered. When it exceeds +1.0, the redness is increased and the blackness is lowered. Preferably -1.0 to +
It is 0.8.
【００３４】次に、本発明に係る黒色磁性酸化鉄粒子粉
末の製造法について述べる。Next, a method for producing the black magnetic iron oxide particle powder according to the present invention will be described.
【００３５】出発原料である被処理粒子粉末としては、
マグネタイト粒子粉末やヘマタイト粒子粉末等を挙げる
ことができる。As the starting material powder to be treated,
Examples thereof include magnetite particle powder and hematite particle powder.
【００３６】先ず、被処理粒子のマグネタイト粒子粉末
は、第一鉄塩水溶液と該第一鉄塩水溶液中のＦｅ2+に
対し当量以上の水酸化アルカリ水溶液とを反応して得ら
れたｐＨ値が１０以上の水酸化第一鉄コロイドを含む懸
濁液に、酸素含有ガスを通気する酸化反応により八面体
を呈したマグネタイト粒子粉末を得る方法（特公昭４４
−６６８号公報）、第一鉄塩水溶液と該第一鉄塩水溶
液中のＦｅ2+に対し当量以下の水酸化アルカリ水溶液と
を反応して得られたｐＨ値が６〜７．５の範囲の水酸化
第一鉄コロイドを含む懸濁液に、酸素含有ガスを通気し
て部分的に酸化してマグネタイト核粒子を生成させ、次
いで、該マグネタイト核粒子及び水酸化第一鉄コロイド
を含む懸濁液にｐＨ値が８〜９．５の範囲において酸素
含有ガスを通気することにより前記マグネタイト核粒子
の成長反応を行うことにより六面体を呈したマグネタイ
ト粒子粉末を得る方法（特開平３−２０１５０９号）及
び第一鉄塩水溶液と該第一鉄塩水溶液中のＦｅ2+に対
し０．８０〜０．９９当量の水酸化アルカリとを反応し
て得られた水酸化第一鉄コロイドを含む懸濁液に、酸素
含有ガスを通気することにより、球状マグネタイト粒子
を生成させる第一段と、該第一段反応終了後、残存Ｆｅ
2+に対し１．００当量以上の水酸化アルカリを添加して
ｐＨ値が１０以上で酸化反応することにより球状を呈し
たマグネタイト粒子粉末を得る方法（特公昭６２−５１
２０８号公報）等により得られる。First, the magnetite particle powder as the particles to be treated has a pH value obtained by reacting an aqueous ferrous salt solution and an aqueous alkali hydroxide solution in an amount equal to or more than Fe 2+ in the aqueous ferrous salt solution. A method of obtaining octahedral magnetite particle powder by an oxidation reaction in which an oxygen-containing gas is passed through a suspension containing a ferrous hydroxide colloid having a ratio of 10 or more (JP-B-44).
-668 gazette), the pH value obtained by reacting an aqueous solution of ferrous salt and an aqueous solution of alkali hydroxide in an equivalent amount or less to Fe 2+ in the aqueous solution of ferrous salt is in the range of 6 to 7.5. The suspension containing ferrous hydroxide colloid is aerated with oxygen-containing gas to partially oxidize the suspension to generate magnetite core particles, and then the suspension containing the magnetite core particles and ferrous hydroxide colloid. A method of obtaining a magnetite particle powder exhibiting a hexahedron by carrying out a growth reaction of the magnetite nucleus particles by aerating an oxygen-containing gas in the suspension in the range of pH value of 8 to 9.5 (JP-A-3-201509). ) And a ferrous hydroxide colloid obtained by reacting an aqueous solution of ferrous salt with 0.80 to 0.99 equivalents of alkali hydroxide with respect to Fe 2+ in the aqueous solution of ferrous salt. Oxygen-containing gas should be passed through the suspension. Accordingly, a first stage to produce spherical magnetite particles, one stage after the completion of the reaction said residual Fe
A method of obtaining spherical magnetite particle powder by adding 1.00 equivalent or more of alkali hydroxide to 2+ and performing an oxidation reaction at a pH value of 10 or more (JP-B-62-51).
No. 208) and the like.
【００３７】次に、被処理粒子のヘマタイト粒子粉末
は、前記〜の方法により得られた各マグネタイト粒
子粉末を空気中５００〜９００℃の温度範囲で加熱して
酸化する方法等により得られる。Next, the hematite particle powder of the particles to be treated is obtained by, for example, heating each of the magnetite particle powders obtained by the above-mentioned methods in the air in the temperature range of 500 to 900 ° C. to oxidize them.
【００３８】また、水溶液中から直接ヘマタイト粒子粉
末を生成させる場合には、例えば、特公昭３８−９８５
２号公報、特公昭６０−３０１２号公報、特開昭５１−
８１９３号公報、特開昭６２−１２８９２７号公報及び
特開昭６２−１２８９３０号公報等に挙げられる方法を
採ることができる。When the hematite particle powder is produced directly from the aqueous solution, for example, Japanese Patent Publication No. 38-985.
No. 2, JP-B No. 60-3012, JP-A No. 51-
The methods described in JP-A-8193, JP-A-62-128927 and JP-A-62-128930 can be adopted.
【００３９】被処理粒子粉末としてのマグネタイト粒子
粉末やヘマタイト粒子粉末は、粒状や球状等の形態の粒
子でよく、また、大きさは０．０５〜０．３５μｍ程度
の粒子を用いることができる。被処理粒子のサイズと生
成物粒子のサイズには、相関があり、小さいサイズの被
処理粒子を用いると小さいサイズの生成物粒子が、大き
いサイズの被処理粒子を用いると大きいサイズの生成物
粒子が得られる傾向にある。The magnetite particle powder and the hematite particle powder as the particles to be treated may be particles in the form of particles or spheres, and particles having a size of about 0.05 to 0.35 μm can be used. There is a correlation between the size of the particles to be treated and the size of the product particles, and when the particles to be treated having a small size have a small product particle size, when the particles to be treated having a large size have a large size product particles. Tends to be obtained.
【００４０】本発明に係る黒色磁性酸化鉄粒子粉末は、
例えば、粒子表面をチタン化合物で被覆したマグネタイ
ト粒子粉末、又は粒子表面をチタン化合物で被覆したヘ
マタイト粒子粉末を還元して得られた還元粉末のそれぞ
れを、非酸化性雰囲気下、６５０〜８５０℃の温度で加
熱焼成した後粉砕する方法によって製造できる。The black magnetic iron oxide particle powder according to the present invention is
For example, a magnetite particle powder whose particle surface is coated with a titanium compound, or a reduced powder obtained by reducing a hematite particle powder whose particle surface is coated with a titanium compound, is treated at 650 to 850 ° C. under a non-oxidizing atmosphere. It can be manufactured by a method of calcination after heating at temperature.
