JPS63184764A - Carrier for electrophotographic developer and production thereof - Google Patents
Carrier for electrophotographic developer and production thereofInfo
- Publication number
- JPS63184764A JPS63184764A JP61284270A JP28427086A JPS63184764A JP S63184764 A JPS63184764 A JP S63184764A JP 61284270 A JP61284270 A JP 61284270A JP 28427086 A JP28427086 A JP 28427086A JP S63184764 A JPS63184764 A JP S63184764A
- Authority
- JP
- Japan
- Prior art keywords
- carrier
- oxide
- hematite
- magnetite
- electrophotographic developer
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 20
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 19
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052595 hematite Inorganic materials 0.000 claims abstract description 15
- 239000011019 hematite Substances 0.000 claims abstract description 15
- 229910052802 copper Inorganic materials 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 10
- 239000012298 atmosphere Substances 0.000 claims abstract description 8
- 229910052745 lead Inorganic materials 0.000 claims abstract description 8
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 8
- 229910052718 tin Inorganic materials 0.000 claims abstract description 8
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 7
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 7
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 6
- 229910052742 iron Inorganic materials 0.000 claims abstract description 6
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 6
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 5
- 229910052782 aluminium Inorganic materials 0.000 claims abstract 4
- 238000010304 firing Methods 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- UCNNJGDEJXIUCC-UHFFFAOYSA-L hydroxy(oxo)iron;iron Chemical compound [Fe].O[Fe]=O.O[Fe]=O UCNNJGDEJXIUCC-UHFFFAOYSA-L 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 4
- 229910000859 α-Fe Inorganic materials 0.000 abstract description 11
- 238000003756 stirring Methods 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 4
- 239000011159 matrix material Substances 0.000 abstract description 2
- 230000008021 deposition Effects 0.000 abstract 1
- 239000000969 carrier Substances 0.000 description 12
- 230000005415 magnetization Effects 0.000 description 10
- 239000002245 particle Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 238000011161 development Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000011572 manganese Substances 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 239000011575 calcium Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000011133 lead Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- -1 clays Chemical compound 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229940005740 hexametaphosphate Drugs 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 108091008695 photoreceptors Proteins 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/10—Developers with toner particles characterised by carrier particles
- G03G9/107—Developers with toner particles characterised by carrier particles having magnetic components
- G03G9/108—Ferrite carrier, e.g. magnetite
- G03G9/1085—Ferrite carrier, e.g. magnetite with non-ferrous metal oxide, e.g. MgO-Fe2O3
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Developing Agents For Electrophotography (AREA)
Abstract
Description
【発明の詳細な説明】
(産業上の利用分野)
本発明は、電子写真の現像剤、詳しくは電子複写機の2
成分磁気ブラシ現像剤のキャリア及びその製造方法に関
するものである。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to an electrophotographic developer, specifically a developer for an electrophotographic copying machine.
The present invention relates to a carrier for a component magnetic brush developer and a method for manufacturing the same.
(従来の技術)
電子写真の2成分磁気ブラシ現像剤用のキャリアとして
は、従来鉄粉やフェライトが用いられている。(Prior Art) Iron powder and ferrite have conventionally been used as carriers for two-component magnetic brush developers for electrophotography.
キャリアには、106〜10I5Ω・ω程度の高い比抵
抗が求められるため、鉄粉キャリアは表面を酸化するか
樹脂で被覆するなどして用いられる。このような表面の
酸化層は、現像剤としての使用中の攪拌による摩擦や衝
撃によって摩耗し易く、また鉄粉と樹脂被覆の密着性は
十分でないことが多くはがれが生じ易い。従って長時間
の使用に耐えないことが鉄粉キャリアの欠点となってい
る。Since the carrier is required to have a high specific resistance of about 10 6 to 10 I 5 Ω·ω, the iron powder carrier is used by oxidizing the surface or coating it with a resin. Such an oxidized layer on the surface is easily abraded by friction and impact caused by stirring during use as a developer, and the adhesion between the iron powder and the resin coating is often insufficient and peeling is likely to occur. Therefore, the disadvantage of iron powder carriers is that they cannot withstand long-term use.
