JPS59111159A

JPS59111159A - Electrophotographic ferrite carrier

Info

Publication number: JPS59111159A
Application number: JP57219589A
Authority: JP
Inventors: Tsutomu Iimura; 飯村　勉; Kiyoshi Eguchi; 江口　潔
Original assignee: Hitachi Metals Ltd
Current assignee: Proterial Ltd
Priority date: 1982-12-15
Filing date: 1982-12-15
Publication date: 1984-06-27

Abstract

PURPOSE:To obtain a spherical electrophotographic ferrite carrier having long life and high electric resistance and forming an image superior in sharpness etc. by heat-treating a ferrite contg. Fe2O3 as an essential component and MgO and MnO in a specified molar ratio. CONSTITUTION:Starting materials are weighed and mixed to obtain a ferrite composed of 1-40mol% MgO, 5-30mol% MnO, and 45-70mol% Fe2O3, or a ferrite having a part of this compsn. substd. by a monovalent or higher valent metal, such as ZnO. This powder mixture is calcined, pulverized, granulated, burned at 1,100-1,400 deg.C, and finally heat-treated at about 700 deg.C for about 2hr in a nitrogen atm. to obtain the intended electrophotographic ferrite carrier. The obtained carrier has 10<2>-10<13>OMEGA-cm resistivity, >=10emu/g saturation magnetization, >=10mu magnetic permeability, >=100 deg.C Curie. temp., and >=1,000g/cm<2> particle strength.

Description

【発明の詳細な説明】本発明は電気抵抗を改良した電子写真用トナーキＡＩリ
アに関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an electrophotographic toner cartridge AI rear with improved electrical resistance.

電子写真の現像法としては、カスケード現像法。The cascade development method is used as a development method for electrophotography.

磁気ブラシ現像法やイの他の方法があるが、キャリアど
しで要求される特性は適当な摩擦帯電性をもち］−ナー
粒子を吸引すること、、緻密であり粒子の強度が十分で
粒の破壊を生じさせない、粒子が流動↑１に冨むこと、
粒子が均一であること、表面の状態が湿度等によって種
々の特性が変らず安定してＣること、引張り，圧縮強度
を有すること、また適切な飽和磁化，透磁率あるいは保
磁力を有する等である。特に電気抵抗は摩擦帯電と密接
に関係し、画（り：１、ζ性に人さく影ツ２を及ぼすこ
とが知られでいる。There are magnetic brush development methods and other methods, but the characteristics required for the carriers are appropriate triboelectric charging properties, suction of the toner particles, dense particles with sufficient strength, and Particles are concentrated in a flow ↑1 that does not cause destruction of
The particles must be uniform, the surface condition must be stable without changing various properties due to humidity, etc., it must have tensile and compressive strength, and it must have appropriate saturation magnetization, magnetic permeability, or coercive force. be. In particular, electrical resistance is closely related to triboelectrification, and is known to have an adverse effect on image resistance (1) and ζ property (2).

イＩ、来１−ナー：（トリア粒子として種々の材オ′シ
が使用されてさく−いるか、最も多く用いられたものと
して３′）、杓がある。′ｉ久粉の表面を適当な処理を
して使用しているか、艮０１間便用りると粒子の表面が
物理的あるいは化学的に変（シシ、１−ナーがｆ”ｌ　
ｒ４シてしまったりあるいは使用環境の湿度に敏感にな
一〕て画１象の鮮明度がうすれたりし寿命はり、σいと
いう欠点がある。(1) A variety of materials have been used as the thorium particles, and 3' is the most commonly used material. If the surface of the powder has been properly treated, or if it is used, the surface of the particles may be physically or chemically changed.
It has the disadvantage that it may become unstable or become sensitive to the humidity of the environment in which it is used, causing the sharpness of the image to fade, resulting in a long service life.

また、キＡ・リアとして酸１ヒ物磁・１′１材＄！１で
ある７１　ノで１・を用いることはｆｉ間昭５２−、５
　Ｇ　５３　Ｇ等で報）ｊｉされている７ノく、ｒａｔ
来のフＴライ１−キトリアは画像時１′１あるいは寿命
の点て必ずしも渦足しうるちの−ではない。Also, as Ki A/Rear, Acid 1 Hibimagi/1'1 material $! The use of 1 in 71 ノ, which is 1, is fi period 52-5.
G 53 Reported in G etc.) 7th place, rat
The conventional fly T fly 1-kitria is not necessarily vortex-added in terms of image time 1'1 or lifespan.