【００４１】粒子表面をチタン化合物で被覆したマグネ
タイト粒子粉末を用いた場合には、磁化値σ1000が小さ
い粒子が得られやすいという点から好ましい。It is preferable to use the magnetite particle powder having the particle surface coated with the titanium compound, since particles having a small magnetization value σ 1000 are easily obtained.
【００４２】尚、粒子表面をチタン化合物で被覆したヘ
マタイト粒子粉末を用いた場合には、あらかじめ当該被
覆したヘマタイト粒子粉末を還元性雰囲気（例えば、水
素ガス等）中、３５０〜５００℃で還元して粒子表面を
チタン化合物で被覆したマグネタイト粒子とし、非酸化
性雰囲気下６５０〜８５０℃の温度で加熱焼成する。When using a hematite particle powder whose particle surface is coated with a titanium compound, the hematite particle powder coated in advance is reduced at 350 to 500 ° C. in a reducing atmosphere (for example, hydrogen gas). To form magnetite particles whose surface is coated with a titanium compound, and the particles are heated and fired at a temperature of 650 to 850 ° C. in a non-oxidizing atmosphere.
【００４３】チタン化合物としては、硫酸チタニル（Ｔ
ｉＯＳＯ4 ）、四塩化チタン、三塩化チタン等を挙げる
ことができる。As the titanium compound, titanyl sulfate (T
iOSO 4 ), titanium tetrachloride, titanium trichloride and the like.
【００４４】チタン化合物の添加量は、被処理粒子粉末
中の全Ｆｅに対してＴｉ換算で０．５〜１０．０原子％
である。チタン化合物の添加量が０．５原子％未満の場
合には、磁化値σ1000が５０ｅｍｕ／ｇ以下とはなら
ず、帯電量も小さい。１０．０原子％を越える場合に
は、磁化値σ1000が２０ｅｍｕ／ｇ未満となるため、磁
性トナー用材料粉末としては好ましくない。好ましい含
有量としては０．５〜８．０原子％であり、より好まし
くは１．０〜８．０原子％である。The amount of the titanium compound added is 0.5 to 10.0 atomic% in terms of Ti based on the total Fe in the particles to be treated.
Is. When the addition amount of the titanium compound is less than 0.5 atom%, the magnetization value σ 1000 does not become 50 emu / g or less and the charge amount is small. If it exceeds 10.0 atomic%, the magnetization value σ 1000 becomes less than 20 emu / g, which is not preferable as a magnetic toner material powder. The preferable content is 0.5 to 8.0 atom%, and more preferably 1.0 to 8.0 atom%.
【００４５】非酸化性雰囲気としては、Ｎ2 ガス等を用
いることができる。雰囲気が酸化性或いは還元性雰囲気
である場合には、目的とする黒色磁性酸化鉄粒子粉末を
得ることができない。N 2 gas or the like can be used as the non-oxidizing atmosphere. When the atmosphere is an oxidizing or reducing atmosphere, the target black magnetic iron oxide particle powder cannot be obtained.
【００４６】加熱焼成温度は６５０〜８５０℃の範囲で
ある。６５０℃未満である場合には、マグネタイト粒子
とチタン化合物の固相反応が十分生起せず、目的とする
黒色磁性酸化鉄粒子粉末が得られない。８５０℃を越え
る場合には、黒色磁性粒子粉末の粒子間の焼結が著し
く、焼結防止の効果が得られ難くなる。好ましくは６５
０〜７５０℃である。The heating and firing temperature is in the range of 650 to 850 ° C. When the temperature is lower than 650 ° C., the solid phase reaction between the magnetite particles and the titanium compound does not sufficiently occur, and the desired black magnetic iron oxide particle powder cannot be obtained. When the temperature exceeds 850 ° C., sintering between particles of the black magnetic particle powder is remarkable and it becomes difficult to obtain the effect of preventing sintering. Preferably 65
It is 0-750 degreeC.
【００４７】尚、必要により、加熱焼成前にあらかじめ
周知の焼結防止剤で被処理粒子を被覆しておいてもよ
い。この場合には、加熱焼成時における粒子及び粒子相
互間の焼結を防止することが出来、分散性に優れた黒色
磁性酸化鉄粒子粉末を得ることができる。If desired, the particles to be treated may be coated with a known sintering inhibitor before heating and firing. In this case, it is possible to prevent the particles and the sintering between the particles during heating and firing, and it is possible to obtain black magnetic iron oxide particle powder having excellent dispersibility.
【００４８】また、目的とする黒色磁性酸化鉄粒子粉末
の諸特性を損なわない焼結防止剤としては、Ａｌ、Ｓ
ｉ、Ｚｒ及びＰから選ばれた元素の１種又は２種以上か
らなる化合物を用いることができる。適度な焼結防止剤
を用いることにより帯電性を向上させることもできる。Further, as a sintering inhibitor which does not impair the various properties of the target black magnetic iron oxide particle powder, Al, S
A compound consisting of one or more elements selected from i, Zr and P can be used. The chargeability can be improved by using an appropriate sintering inhibitor.
【００４９】焼結防止剤の量は、黒色磁性酸化鉄粒子粉
末中の全Ｆｅに対して０．１〜１５．０原子％である。
十分な焼結防止効果を得る為には０．１原子％以上であ
ることが好ましく、１５．０原子％を越える場合には、
被処理粒子とチタン化合物の固相反応が十分生起しない
ため、本発明の目的とする黒色磁性酸化鉄粒子粉末を得
ることが困難である。The amount of the sintering inhibitor is 0.1 to 15.0 atomic% with respect to the total Fe in the black magnetic iron oxide particle powder.
In order to obtain a sufficient effect of preventing sintering, the content is preferably 0.1 atom% or more, and when it exceeds 15.0 atom%,
Since the solid-phase reaction between the particles to be treated and the titanium compound does not sufficiently occur, it is difficult to obtain the black magnetic iron oxide particle powder which is the object of the present invention.