また、キャリアの寿命を左右するもうひとつの要素がト
ナーフィルミングである。現像中のキャリアの重要な役
割は、トナーに均一な摩擦電荷を付与し、感光体の潜像
部へ搬送することであるが、現像剤の攪拌によってキャ
リアとトナーが相互に衝突をくり返す際に、衝撃で破壊
したトナー粒の一部がキャリア表面を覆うようにして付
着して膜を形成することがある。このような現像をトナ
ーフィルミングという。トナーフィルミングを生じると
、キャリアのトナーに対する摩擦帯電能力が低下し、ト
ナー搬送能力が不足して画像濃度が低下してしまう。ト
ナーフィルミングの発生には現像時の攪拌抵抗が関与し
ている。攪拌抵抗が増すと、キャリアとトナー間の衝突
時の圧力が増して、トナーフィルミングを生じ易くなる
。そこで、キャリアを長寿命化するためには、攪拌抵抗
を下げる必要がある。鉄粉キャリアは比重が大きいため
攪拌抵抗が大きく、トナーフィルミングを生じ易い。従
って、この観点からも鉄粉キャリアは長時間の使用に耐
えないと言える。Another factor that affects the lifespan of the carrier is toner filming. The important role of the carrier during development is to impart a uniform frictional charge to the toner and transport it to the latent image area of the photoreceptor. However, when the carrier and toner repeatedly collide with each other due to agitation of the developer, In addition, some of the toner particles destroyed by the impact may adhere to the carrier surface to form a film. This type of development is called toner filming. When toner filming occurs, the carrier's ability to triboelectrically charge toner decreases, resulting in insufficient toner conveying ability and a decrease in image density. The agitation resistance during development is involved in the occurrence of toner filming. When the stirring resistance increases, the pressure at the time of collision between the carrier and the toner increases, making toner filming more likely to occur. Therefore, in order to extend the life of the carrier, it is necessary to lower the stirring resistance. Since the iron powder carrier has a high specific gravity, the stirring resistance is large and toner filming is likely to occur. Therefore, from this point of view as well, it can be said that iron powder carriers cannot withstand long-term use.
また、鉄粉キャリアの飽和磁化は約200emu/g程
度であるが、このような高い飽和磁化のキャリアを用い
ると、現像時の磁気ブラシの強度が過大となって、現像
されたトナー像を硬いブラシで掃くことによってコピー
画面に刷毛目状の痕跡が残るいわゆるブラシマークを生
じることが多い。In addition, the saturation magnetization of iron powder carrier is about 200 emu/g, but if a carrier with such high saturation magnetization is used, the strength of the magnetic brush during development becomes excessive, making the developed toner image hard. Sweeping with a brush often leaves so-called brush marks on the copy screen.
(発明が解決しようとする問題点)
鉄粉キャリアのこれらの欠点を解消するために、特公昭
56−52305号公報などに見られるフェライトキャ
リアが使用されている。フェライトキャリアは高比抵抗
で内部まで均一で化学的に安定な酸化物であることに加
えて、鉄粉キャリアの見掛密度約4.5g/cm3に対
して約2.5g/c+n″と軽量であるため、長寿命で
あることを特徴とし、更に飽和磁化が40〜60en+
u/g程度であり、コピー印画にブラシマークが無く、
高解像度であることを特徴とする。しかしながら、この
フェライトキャリアは、特公昭56−52305号公報
、特開昭58−171059号°公報などに見られるよ
うに、ニッケル、マンガン、銅などの高価な金属を含有
するため、コスト面で問題がある。フェライトに類似の
物質で安価なマグネタイトを使用したキャリアも特開昭
60−458号公報に開示されているが、マグネタイト
キャリアは軽量で長寿命ではあっても、低比抵抗のため
樹脂被覆を要し、約92emu/gと高飽和磁化のため
磁気ブラシ強度が過大となってブラシマークを生じるな
どの欠点もあった。(Problems to be Solved by the Invention) In order to eliminate these drawbacks of iron powder carriers, ferrite carriers such as those disclosed in Japanese Patent Publication No. 56-52305 have been used. In addition to being a chemically stable oxide with high resistivity and uniform internally, ferrite carriers are lightweight at approximately 2.5 g/c+n'' compared to the apparent density of iron powder carriers, which is approximately 4.5 g/cm3. Therefore, it is characterized by long life, and has a saturation magnetization of 40 to 60 en+.