本発明は電気抵抗を任意に変えることにＪ：り印字潤度
を増し、これら従来の電子写真用１−ナールＡ・リアの
欠点をなくし両ｍｒ　’Ｍ性の１暴れた、また寿命の艮
い主１１リアを提供するものＣある。The present invention improves the printing moisture by arbitrarily changing the electrical resistance, eliminates the drawbacks of the conventional 1-Nar A/R for electrophotography, and improves both the MR 'M property and the life expectancy. There are those who provide 11 rears.

本発明において、電気抵抗率は１０２０ｃｍ以上が良く
、本範囲外では摩擦帯重重を適当な艙に制御できず、ま
た湿度等の影響を受け１′）すく目的とする鮮明な画像
を得ることは困ｔ「である。また飽和磁化の値は１０　
ｅｍｌｌ／’（］以」＝が適りて、この値より小さい場
合には磁気ロールとの吸着力は落ち目標どり゛るｉｆｆ
　ｎＪｌな画色（を冑ることは回動である。In the present invention, the electrical resistivity is preferably 1020 cm or more; outside this range, the friction band weight cannot be controlled to an appropriate level, and it is affected by humidity etc. 1') It is difficult to obtain the desired clear image. The value of saturation magnetization is 10.
If emll/'(] or '= is true and is smaller than this value, the adhesion force with the magnetic roll will drop and the target will be reached.
It is a rotation to remove the nJl color.

またｌｊＣが１０００ｃ以上では粒子そのものが磁石の
ｔ’ｌ買を持ち、種々の部品に付着し良い画像は得られ
ない。また透磁率μが１０以下では磁気ロールｌ＼の反
応が悪くなり画質に影響を与える。Moreover, if ljC is 1000c or more, the particles themselves have the t'l resistance of the magnet and adhere to various parts, making it impossible to obtain a good image. Further, if the magnetic permeability μ is less than 10, the response of the magnetic roll l\ becomes poor, which affects the image quality.

１メ下実施例によって詳細に説明する。This will be explained in detail using one example below.

実１進　１列　１ −Ｅ／ｌ、化ＣＬｉ　！Ｉ　Ｏ２３％、　Ｍ　ＩＩ　Ｏ
２３％、Ｆｅ２０３５４９６どなるように秤吊し混合し
た。Real decimal 1 sequence 1 -E/l, CLi! IO23%, M II O
23% Fe2035496 was mixed on a scale.

混合機としては、ボールミル、振動ミル、ミキリー等を
用いた。混合粉は８００〜１２００℃で仮焼をした。１
縦焼した試わ１は、ボールミル、振動ミル。As a mixer, a ball mill, a vibration mill, a millimeter, etc. were used. The mixed powder was calcined at 800 to 1200°C. 1
Vertical firing trial 1 was done using a ball mill and a vibration mill.

アトライター等の粉砕機を用い粉砕した。粉砕後の粒径
は、空気透過法を用い測定した結果、平均粒径で０．３
・−２，０μであった。It was pulverized using a pulverizer such as Attritor. The particle size after pulverization was measured using an air permeation method, and the average particle size was 0.3.
・It was -2.0μ.

Ｈｌ：５）伜した試オ′）↓はバインターとしてＰ、Ｖ
、Ａ（ボｌ」ビニルアルコノル）の水溶１ｆｆｌ（Ｐ、
Ｖ、Ａの出どしては０．０５〜５．０ｗｔ％）を使用し
、スプレードライＶ−，ニーグー、ミキサー哲の）１５
粒器を用い槓粒した。Hl:5) Improved test O') ↓ is P, V as a binder
, 1 ffl aqueous solution of A (vinylalkonol) (P,
V, A (0.05 to 5.0 wt%) was used, and spray-dried V-, Nygoo, Mixer Tetsu's) 15
It was granulated using a granulator.

次に迅粒扮を１１００−１４００°Ｃて焼成した。焼成
方法どしてはアルミナ等の容器に漬粒扮を入れて焼成し
ても良いが、多量に容器に入れて焼成する場合には焼成
の際に粒成長し、粒同士が接合する場合があるためロー
ターキルン等で試お１を回転しながら焼成しても良い。Next, the cypress was fired at 1100-1400°C. As for the firing method, pickled grains may be placed in a container such as alumina and fired, but if a large amount is placed in a container and fired, the grains may grow during firing and the grains may join together. Therefore, it is also possible to bake the sample while rotating it in a rotor kiln or the like.

次に　７００°Ｃて　２時間窒素中雰囲気て熱速埋を行
ζ蒙った。このようにして得られたフェライトの特↑１
を第１表に示す。Then, it was subjected to thermal rapid burial at 700°C for 2 hours in a nitrogen atmosphere. Characteristics of the ferrite obtained in this way ↑1
are shown in Table 1.