【００５０】粉砕は、通常用いられるボールミル、アト
ライター、振動ミル等の粉砕機、シンプソンミックスマ
ーラー、マルチミル、ストッツミル、逆流混練機、アイ
リッヒミル、ウエットパンミル、メランジャ、ワールミ
ックス、速練機等のホイール型混練機、ブレード型混練
機等の混練機、らいかい機などを用いて行うことができ
る。The crushing is carried out using a commonly used crusher such as a ball mill, an attritor, a vibration mill, a Simpson mix muller, a multi-mill, a Stuts mill, a reverse flow kneader, an Eyrich mill, a wet pan mill, a melanger, a whirl mix, and a wheel of a quick kneader. It can be carried out using a kneading machine such as a mold kneader, a blade type kneader, or a kneader.
【００５１】本発明に係る黒色磁性酸化鉄粒子粉末を、
カップリング剤、シリコーン、高級脂肪酸等の周知の疎
水化処理剤によって被覆処理してもよい。疎水化処理剤
の被覆量は、黒色磁性粒子粉末に対して炭素元素に換算
して０．０５〜２．０重量％である。０．０１重量％未
満の場合、疎水化が不十分で分散性の改良が不十分であ
る。２．０重量％を越える場合には、疎水化処理剤の全
量が黒色磁性酸化鉄粒子表面に被覆されず、疎水化処理
剤が単独に存在することとなり、好ましくない。The black magnetic iron oxide particle powder according to the present invention is
The coating treatment may be performed with a known hydrophobizing agent such as a coupling agent, silicone, or higher fatty acid. The coating amount of the hydrophobizing agent is 0.05 to 2.0% by weight in terms of carbon element with respect to the black magnetic particle powder. If it is less than 0.01% by weight, the hydrophobicity is insufficient and the dispersibility is insufficiently improved. If it exceeds 2.0% by weight, the total amount of the hydrophobizing agent is not covered on the surface of the black magnetic iron oxide particles, and the hydrophobizing agent is present alone, which is not preferable.
【００５２】カップリング剤としては、シランカップリ
ング剤、チタネートカップリング剤、アルミネートカッ
プリング剤等、シリコーンとしては、シリコンオイル
等、高級脂肪酸としては、ステアリン酸、イソステアリ
ン酸、パルミチン酸、イソパルミチン酸、オレイン酸等
である。The coupling agent is a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, etc., the silicone is silicon oil, etc., and the higher fatty acid is stearic acid, isostearic acid, palmitic acid, isopalmitin. Acid, oleic acid and the like.
【００５３】尚、帯電性を向上させるためには、前記疎
水化処理剤の１分子当たりの被覆面積から計算される単
分子量を磁性酸化鉄粒子粉末の粒子表面に処理すること
が好ましく、特に、シランカップリング剤のうちγ−ク
ロロプロピルトリメトキシシラン、メチルトリメトキシ
シラン、メチルトリエトキシシラン等やシリコンオイル
などを、本発明で得られた黒色磁性酸化鉄粒子粉末に疎
水化処理した場合には、当該黒色磁性酸化鉄粒子粉末の
負の帯電量をより大きくすることができるので好まし
い。In order to improve the charging property, it is preferable to treat the particle surface of the magnetic iron oxide particle powder with a monomolecular weight calculated from the coating area per molecule of the hydrophobizing agent. When γ-chloropropyltrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, etc. or silicon oil among the silane coupling agents is subjected to hydrophobic treatment on the black magnetic iron oxide particle powder obtained in the present invention, It is preferable because the negative charge amount of the black magnetic iron oxide particle powder can be further increased.
【００５４】疎水化処理は乾式処理又は湿式処理のいず
れの方法でもよいが、好ましくは乾式処理で行うのがよ
く、この場合、ホイール型混練機、らいかい機、ヘンシ
ェルミキサー等を用いることができる。添加量は黒色磁
性酸化鉄粒子に対して０．２５〜５．０重量％が好まし
く、０．２５重量％未満の場合は、疎水化が不十分であ
り、また、５．０重量％を越える場合は疎水化処理剤が
全量粒子表面に吸着されず、吸着していない疎水化処理
剤が単独に存在する。The hydrophobizing treatment may be carried out by either a dry treatment or a wet treatment, but preferably it is carried out by a dry treatment. In this case, a wheel type kneader, a raider, a Henschel mixer or the like can be used. . The addition amount is preferably 0.25 to 5.0% by weight with respect to the black magnetic iron oxide particles, and if less than 0.25% by weight, the hydrophobization is insufficient and exceeds 5.0% by weight. In this case, the hydrophobizing agent is not entirely adsorbed on the particle surface, and the non-adsorbing hydrophobizing agent is solely present.
【００５５】[0055]
【作用】前述した通りの構成を採る本発明の作用は、次
の通りである。The operation of the present invention having the above-described structure is as follows.
【００５６】前掲特開平４−１８４３５４号公報に記載
される方法と同様にして得られた後出比較例１に示され
る亜鉛フェライト粒子粉末は、磁化値σ1000が３１．５
ｅｍｕ／ｇ、帯電量が−１０μＣ／ｇであり、Ｌ* 値が
２０であるが、ａ* 値が＋１．２であり、茶褐色を呈し
ている。The zinc ferrite particle powder shown in Comparative Example 1 below obtained by the same method as described in JP-A-4-184354 has a magnetization value σ 1000 of 31.5.
It has an emu / g, a charge amount of −10 μC / g, an L * value of 20, but an a * value of +1.2, which is dark brown.
【００５７】また、前掲特開平３−２２７６号公報に記
載の黒色顔料粒子粉末は、黒色のＦｅ2 ＴｉＯ5 とＦｅ
2 Ｏ3 −ＦｅＴｉＯ3 固溶体との混合組成を有する多結
晶粒子粉末であるが、磁化値σ1000は０．５〜５．０ｅ
ｍｕ／ｇ程度であり、ほとんど磁性を有していない黒色
顔料粒子粉末である。The black pigment particle powder described in JP-A-3-2276 is black Fe 2 TiO 5 and Fe.
Although it is a polycrystalline particle powder having a mixed composition with a 2 O 3 —FeTiO 3 solid solution, the magnetization value σ 1000 is 0.5 to 5.0 e.
It is about mu / g, and is a black pigment particle powder having almost no magnetism.
【００５８】本発明者は、前掲特開平３−２２７６号公
報に記載の黒色顔料粒子粉末に着目し、この顔料粒子粉
末を改善することによって、磁性トナー用として優れた
黒色磁性酸化鉄粒子粉末が得られないかと考え、更に検
討した。The present inventor has paid attention to the black pigment particle powder described in JP-A-3-2276, and by improving this pigment particle powder, an excellent black magnetic iron oxide particle powder for magnetic toner is obtained. I thought it would be possible to obtain more and studied further.