It is about U/g, there are no brush marks on the copy print,
It is characterized by high resolution. However, as seen in Japanese Patent Publication No. 56-52305 and Japanese Patent Application Laid-open No. 58-171059, this ferrite carrier has problems in terms of cost because it contains expensive metals such as nickel, manganese, and copper. There is. A carrier using magnetite, which is a material similar to ferrite and is inexpensive, is also disclosed in JP-A-60-458, but although magnetite carriers are lightweight and have a long life, they require resin coating due to their low resistivity. However, due to the high saturation magnetization of approximately 92 emu/g, the strength of the magnetic brush becomes excessive, resulting in the formation of brush marks.
本発明は、マグネタイトキャリアの低比抵抗、高飽和磁
化の欠点を解消し、更に軽量で長寿命であるとともに、
安価にして優秀な特性を持つ電子写真現像剤用キャリア
及びその製造方法を提供することを目的とするものであ
る。The present invention eliminates the drawbacks of magnetite carriers such as low resistivity and high saturation magnetization, and is also lightweight and has a long life.
The object of the present invention is to provide a carrier for an electrophotographic developer that is inexpensive and has excellent properties, and a method for producing the same.
(問題点を解決するための手段)
本発明の電子写真現像剤用キャリアは、主としてマグネ
タイト(Fe+0*)からなる母権中に、Si。(Means for Solving the Problems) The electrophotographic developer carrier of the present invention contains Si in a matrix mainly composed of magnetite (Fe+0*).
Ca、 At、 Mg+ Fe+ L Sb+ Sn、
pb、 Cu、 Mnの1種または2種以上からなる
非磁性酸化物相が散在していることを特徴とするもので
ある。このとき、散在とは粒界析出、表面析出などを含
む概念である。Ca, At, Mg+ Fe+ L Sb+ Sn,
It is characterized in that a non-magnetic oxide phase consisting of one or more of pb, Cu, and Mn is scattered therein. At this time, the term "scattering" is a concept that includes grain boundary precipitation, surface precipitation, and the like.
また、本発明の電子写真現像剤用キャリアの製造方法は
、ヘマタイト(F13103)を主成分とする酸化鉄粉
末に、St、 Ca、 AI、 Mg+ Fe+ V、
Sb、 Sn+Pb、 Cu、 Mnの1種または2
種以上からなる非磁性酸化物粉末を混合・造粒し、酸素
濃度5vol%以下の不活性雰囲気中焼成温度1000
℃〜1400℃で熱処理することにより、ヘマタイトの
みを還元してマグネタイトとすることを特徴とするもの
である。Further, the method for producing a carrier for an electrophotographic developer of the present invention includes adding St, Ca, AI, Mg+Fe+V, to iron oxide powder containing hematite (F13103) as a main component.
One or two of Sb, Sn+Pb, Cu, Mn
Mix and granulate non-magnetic oxide powder consisting of seeds or more, and sinter at a temperature of 1000 in an inert atmosphere with an oxygen concentration of 5 vol% or less.
It is characterized in that only hematite is reduced to magnetite by heat treatment at a temperature of 1400°C to 1400°C.
(作 用)
このようなSi+ Ca、八L Mg、 Fe、 V、
Sb、 Sn。(Function) Such Si + Ca, 8L Mg, Fe, V,
Sb, Sn.
Pb、 Cu、 Mnの1種又は2種以上からなる酸化
物非磁性相の存在により、キャリアの粒子全体としての
単位重量あたりの飽和磁化は、マグネタイトの約92e
mu/gから30〜80en+u/g程度まで低下する
。Due to the presence of the oxide nonmagnetic phase consisting of one or more of Pb, Cu, and Mn, the saturation magnetization per unit weight of the carrier particles as a whole is about 92e of magnetite.
It decreases from mu/g to about 30 to 80 en+u/g.
また、St+ Ca、 AI+ Mg、 Fe+ v、
sb、 Sn、Pb、 Cu。Also, St+ Ca, AI+ Mg, Fe+ v,
sb, Sn, Pb, Cu.