第１表この球状フエライ１−をトナーキ（・リアとして使用し
、コピーした結果、従来の鉄粉主１１リアは約１０．０
００Ｊ、７．フエライ１−キレリア５０，０００枚に対
し本発明キＡｊリアを用いることにより７０．（ＩＱＱ
−１００，０００枚の鮮明なコピーが可能であった。Table 1 As a result of using this spherical ferrite 1- as a toner key (rear) and copying it, the conventional iron powder main 11 rear is approximately 10.0
00J, 7. 70. by using the present invention Kirelia for 50,000 pieces of Ferai 1-Kirelia. (IQQ
-100,000 clear copies were possible.

実施例２モル比てＭ　ＩＪ　０２３％、ｔｖ１ｎ０２３％、Ｚｎ
０４％。Example 2 M IJ 023%, tv1n023%, Zn in molar ratio
04%.

Ｆｅ２０３５０％となるように秤量し、実施例１と同様
４丁処理により、はぼ同特性をもつ球状のフエライ１〜
を作成した。この球状フェライトをフエライ１〜キトリ
アとしてコピー試験した結果、実施例１と同様の］ピー
性能を得た。Weighed so that Fe20350% was obtained, and processed 4 pieces in the same manner as in Example 1 to obtain spherical Fe-rays 1 to 3 with approximately the same characteristics.
It was created. As a result of a copy test of this spherical ferrite as Ferrai 1 to Kitria, the same pea performance as in Example 1 was obtained.

以トの如く、本発明フエライ１−キャリアは従来使用さ
れている鉄粉キャリアに比べ、高抵抗でかつ長寿命であ
ることが判明し、電子写真用の現像材１１どして卓越し
た効果を示しイの工業的応用価値は人である。As described above, the Ferray 1-carrier of the present invention has been found to have higher resistance and longer life than conventionally used iron powder carriers, and has excellent effects as a developing material 11 for electrophotography. The industrial application value of the invention is people.

Claims

【特許請求の範囲】１、モル比でＭｇＯ１％・〜４０％、ＭｎＱ５％・”３
０％、ｒ４；２０＜４５％〜７０％又は該組成の一部を
１１ｉ１１ｉ以１−の金属の１種まだは２種以上で買換
してなるフエライ［・を熱処理することにより、電気抵
抗を１０２・〜１０１３Ω−ａｍに改良したことを特徴
とする球状の電子写真用フエライ［・キＡ・リア。２、特許請求の範囲第１項記載のものにおいて、飽和磁
イヒが１００ｍＵ、’ＣＩ以上Ｃ′あることを特徴とＪ
る電子写真用フエライ１〜キトリア。３、特許請求の範囲第１項記載のものにおいて、透磁率
μｍ０以上であることを特徴どする電子写真用フェライ
ト・キ１！リア。４、特許請求の範囲第１項記載のものに、１３いて、キ
ュリー渇麻王Ｃが１００℃以上であることを特徴とする
電子写真用フェライトキャリア５、特許請求の範囲第１項記載のものにおいて、粒子の
強度か１０００　ｇ／ａｍ’以」−であることを特徴ど
する電子写真用フエライトキＡｌリア。６、特許請求の範囲第１項から第５項記載のものにおい
て、粒子の表面を酸化させたことを特徴とする電子写真
用フェライ４・主１１リア。７、特許請求の範囲第１項から第５項記載のものにおい
て、粒子の表面を樹脂等で被覆したことを特徴とする電
子写真用フェライトキャリア。[Claims] 1. MgO 1%・~40%, MnQ 5%・”3 in molar ratio
0%, r4; 20 < 45% to 70% or a part of the composition is replaced with one or more metals from 11i11i to 2 or more by heat-treating the electrical resistance. This is a spherical electrophotographic magnet characterized by improved resistance to 102.about.1013 Ω-am. 2. The product described in claim 1, characterized in that the saturation magnetism is 100 mU, 'C' or more than 'CI'.
Ferrai 1 to Kitria for electrophotography. 3. A ferrite for electrophotography according to claim 1, characterized in that it has a magnetic permeability of μm0 or more. rear. 4. The ferrite carrier for electrophotography, which is characterized in that it has a Curie C of 100° C. or higher; 13. The carrier as described in claim 1; A ferrite crystal for electrophotography, characterized in that the strength of the particles is 1000 g/am' or more. 6. Ferrite 4/main 11 rear for electrophotography according to claims 1 to 5, characterized in that the surface of the particles is oxidized. 7. A ferrite carrier for electrophotography according to claims 1 to 5, characterized in that the surfaces of the particles are coated with a resin or the like.