【００５９】先ず、上記黒色顔料粒子粉末の帯電量を測
定した結果、帯電量は−１５〜−３０μＣ／ｇ程度であ
った。このことからマグネタイト粒子粉末にチタン化合
物を含有させることにより帯電量を高めた。First, as a result of measuring the charge amount of the black pigment particle powder, the charge amount was about -15 to -30 μC / g. From this, the charge amount was increased by incorporating the titanium compound into the magnetite particle powder.
【００６０】次に、マグネタイト粒子粉末に含有させる
チタン化合物の含有量と磁化値σ1000との関係について
種々検討した結果、図１に示すように磁性酸化鉄粒子粉
末中の全Ｆｅに対してＴｉ換算で０．５〜１０．０原子
％のチタン化合物を含有させた場合には、磁化値σ1000
が２０〜５０ｅｍｕ／ｇの磁性酸化鉄粒子粉末が得られ
ることが分かった。Next, as a result of various studies on the relationship between the content of the titanium compound contained in the magnetite particle powder and the magnetization value σ 1000 , as shown in FIG. 1, Ti was calculated for all Fe in the magnetic iron oxide particle powder. When 0.5 to 10.0 atomic% of the titanium compound is included, the magnetization value σ 1000
It was found that a magnetic iron oxide particle powder having a viscosity of 20 to 50 emu / g was obtained.
【００６１】また、図２に示すように磁性酸化鉄粒子粉
末中の全Ｆｅに対してＴｉ換算で０．５原子％を越える
チタン化合物を含有させた場合には、磁性酸化鉄粒子粉
末の帯電量が−１０μＣ／ｇを越える磁性酸化鉄粒子粉
末が得られることが分かった。Further, as shown in FIG. 2, when a titanium compound exceeding 0.5 atom% in terms of Ti is contained with respect to all Fe in the magnetic iron oxide particle powder, the magnetic iron oxide particle powder is charged. It was found that a magnetic iron oxide particle powder having an amount exceeding -10 μC / g was obtained.
【００６２】更に、磁性酸化鉄粒子粉末中の全Ｆｅに対
してＴｉ換算で０．５〜１０．０原子％のチタン化合物
を含有させた場合の磁性酸化鉄粒子粉末の黒色度は、明
度Ｌ* 値が０〜２５の範囲であり、ａ* 値が−１．０〜
＋１．０の範囲であることから、黒色度にも優れている
ことが分かった。Further, the blackness of the magnetic iron oxide particle powder when the titanium compound is contained in an amount of 0.5 to 10.0 atom% in terms of Ti based on the total Fe in the magnetic iron oxide particle powder has a lightness L. * Value is in the range of 0 to 25, and a * value is from -1.0 to
From the range of +1.0, it was found that the blackness was also excellent.
【００６３】以上の結果から、粒状マグネタイト粒子粉
末の磁化値σ1000が５０〜７０ｅｍｕ／ｇで帯電量が−
５〜−１０μＣ／ｇ程度であったものが、磁化値σ1000
が２０〜４５ｅｍｕ／ｇで帯電量が−２０〜−４０μＣ
／ｇ程度となった。From the above results, the magnetization value σ 1000 of the granular magnetite particle powder is 50 to 70 emu / g and the charge amount is −
What was about 5 to -10 μC / g, the magnetization value σ 1000
Is 20 to 45 emu / g and the charge amount is -20 to -40 μC
/ G.
【００６４】また、球状マグネタイト粒子粉末の磁化値
σ1000が６０〜７５ｅｍｕ／ｇで帯電量が０〜−７μＣ
／ｇ程度であったものが、磁化値σ1000が２０〜４５ｅ
ｍｕ／ｇで帯電量が−１５〜−３５μＣ／ｇ程度となっ
た。The spherical magnetite particles have a magnetization value σ 1000 of 60 to 75 emu / g and a charge amount of 0 to -7 μC.
/ G was about, but the magnetization value σ 1000 was 20 to 45e
The charge amount was about −15 to −35 μC / g at mu / g.
【００６５】このように、被処理粒子であるマグネタイ
ト粒子粉末に比べ、磁化値σ1000を３０ｅｍｕ／ｇ程度
低下させることができ、負の帯電量も２倍以上高くする
ことができたのである。As described above, the magnetization value σ 1000 could be reduced by about 30 emu / g, and the negative charge amount could be doubled or more, as compared with the magnetite particle powder as the particles to be treated.
【００６６】即ち、本発明に係る黒色磁性酸化鉄粒子粉
末は、磁化値σ1000が小さく、しかも、負の帯電量が大
きく、黒色度にも優れている粒子粉末である。従って、
樹脂中に分散混合して磁性トナーとする場合の磁性トナ
ー中に含まれる磁性酸化鉄粒子粉末の含有量を多くする
ことができるので、高濃度現像及び高解像度の負に帯電
させる磁性トナー用材料粒子粉末としても優れている。That is, the black magnetic iron oxide particle powder according to the present invention is a particle powder having a small magnetization value σ 1000 , a large negative charge amount, and an excellent blackness. Therefore,
Since the content of the magnetic iron oxide particle powder contained in the magnetic toner when dispersed and mixed in a resin to form a magnetic toner can be increased, a high-concentration development and high-resolution negatively charged material for magnetic toner It is also excellent as a particle powder.
【００６７】尚、前掲特開平３−２２７６号公報の「‥
‥マグネタイト粒子粉末、ヘマタイト粒子粉末として
は、粒状、球状、針状等いかなる形態の粒子でもよく、
‥‥使用することができる。‥‥」なる記載及び「‥‥
粒子表面をチタン化合物で被覆したマグネタイト粒子粉
末、マグネタイト粒子粉末とチタン化合物との混合粉末
又は粒子表面をチタン化合物で被覆したヘマタイト粒子
粉末を還元して得られた還元粉末のそれぞれを非酸化性
雰囲気下７００℃以上の温度で加熱焼成した後粉砕する
方法によって得られる。‥‥」なる記載の通り、針状粒
子も使用することができ、また、マグネタイト粒子粉末
とチタン化合物との混合粉末を非酸化性雰囲気下７００
℃以上の温度で加熱焼成しても得られるとされている。Incidentally, "...
The magnetite particle powder and hematite particle powder may be particles of any shape such as granular, spherical, needle-like,
Can be used. "..." and "...