Mnからなる酸化物非磁性相は同時に高電気抵抗である
ため、微細に分散あるいは粒界や表面に存在することに
よってマグネタイトによる電気伝導径路を細かく分断し
て、キャリアの比抵抗をマグネタイトキャリアの約10
4Ω・備から10h〜10′2Ω・1種度に向上させる
。The oxide nonmagnetic phase consisting of Mn also has high electrical resistance, so by being finely dispersed or existing at grain boundaries or on the surface, it finely divides the electrical conduction path by magnetite, reducing the specific resistance of the carrier to about the same as that of the magnetite carrier. 10
Increase from 4Ω to 10h to 10'2Ω/1 degree.
また、5to2. Cab、 AltOs+ Mgo、
VzOs+ 5bzO3゜Snug、 pbo、 C
ub、 MnOなどの非磁性相は比重が約2.6〜4.
0g/cm3であり、マグネタイトの約5.2g/c−
3より小さいため、本発明の電子写真現像剤用キャリア
の見掛密度は1.8〜2.2g/cm’となり約2.5
g/cI113のフェライトキャリアより軽量であり、
トナーフィルミングが生じにり<、長時間にわたって高
品位のコピー画質を保つことができる。Also, 5to2. Cab, AltOs+ Mgo,
VzOs+ 5bzO3゜Snug, pbo, C
Non-magnetic phases such as ub and MnO have a specific gravity of about 2.6 to 4.
0g/cm3, and about 5.2g/c- of magnetite.
3, the apparent density of the carrier for electrophotographic developer of the present invention is 1.8 to 2.2 g/cm', which is approximately 2.5
It is lighter than a ferrite carrier with a g/cI of 113,
Toner filming does not occur, and high quality copy images can be maintained for a long time.
(実施例)
本発明の電子写真現像剤用キャリアは、主としてヘマタ
イトからなる酸化鉄とSi、 Cat AI+ Mg+
Fe、ν+ Sb+ Sn、 pb、 Cu、 Mnの
1種または2種以上からなる非磁性酸化物粉末を混合し
、不活性雰囲気で焼成し、ヘマタイトのみを還元してマ
グネタイトとすることにより得られる。以下にその具体
的な製造方法を述べる。(Example) The carrier for an electrophotographic developer of the present invention contains iron oxide mainly consisting of hematite and Si, Cat AI+ Mg+
It is obtained by mixing nonmagnetic oxide powders consisting of one or more of Fe, ν+Sb+Sn, pb, Cu, and Mn, firing in an inert atmosphere, and reducing only hematite to form magnetite. The specific manufacturing method will be described below.
粒径0.1〜10μmの主としてヘマタイトからなる酸
化鉄に粒径0.1〜10μmのSi、 Ca、 AI+
MLFe、 V、 Sb、 Sn、 Pb、 Cu、
Mnの1種又は2種以上からなる非磁性酸化物粉末を
好ましくは0.01〜40wtXの範囲で加え、分散剤
を添加した水に分散させて、アトライターミル、ボール
ミルなどを用いて湿式粉砕・混合しスラリーを得る。非
磁性酸化物粉末のうちSt 、 Ca r Al源とし
ては、カオリナイト、珪砂、粘土類、シリカ粉末、アル
ミナ粉末などが適し、又他の金属源としては各々の酸化
物が適する。分散材としては、ヘキサメタリン酸アンモ
ニウム塩、ヒロリン酸アンモニウム塩、ポリカルボン酸
アンモニウム塩などが適する。得られたスラリーにバイ
ンダを加えてスプレードライヤで乾燥・造粒する。バイ
ンダにはポリビニルアルコールを0.1〜1轄tχ用い
る。Si, Ca, AI+ with a particle size of 0.1 to 10 μm to iron oxide mainly composed of hematite with a particle size of 0.1 to 10 μm
MLFe, V, Sb, Sn, Pb, Cu,
A non-magnetic oxide powder consisting of one or more types of Mn is preferably added in a range of 0.01 to 40 wtX, dispersed in water with a dispersant added, and wet-pulverized using an attritor mill, a ball mill, etc.・Mix to obtain slurry. Among the non-magnetic oxide powders, kaolinite, silica sand, clays, silica powder, alumina powder, etc. are suitable as the St 2 , Car Al source, and each oxide is suitable as the other metal source. Suitable dispersants include ammonium hexametaphosphate, ammonium hyrophosphate, ammonium polycarboxylate, and the like. A binder is added to the resulting slurry, which is dried and granulated using a spray dryer. Polyvinyl alcohol is used as a binder in an amount of 0.1 to 1 tχ.