A magnetite particle powder whose particle surface is coated with a titanium compound, a mixed powder of a magnetite particle powder and a titanium compound, or a reduced powder obtained by reducing a hematite particle powder whose particle surface is coated with a titanium compound is used in a non-oxidizing atmosphere. It is obtained by a method of calcination after heating and baking at a temperature of 700 ° C. or lower. Needle-shaped particles can be used as described above, and a mixed powder of magnetite particle powder and a titanium compound can be used in a non-oxidizing atmosphere at 700
It is said that it can be obtained by heating and firing at a temperature of ℃ or more.
【００６８】しかし、後出比較例４に示す通り、被処理
粒子を針状のマグネタイト粒子粉末とした場合には、磁
化値σ1000が３６．０ｅｍｕ／ｇ、帯電量が−１５μＣ
／ｇであり、ａ* 値が＋０．８であるが、Ｌ* 値が２７
であるので、明度Ｌ* 値が大きく、黒色度に問題がある
から、本発明の目的とする黒色磁性酸化鉄粒子粉末が得
られない。また、得られた黒色磁性酸化鉄粒子粉末の磁
場１ｋＯｅにおける残留磁化値σｒが２５ｅｍｕ／ｇと
大きいので、磁気凝集が起こり易く、分散不良になるこ
ともあり、好ましくない。However, as shown in Comparative Example 4 below, when the particles to be treated were magnetite particles in the form of needles, the magnetization value σ 1000 was 36.0 emu / g and the charge amount was −15 μC.
/ G and the a * value is +0.8, but the L * value is 27.
Therefore, since the lightness L * value is large and the blackness is problematic, the black magnetic iron oxide particle powder intended by the present invention cannot be obtained. In addition, since the remanent magnetization value σr of the obtained black magnetic iron oxide particle powder in a magnetic field of 1 kOe is as large as 25 emu / g, magnetic aggregation is likely to occur, resulting in poor dispersion, which is not preferable.
【００６９】また、後出比較例５に示す通り、マグネタ
イト粒子粉末とチタン化合物との混合粉末を、非酸化性
雰囲気下７００℃の温度で加熱焼成した場合には、磁化
値σ1000が４５．０ｅｍｕ／ｇ、帯電量が−１２μＣ／
ｇであり、Ｌ* 値が２３であるが、ａ* 値が＋１．２で
あり、赤味が強いので黒色度に問題があるから、本発明
の目的とする黒色磁性酸化鉄粒子粉末は得られない。As shown in Comparative Example 5 below, when a mixed powder of magnetite particle powder and a titanium compound was heated and fired at a temperature of 700 ° C. in a non-oxidizing atmosphere, the magnetization value σ 1000 was 45. 0 emu / g, charge amount -12 μC /
g, L * value is 23, a * value is +1.2, and there is a problem with blackness due to a strong reddish color. Therefore, the black magnetic iron oxide particle powder of the present invention is obtained. I can't.
【００７０】また、本発明における所定範囲内のチタン
化合物をマグネタイト粒子と混合した場合には、チタン
化合物とマグネタイト粒子とを均一に混合することは難
しく、得られた磁性酸化鉄粒子粉末を用いて磁性トナー
とした場合には、均一に分散させることができないので
磁性現像剤粒子間の帯電性、磁気特性の差を小さくする
ことが困難である。Further, when a titanium compound within the predetermined range in the present invention is mixed with magnetite particles, it is difficult to uniformly mix the titanium compound and magnetite particles, and the obtained magnetic iron oxide particle powder is used. When the magnetic toner is used, it is difficult to uniformly disperse it, and therefore it is difficult to reduce the difference in charging property and magnetic property between the magnetic developer particles.
【００７１】[0071]
【実施例】次に、実施例及び比較例により、本発明を説
明する。The present invention will be described below with reference to examples and comparative examples.
【００７２】尚、以下の実施例及び比較例における粒子
の形状は、透過型電子顕微鏡及び走査型電子顕微鏡によ
り観察したものである。The shapes of the particles in the following examples and comparative examples were observed with a transmission electron microscope and a scanning electron microscope.
【００７３】Ｔｉ量は、誘導結合プラズマ発光分光分析
装置（ＩＣＡＰ−５７５、（株）日本ジャーレル・アッ
シュ製）で測定した値である。The Ti amount is a value measured by an inductively coupled plasma emission spectroscopic analyzer (ICAP-575, manufactured by Nippon Jarrell Ash Co., Ltd.).
【００７４】磁性粒子粉末の磁気特性は、「振動試料型
磁力計ＶＳＭ−３Ｓ−１５」（東英工業（株）製）を用
いて磁場１ｋＯｅの下で測定した値である。The magnetic property of the magnetic particle powder is a value measured under a magnetic field of 1 kOe using a "vibrating sample magnetometer VSM-3S-15" (manufactured by Toei Industry Co., Ltd.).
【００７５】帯電量は、ブローオフ測定法により求め
た。測定機としてＴＢ−２００（東芝ケミカル社製）を
用い、キャリアはＴＥＦＶ２００／３００（パウダーテ
ック社製）を用いて磁性酸化鉄粒子粉末の濃度を５％と
し、混合時間を３０分間として測定した。The charge amount was determined by the blow-off measuring method. TB-200 (manufactured by Toshiba Chemical Co., Ltd.) was used as a measuring machine, TEFV200 / 300 (manufactured by Powder Tech Co.) was used as a carrier, and the concentration of the magnetic iron oxide particles was set to 5%, and the mixing time was 30 minutes.
【００７６】黒色度は、Ｌ* （明度）及びａ* 値で示さ
れ、これらは、測色用試験片を光源分光測色計ＭＳＣ−
ＩＳ−２Ｄ（スガ試験機（株）製）を用いてＨｕｎｔｅ
ｒのＬａｂ空間によりＬ* 値及びａ* 値をそれぞれ測色
し、ＣＩＥ（国際照明委員会：Ｃｏｍｍｉｓｓｉｏｎ
Ｉｎｔｅｒｎａｔｉｏｎａｌｅ ｄｅ １’Ｅｃｌａｉ
ｒａｇｅ）１９７６（Ｌ* 、ａ* 、ｂ* ）均等知覚色空
間に従って表示した値で示した。Blackness is indicated by L * (brightness) and a * values, which are obtained by measuring a colorimetric test piece with a light source spectrocolorimeter MSC-
Hunte using IS-2D (Suga Test Instruments Co., Ltd.)
The L * value and the a * value are measured by the Lab space of r respectively, and CIE (International Commission on Illumination: Commission)
International de 1'Eclai
rage) 1976 (L * , a * , b * ) shown by the value displayed according to the uniform perceptual color space.
【００７７】黒色度の測定用試料片は、チタン化合物を
含有する黒色磁性酸化鉄粒子粉末０．５ｇとヒマシ油
０．５ｃｃをフーバー式マーラーで練ってペースト状と
し、このペーストにクリヤラッカー４．５ｇを加え混練
し塗料化して、キャストコート紙上に６ｍｉｌのアプリ
ケータを用いて塗布することによって得た。A sample piece for measuring blackness was prepared by kneading 0.5 g of black magnetic iron oxide particle powder containing a titanium compound and 0.5 cc of castor oil with a Hoover type muller to form a paste. 5 g was added and kneaded to form a paint, which was obtained by applying it onto cast-coated paper using a 6-mil applicator.
【００７８】＜黒色磁性酸化鉄粒子の製造＞ 実施例１〜１１、比較例１〜６；<Production of Black Magnetic Iron Oxide Particles> Examples 1 to 11 and Comparative Examples 1 to 6;
【００７９】実施例１ 平均径０．２μｍであって磁化値σ1000が６６．０ｅｍ
ｕ／ｇ、帯電量が−４μＣ／ｇである球状マグネタイト
粒子粉末１０ｋｇをＴｉＯＳＯ4 を０．０６５ｍｏｌ含
有する水溶液中 (磁性酸化鉄粒子粉末中の全Ｆｅに対し
てＴｉ換算で５．０原子％に相当する。) に分散させ、
次いで、該混合液中にＮａＯＨを添加・中和してｐＨ値
を９．０にし、粒子表面にチタンの水酸化物を沈着させ
た後、希硫酸を加えてｐＨ値を７．０にし、濾別、水
洗、乾燥して粒子表面がチタンの水酸化物で被覆されて
いる球状黒色磁性酸化鉄粒子粉末を得た。Example 1 The average diameter was 0.2 μm and the magnetization value σ 1000 was 66.0 em.
u / g, 10 kg of spherical magnetite particle powder having a charge amount of -4 μC / g in an aqueous solution containing 0.065 mol of TiOSO 4 (5.0 atomic% in terms of Ti with respect to all Fe in the magnetic iron oxide particle powder) Equivalent to.),
Then, NaOH was added to the mixed solution and neutralized to adjust the pH value to 9.0, and after titanium hydroxide was deposited on the surface of the particles, diluted sulfuric acid was added to adjust the pH value to 7.0. It was filtered, washed with water, and dried to obtain spherical black magnetic iron oxide particle powder whose particle surface is coated with titanium hydroxide.
【００８０】上記粒子表面がチタンの水酸化物で被覆さ
れている球状黒色磁性酸化鉄粒子粉末１０ｋｇをＮ2 ガ
ス流下７００℃で６０分間加熱焼成した後、シンプソン
ミックスマーラー（サンドミルＭＰＵＶ−２：（株）松
本鋳造鉄工所製）で線荷重３０ｋｇ／ｃｍで６０分間処
理して、黒色磁性酸化鉄粒子粉末を得た。10 kg of spherical black magnetic iron oxide particles whose surfaces were coated with titanium hydroxide were heated and calcined at 700 ° C. for 60 minutes under N 2 gas flow, and then Simpson Mix Mahler (Sandmill MPUV-2 :( Manufactured by Matsumoto Foundry Co., Ltd.) with a linear load of 30 kg / cm for 60 minutes to obtain a black magnetic iron oxide particle powder.
【００８１】この黒色磁性酸化鉄粒子粉末のＴｉ量は、
粒子粉末中の全Ｆｅに対して５．２原子％であった。ま
た、磁化値σ1000が３５．０ｅｍｕ／ｇ、帯電量が−２
１μＣ／ｇであり、Ｌ* 値が１８、ａ* 値が＋０．４で
あった。The amount of Ti in this black magnetic iron oxide particle powder is
It was 5.2 atom% with respect to the total Fe in the particle powder. Further, the magnetization value σ 1000 is 35.0 emu / g, and the charge amount is -2.
1 * C / g, L * value was 18, and a * value was +0.4.
【００８２】比較例１ 内容積１８０ｌの気泡酸化型反応塔に、ＮａＯＨ濃度１
８３ｇ／ｌの溶液４０ｌを投入し、次いで、Ｆｅ2+濃度
１３５ｇ／ｌの溶液３６ｌを、当該ＮａＯＨ溶液中に攪
拌しながら加えて中和を行った（残留ＮａＯＨは約４．
７ｇ／ｌであった。）。これに水酸化亜鉛を溶解したｐ
Ｈ値が１１．３の溶液を５０ｌ（Ｚｎ濃度が４０ｇ／ｌ
である。）加え、Ｆｅ2+濃度が約３９ｇ／ｌの反応液を
準備した。Comparative Example 1 In a bubble oxidation type reaction column having an internal volume of 180 l, a NaOH concentration of 1 was added.
40 l of 83 g / l solution was added, and then 36 l of Fe 2+ concentration 135 g / l solution was added to the NaOH solution with stirring to neutralize (residual NaOH was about 4.
It was 7 g / l. ). P in which zinc hydroxide was dissolved
50l of solution with H value 11.3 (Zn concentration 40g / l
Is. ) In addition, a reaction liquid having an Fe 2+ concentration of about 39 g / l was prepared.
【００８３】上記反応液の温度８０℃を維持しながら空
気を１０ｌ／ｍｉｎの割合で吹き込み酸化反応を行っ
た。反応は７時間で終了した。次いで、この反応沈殿物
を濾別、水洗、乾燥して亜鉛フェライト粒子粉末を得
た。While maintaining the temperature of the reaction solution at 80 ° C., air was blown at a rate of 10 l / min to carry out the oxidation reaction. The reaction was completed in 7 hours. Then, the reaction precipitate was filtered, washed with water, and dried to obtain zinc ferrite particle powder.
【００８４】上記亜鉛フェライト粒子粉末１０ｋｇをシ
ンプソンミックスマーラー（サンドミルＭＰＵＶ−２：
（株）松本鋳造鉄工所製）で線荷重３０ｋｇ／ｃｍで６
０分間処理した。10 kg of the above zinc ferrite particle powder was added to Simpson Mix Marlar (Sandmill MPUV-2:
6 with a linear load of 30 kg / cm manufactured by Matsumoto Foundry Co., Ltd.