造粒した原料を、不活性雰囲気で焼成することによって
例えばSiO□、 Cab、 A1gO+などの非磁性
相をそのままに、ヘマタイトのみマグネタイトに還元・
焼結し、マグネタイト中に非磁性相が分散あるいは粒界
や表面に存在した組織とする。このとき、Sing、
Cab、 Al2O5などの非磁性相とへマタイトまた
は還元したマグネタイトが反応しないためには、焼成温
度を1400℃以下とすることが必要である。また、そ
の後の実験の結果わかったことであるが、キャリアとし
て必要な飽和磁化を得るためにはへマタイトの還元を十
分に行うことが肝要で、少なくとも1000℃以上の焼
成温度とすべきである。従って、焼成温度範囲は100
0〜1400℃である。焼成雲囲気は、窒素またはアル
ゴンの不活性ガスを用いるが、必要に応じて5volχ
程度までの酸素を雰囲気に混合して、ヘマタイトの還元
率を制御して飽和磁化を下げることができる。この場合
、酸素濃度が5volχを超えるとヘマタイトの還元が
十分行われず、キャリアとして必要な飽和磁化が得られ
ない。By firing the granulated raw material in an inert atmosphere, only hematite is reduced to magnetite while leaving non-magnetic phases such as SiO□, Cab, and AlgO+ intact.
It is sintered to form a structure in which a nonmagnetic phase is dispersed in magnetite or exists at grain boundaries or on the surface. At this time, Sing,
In order to prevent hematite or reduced magnetite from reacting with non-magnetic phases such as Cab and Al2O5, it is necessary to set the firing temperature to 1400° C. or lower. In addition, as a result of subsequent experiments, it was found that in order to obtain the saturation magnetization required as a carrier, it is important to sufficiently reduce hematite, and the firing temperature should be at least 1000°C or higher. . Therefore, the firing temperature range is 100
The temperature is 0 to 1400°C. An inert gas such as nitrogen or argon is used for the firing cloud atmosphere, but if necessary, 5 volχ
By mixing up to a certain amount of oxygen into the atmosphere, the reduction rate of hematite can be controlled to lower the saturation magnetization. In this case, if the oxygen concentration exceeds 5 vol.chi., hematite will not be sufficiently reduced, and the saturation magnetization required as a carrier will not be obtained.
前述の酸化鉄に混合する非磁性成分の量は、その酸化物
相を微細に分散させる場合には10〜40−tχが好適
であり、又粒界析出させる程度で良い場合には0.01
〜10wtχが好適である。The amount of the non-magnetic component to be mixed with the iron oxide is preferably 10-40-tχ when the oxide phase is finely dispersed, and 0.01-tχ when it is sufficient to cause grain boundary precipitation.
~10wtχ is suitable.
また、前述の非磁性酸化物相を微細に分散させる場合で
あって該酸化物相が高融点である場合には、マグネタイ
トのみからなるキャリアに比較して焼結性が低下してい
て結晶粒の成長が抑えられているので、この焼結性を補
うために前述の酸化物中低融点の酸化物を添加すること
は好適である。In addition, when the non-magnetic oxide phase mentioned above is finely dispersed and the oxide phase has a high melting point, the sinterability is lower than that of a carrier consisting only of magnetite, resulting in crystal grains. Since the growth of oxides is suppressed, it is preferable to add an oxide having a low melting point among the oxides mentioned above in order to compensate for this sinterability.
この場合、低融点酸化物としてはCub、 Vt08s
5btosSnO*+ PbOが適当である。添加量
は0.1〜5wtχが適当であるが、中でも1.0〜2
.Owtχが最適である。In this case, the low melting point oxide is Cub, Vt08s
5btosSnO*+PbO is suitable. The appropriate amount of addition is 0.1 to 5 wtχ, especially 1.0 to 2 wtχ.