It was processed for 0 minutes.
【００８５】得られた亜鉛フェライト粒子粉末は、磁化
値σ1000が３１．５ｅｍｕ／ｇ、帯電量が−１０μＣ／
ｇであり、Ｌ* 値が２０、ａ* 値が＋１．２であり、茶
褐色を呈していた。The obtained zinc ferrite particle powder has a magnetization value σ 1000 of 31.5 emu / g and a charge amount of −10 μC /
g, the L * value was 20, and the a * value was +1.2, which was a dark brown color.
【００８６】実施例２〜１１、比較例２〜６ 被処理粒子粉末の種類、チタン化合物による被覆工程に
おけるチタン化合物の種類、添加量及び中和時のｐＨ
値、焼結防止剤による処理の有無、種類及び量、熱処理
工程における温度及び時間並びに粉砕処理における線荷
重を種々変化させた以外は、実施例１と同様にして磁性
酸化鉄粒子粉末を得た。尚、比較例５は、球状マグネタ
イト粒子粉末とＴｉＯＳＯ4 粉末とを乾式で混合した
後、熱処理を行った。Examples 2 to 11 and Comparative Examples 2 to 6 Type of powder to be treated, type of titanium compound in coating step with titanium compound, addition amount and pH at neutralization
Magnetic iron oxide particle powder was obtained in the same manner as in Example 1 except that the value, the presence or absence of the treatment with the sintering inhibitor, the type and amount, the temperature and time in the heat treatment step, and the linear load in the pulverization treatment were changed variously. . In Comparative Example 5, the spherical magnetite particle powder and the TiOSO 4 powder were dry-mixed and then heat-treated.
【００８７】この時の主要製造条件及び諸特性を表１及
び表２に示す。The main manufacturing conditions and various characteristics at this time are shown in Tables 1 and 2.
【００８８】[0088]
【表１】 [Table 1]
【００８９】[0089]
【表２】 [Table 2]
【００９０】＜黒色磁性酸化鉄粒子粉末の疎水化処理＞ 実施例１２〜１５；<Hydrophobic treatment of black magnetic iron oxide particles> Examples 12 to 15;
【００９１】実施例１２ 実施例１で得られた磁化値σ1000が３５．０ｅｍｕ／
ｇ、帯電量が−２０μＣ／ｇであり、Ｌ* 値が１８、ａ
* 値が＋０．５である黒色磁性酸化鉄粒子粉末１０ｋｇ
をシンプソンミックスマーラー（サンドミルＭＰＵＶ−
２：（株）松本鋳造鉄工所製）に投入し、シランカップ
リング剤（γ−クロロプロピルトリメトキシシラン：Ａ
−１４３：日本ユニカー製）を１００ｇを添加してで線
荷重３０ｋｇ／ｃｍで６０分間処理した。Example 12 The magnetization value σ 1000 obtained in Example 1 is 35.0 emu /
g, the charge amount is −20 μC / g, and the L * value is 18, a
* 10kg of black magnetic iron oxide particle powder with a value of +0.5
The Simpson Mix Mahler (Sandmill MPUV-
2: Charged to Matsumoto Foundry Iron Works Co., Ltd., and a silane coupling agent (γ-chloropropyltrimethoxysilane: A
-143: manufactured by Nippon Unicar Co., Ltd.) was added and treated with a linear load of 30 kg / cm for 60 minutes.
【００９２】得られた疎水化処理された黒色磁性酸化鉄
粒子粉末は、磁化値σ1000が３４．５ｅｍｕ／ｇ、帯電
量が−５５μＣ／ｇであり、Ｌ* 値が１７、ａ* 値が＋
０．５であった。The resulting hydrophobically treated black magnetic iron oxide particle powder had a magnetization value σ 1000 of 34.5 emu / g, a charge amount of −55 μC / g, an L * value of 17, and an a * value of +
It was 0.5.
【００９３】実施例１３〜１５ 疎水化処理剤の種類を変えた以外は実施例１２と同様に
して疎水化処理された黒色磁性酸化鉄粒子粉末を得た。Examples 13 to 15 Hydrophobized black magnetic iron oxide particles were obtained in the same manner as in Example 12 except that the kind of the hydrophobizing agent was changed.
【００９４】この時の諸特性を表３に示す。Table 3 shows various characteristics at this time.
【００９５】[0095]
【表３】 [Table 3]
【００９６】[0096]
【発明の効果】本発明に係る黒色磁性酸化鉄粒子粉末
は、前出実施例にも示す通り、磁化値σ1000が小さく、
しかも、負の帯電量が大きく、黒色度に優れている黒色
磁性酸化鉄粒子粉末であるから、樹脂中への分散性にも
優れているので、負に帯電させる磁性トナー用、磁性キ
ャリア用材料粒子粉末として好適である。The black magnetic iron oxide particle powder according to the present invention has a small magnetization value σ 1000 as shown in the above Examples,
Moreover, since it is a black magnetic iron oxide particle powder that has a large amount of negative charge and is excellent in blackness, it is also excellent in dispersibility in resin, so it is a material for magnetic toner and magnetic carrier that is negatively charged. It is suitable as a particle powder.
【００９７】また、本発明に係る黒色磁性酸化鉄粒子粉
末は、磁性トナー中に含まれる磁性酸化鉄粒子粉末の含
有量を多くすることができるので、高濃度現像及び高解
像度の負に帯電させる磁性トナー用材料粒子粉末として
好適である。Further, since the black magnetic iron oxide particle powder according to the present invention can increase the content of the magnetic iron oxide particle powder contained in the magnetic toner, it can be negatively charged with high density development and high resolution. It is suitable as a material particle powder for magnetic toner.
【００９８】また、本発明に係る黒色磁性酸化鉄粒子粉
末は、黒色度に優れているから塗料用、印刷インキ用、
ゴム・プラスチック用の黒色着色顔料粉末としても使用
できる。Since the black magnetic iron oxide particle powder according to the present invention is excellent in blackness, it can be used for paints, printing inks,
It can also be used as a black color pigment powder for rubber and plastics.
【図１】 磁性酸化鉄粒子粉末のチタン化合物の含有量
と磁化値σ1000との関係を示す図である。FIG. 1 is a diagram showing a relationship between a content of a titanium compound in magnetic iron oxide particle powder and a magnetization value σ 1000 .