.. Owtχ is optimal.
スJJLL
鉄鋼酸洗廃液から回収された酸化鉄(平均粒径0.8μ
m、ヘマタイト99.42)に、第1表に示す非磁性成
分を加えて試料1〜4とした。SJJLL Iron oxide recovered from steel pickling waste (average particle size 0.8μ
Samples 1 to 4 were prepared by adding the non-magnetic components shown in Table 1 to hematite 99.42).
第1表
1)平均粒径3μmまでアトマイザで粉砕配合した原料
をヘンシェルミキサで予備混合した後、水30kgと分
散剤としてポリカルボン酸アンモニウム塩150g(0
,5wtχ)を加え、アトライター中1 で60分間粉
砕・混合してスラリー化した。得られたスラリーをスプ
レードライヤで乾燥・造粒した後、篩で分級し88〜1
25μmの粒径としたものをアルミナ製容器を用いて窒
素雰囲気中で焼成した・焼成温度は1350℃で5時間
保持の後炉冷した。得られたキャリアの特性を第2表に
示す。Table 1 1) After premixing the raw materials pulverized with an atomizer to an average particle size of 3 μm using a Henschel mixer, 30 kg of water and 150 g of polycarboxylic acid ammonium salt as a dispersant (0
. After drying and granulating the obtained slurry with a spray dryer, it was classified with a sieve and 88-1
The particles having a particle size of 25 μm were fired in a nitrogen atmosphere using an alumina container.The firing temperature was kept at 1350°C for 5 hours, and then cooled in the furnace. The properties of the obtained carrier are shown in Table 2.
第2表
このキャリアに市販のスチレン−アクリル共重合樹脂系
のトナーを5wtχ添加して現像剤とし、市販の複写機
(ノンコートフェライトキャリア使用の中速機)で実写
テストを行った。テストの結果良好な画像濃度、解像度
が得られ、80.000枚のコピー後も画質の低下はな
かった。80.000枚のコピー後のキャリアを回収し
て電子顕微鏡観察したところ、トナーフィルミングは生
じていなかった。Table 2 5 wt.chi. of a commercially available styrene-acrylic copolymer resin toner was added to this carrier to prepare a developer, and a photocopying test was conducted using a commercially available copying machine (medium-speed machine using a non-coated ferrite carrier). As a result of the test, good image density and resolution were obtained, and there was no deterioration in image quality even after copying 80,000 sheets. When the carrier after 80,000 copies was collected and observed under an electron microscope, no toner filming had occurred.
ス11」i
ヘマタイト20kgに対し酸化ケイ素(SiO□)およ
び酸化カルシウム(Cab)の添加量を5iOz/Ca
O= 1/1(重量比)で添加量を100g、 200
g、 300g、 400g。11'i Addition amount of silicon oxide (SiO□) and calcium oxide (Cab) to 20 kg of hematite is 5 iOz/Ca.
O = 1/1 (weight ratio) and the amount added is 100g, 200
g, 300g, 400g.
500g、 700g、 1000g、 1200g、
2000gとして混合し、分散剤を加え、スラリー濃
度50w t!のスラリーとした。次にアトライターに
よりミリング処理し、PVAをバインダーとして加え、
スプレードライヤーにて造粒、乾燥を行った。しかる後
、酸素濃度を制御した窒素ガス中で1300℃、3時間
の焼成を行った。500g, 700g, 1000g, 1200g,
Mix 2000g, add a dispersant, and make a slurry concentration of 50wt! It was made into a slurry. Next, milling is performed using an attritor, PVA is added as a binder,
Granulation and drying were performed using a spray dryer. Thereafter, firing was performed at 1300° C. for 3 hours in nitrogen gas with controlled oxygen concentration.
また、比較例として、添加物(SiO□およびCab)
を加えず、ヘマタイトのみを用いる他前述実施例と同一
条件で電子写真用キャリアを製造した。その後得られた
キャリアに対して磁気特性(飽和磁化)、電気抵抗(比
抵抗)、帯電量を測定した。In addition, as a comparative example, additives (SiO□ and Cab)
An electrophotographic carrier was manufactured under the same conditions as in the previous example, except that only hematite was used without adding. Thereafter, the magnetic properties (saturation magnetization), electrical resistance (specific resistance), and charge amount of the obtained carrier were measured.
結果を第3表に示す。The results are shown in Table 3.
さらにこれらのキャリアを使用して実写テストを行った
。実写テストはキャリア1 kgに対しトナー濃度5w
tχになる様に現像剤を調整して市販の複写機により実
施した。実写テストとして、画像濃度、解像度は画像解
析装置により測定するとともに、ガブリ現象の有無、さ
らには画質の低下なくコピーできる枚数を測定した。画
像特性の結果を第4表に示す。We also conducted live-action tests using these carriers. Live-action test: toner concentration 5W for 1 kg of carrier
The developer was adjusted so that tχ was obtained, and the experiment was carried out using a commercially available copying machine. As a photocopying test, image density and resolution were measured using an image analysis device, as well as the presence or absence of the gabbing phenomenon and the number of copies that could be made without deterioration of image quality. The results of image characteristics are shown in Table 4.
この結果、従来のフェライト系キャリアを使用した場合
は、はぼ45000枚で現像不良を生じたのに対し、本
発明によるキャリアは全て5oooo枚以上の鮮明なコ
ピーが得られた。また、本発明によるキャリアを使用し
た場合、実写テスト後のキャリア粒子の表面状態を調べ
た結果表面の平滑性に変化はなく、また、トナーフィル
ミングの現象も生じてないことがわかった。As a result, when a conventional ferrite carrier was used, development defects occurred after approximately 45,000 copies, whereas with the carrier according to the present invention, clear copies of 5000 copies or more were obtained in all cases. Further, when the carrier according to the present invention was used, the surface condition of the carrier particles after the actual photographic test was examined, and it was found that there was no change in surface smoothness and no toner filming phenomenon occurred.
案1±1
酸化鉄の他に、酸化物VzOs+ 5nOz+ 5bz
O:+、 PbO+MgO,MnO単独で2wtχ含む
組成で、常法に従い球状粒子とした。その後、酸素濃度
0.1volχの雰囲気下で1250℃、3時間焼成処
理をおこない電子写真用キャリアを得た。得られた電子
写真用キャリアの特性を第5表に示す。第5表において
、帯電量は市販のトナーとキャリアとを回転ミル中で混
合調整し、ブローオフで測定したキャリアの値として求
めた。Plan 1±1 In addition to iron oxide, oxide VzOs+ 5nOz+ 5bz
O:+, PbO+MgO, with a composition containing 2wtχ of MnO alone, and made into spherical particles according to a conventional method. Thereafter, baking treatment was performed at 1250° C. for 3 hours in an atmosphere with an oxygen concentration of 0.1 volχ to obtain an electrophotographic carrier. Table 5 shows the properties of the obtained carrier for electrophotography. In Table 5, the amount of charge was determined by mixing and adjusting a commercially available toner and carrier in a rotary mill and measuring the value of the carrier by blow-off.
第5表
酸化物を2種以上用い、実施例3と同様の方法で電子写
真用キャリアを得た。組合せと、得られたキャリアの特
性を第6表に示す。An electrophotographic carrier was obtained in the same manner as in Example 3 using two or more of the oxides shown in Table 5. Table 6 shows the combinations and the characteristics of the obtained carriers.
第6表
(発明の効果)
以上詳細に説明したように、本発明の電子写真現像剤用
キャリアは、鉄粉キャリアより長寿命、高解像度であリ
マグネタイトキャリアの樹脂被覆を要する欠点を補い、
フェライトキャリアと同等の性能をより安価に提供する
ものである。また、本発明の電子写真現像剤用キャリア
は、2成分磁気ブラシ現像用のキャリアとして従来量も
軽量であったフェライトキャリアより更に軽量であるた
め、攪拌抵抗が小さく、複写機の小型化を可能にするも
のである。Table 6 (Effects of the Invention) As explained in detail above, the electrophotographic developer carrier of the present invention has a longer life and higher resolution than the iron powder carrier, and compensates for the drawbacks of the limagnetite carrier that require resin coating.