【図２】 磁性酸化鉄粒子粉末のチタン化合物の含有量
と帯電量との関係を示す図である。FIG. 2 is a diagram showing the relationship between the content of a titanium compound in the magnetic iron oxide particle powder and the charge amount.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｈ０１Ｆ 1/00 (72)発明者 好澤 実 広島県広島市中区舟入南４丁目１番２号戸 田工業株式会社創造センター内 (72)発明者 内田 直樹 広島県広島市中区舟入南４丁目１番２号戸 田工業株式会社創造センター内 (72)発明者 片元 勉 広島県広島市中区舟入南４丁目１番２号戸 田工業株式会社創造センター内─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification number Reference number within the agency FI Technical display location H01F 1/00 (72) Inventor Minoru Yoshizawa 4-1-2, Funairi Minami, Naka-ku, Hiroshima City, Hiroshima Prefecture No. Toda Kogyo Co., Ltd. Creation Center (72) Inventor Naoki Uchida 4-1-2, Funarinami, Naka-ku, Hiroshima City, Hiroshima Prefecture Toda Kogyo Co., Ltd. Creation Center (72) Inventor Tsutomu Katamoto Hiroshima City, Hiroshima Prefecture 4-1-2 Funaruinami, Naka-ku Toda Industry Co., Ltd. Creative Center
Claims (2)
０〜５０ｅｍｕ／ｇであって、黒色磁性酸化鉄粒子粉末
中の全Ｆｅに対してＴｉ換算で０．５〜１０．０原子％
のチタン化合物を含有する黒色磁性酸化鉄粒子粉末。1. A magnetization value σ 1000 at a magnetic field of 1 kOe is 2
0 to 50 emu / g, 0.5 to 10.0 atomic% in terms of Ti with respect to all Fe in the black magnetic iron oxide particle powder
Black magnetic iron oxide particle powder containing the titanium compound of.
請求項１記載の黒色磁性酸化鉄粒子粉末。2. The black magnetic iron oxide particle powder according to claim 1, which has a charge amount of −10 to −70 μC / g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19204194A JP3551204B2 (en) | 1994-07-22 | 1994-07-22 | Black magnetic iron oxide particle powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19204194A JP3551204B2 (en) | 1994-07-22 | 1994-07-22 | Black magnetic iron oxide particle powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0834617A true JPH0834617A (en) | 1996-02-06 |
| JP3551204B2 JP3551204B2 (en) | 2004-08-04 |
Family
ID=16284630
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19204194A Expired - Lifetime JP3551204B2 (en) | 1994-07-22 | 1994-07-22 | Black magnetic iron oxide particle powder |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3551204B2 (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997042125A1 (en) * | 1996-05-08 | 1997-11-13 | Mitsui Mining & Smelting Company, Ltd. | Black ultrafine magnetite particles and process for preparing the same |
| JP2004053863A (en) * | 2002-07-19 | 2004-02-19 | Canon Inc | Magnetic toner |
| US6824943B2 (en) | 2002-02-28 | 2004-11-30 | Dainippon Ink And Chemicals, Inc. | Toner for electrostatic image development |
| JP2005200285A (en) * | 2004-01-19 | 2005-07-28 | Toda Kogyo Corp | Iron-based black particle powder and black toner containing the iron-based black particle powder |
| JP2005225731A (en) * | 2004-02-13 | 2005-08-25 | Toda Kogyo Corp | Ferrous black particle powder and black toner containing the same |
| JP2006027921A (en) * | 2004-07-12 | 2006-02-02 | Mitsui Mining & Smelting Co Ltd | Black compound iron oxide particle |
| JP2006291151A (en) * | 2005-04-15 | 2006-10-26 | Toda Kogyo Corp | Iron base black particle powder for toner |
| JP2007089563A (en) * | 2005-08-31 | 2007-04-12 | Hitachi Metals Ltd | Method for extracting nucleic acid, method for detecting cancer cell, and magnetic bead |
| US7368211B2 (en) | 2004-10-08 | 2008-05-06 | Canon Kabushiki Kaisha | Magnetic toner |
| WO2021200746A1 (en) * | 2020-03-31 | 2021-10-07 | パウダーテック株式会社 | Ferrite powder, ferrite resin composition, resin molded body, electronic component, electronic equipment, or electronic equipment housing |
-
1994
- 1994-07-22 JP JP19204194A patent/JP3551204B2/en not_active Expired - Lifetime
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997042125A1 (en) * | 1996-05-08 | 1997-11-13 | Mitsui Mining & Smelting Company, Ltd. | Black ultrafine magnetite particles and process for preparing the same |
| US6824943B2 (en) | 2002-02-28 | 2004-11-30 | Dainippon Ink And Chemicals, Inc. | Toner for electrostatic image development |
| JP2004053863A (en) * | 2002-07-19 | 2004-02-19 | Canon Inc | Magnetic toner |
| JP2005200285A (en) * | 2004-01-19 | 2005-07-28 | Toda Kogyo Corp | Iron-based black particle powder and black toner containing the iron-based black particle powder |
| JP4497285B2 (en) * | 2004-01-19 | 2010-07-07 | 戸田工業株式会社 | Iron-based black particle powder and black toner containing the iron-based black particle powder |
| JP2005225731A (en) * | 2004-02-13 | 2005-08-25 | Toda Kogyo Corp | Ferrous black particle powder and black toner containing the same |
| JP4534125B2 (en) * | 2004-02-13 | 2010-09-01 | 戸田工業株式会社 | Iron-based black particle powder and black toner containing the iron-based black particle powder |
| JP2006027921A (en) * | 2004-07-12 | 2006-02-02 | Mitsui Mining & Smelting Co Ltd | Black compound iron oxide particle |
| CN100458574C (en) * | 2004-10-08 | 2009-02-04 | 佳能株式会社 | Magnetic toner |
| US7368211B2 (en) | 2004-10-08 | 2008-05-06 | Canon Kabushiki Kaisha | Magnetic toner |
| JP2006291151A (en) * | 2005-04-15 | 2006-10-26 | Toda Kogyo Corp | Iron base black particle powder for toner |
| JP2007089563A (en) * | 2005-08-31 | 2007-04-12 | Hitachi Metals Ltd | Method for extracting nucleic acid, method for detecting cancer cell, and magnetic bead |
| WO2021200746A1 (en) * | 2020-03-31 | 2021-10-07 | パウダーテック株式会社 | Ferrite powder, ferrite resin composition, resin molded body, electronic component, electronic equipment, or electronic equipment housing |
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