It provides the same performance as ferrite carriers at a lower cost. In addition, the carrier for electrophotographic developer of the present invention is lighter than the ferrite carrier, which was conventionally lightweight as a carrier for two-component magnetic brush development, so it has less stirring resistance and allows for the miniaturization of copying machines. It is something to do.
Claims (1)
母相中に、Si、Ca、Al、Mg、Fe、V、Sb、
Sn、Pb、Cu、Mnの1種または2種以上からなる
非磁性酸化物相が散在していることを特徴とする電子写
真現像剤用キャリア。 2、ヘマタイト(Fe_2O_3)を主成分とする酸化
鉄粉末にSi、Ca、Al、Mg、Fe、V、Sb、S
n、Pb、Cu、Mnの1種または2種以上からなる非
磁性酸化物粉末を混合・造粒し、酸素濃度5vol%以
下の不活性雰囲気中焼成温度1000℃〜1400℃で
熱処理することにより、ヘマタイトのみを還元してマグ
ネタイトとする電子写真現像剤用キャリアの製造方法。[Claims] 1. Si, Ca, Al, Mg, Fe, V, Sb,
A carrier for an electrophotographic developer, characterized in that a nonmagnetic oxide phase consisting of one or more of Sn, Pb, Cu, and Mn is scattered therein. 2. Si, Ca, Al, Mg, Fe, V, Sb, S to iron oxide powder whose main component is hematite (Fe_2O_3)
By mixing and granulating non-magnetic oxide powder consisting of one or more of n, Pb, Cu, and Mn, and heat-treating at a firing temperature of 1000°C to 1400°C in an inert atmosphere with an oxygen concentration of 5 vol% or less. , a method for producing a carrier for an electrophotographic developer in which only hematite is reduced to magnetite.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP61-205039 | 1986-09-02 | ||
JP20503986 | 1986-09-02 |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS63184764A true JPS63184764A (en) | 1988-07-30 |
Family
ID=16500433
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP61284270A Pending JPS63184764A (en) | 1986-09-02 | 1986-12-01 | Carrier for electrophotographic developer and production thereof |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS63184764A (en) |
Cited By (15)
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---|---|---|---|---|
WO1995006948A1 (en) * | 1993-08-31 | 1995-03-09 | Fuji Electrochemical Co., Ltd. | Magnetic oxide material and method of its manufacture |
JPH0766023A (en) * | 1993-08-31 | 1995-03-10 | Fuji Elelctrochem Co Ltd | Manufacture of oxide magnetic material |
JPH0766026A (en) * | 1993-08-31 | 1995-03-10 | Fuji Elelctrochem Co Ltd | Oxide magnetic material and manufacture thereof |
JPH0766024A (en) * | 1993-08-31 | 1995-03-10 | Fuji Elelctrochem Co Ltd | Manufacture of oxide magnetic material |
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WO2004088680A3 (en) * | 2003-03-31 | 2005-03-31 | Kanto Denka Kogyo Kk | A mg-based ferrite, an electrophotographic development carrier containing the ferrite, and a developer containing the carrier |
JP2007307738A (en) * | 2006-05-16 | 2007-11-29 | Tohoku Ricoh Co Ltd | Ultraviolet irradiation equipment for fixation of printed matter |
JP2008065106A (en) * | 2006-09-08 | 2008-03-21 | Dowa Holdings Co Ltd | Carrier core material for electrophotographic development, method for manufacturing the same and magnetic carrier |
JP2009237049A (en) * | 2008-03-26 | 2009-10-15 | Dowa Electronics Materials Co Ltd | Carrier core material for electrophotographic developer, and method of manufacturing the same |
JP2010085761A (en) * | 2008-09-30 | 2010-04-15 | Dowa Electronics Materials Co Ltd | Carrier core material for electrophotographic developer, method of manufacturing the same, carrier for electrophotographic developer and electrophotographic developer |
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1986
- 1986-12-01 JP JP61284270A patent/JPS63184764A/en active Pending
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EP0653379A1 (en) * | 1993-05-20 | 1995-05-17 | Fuji Electrochemical Co.Ltd. | Process for manufacturing homogeneous magnetite |
EP0653379A4 (en) * | 1993-05-20 | 1996-02-28 | Fuji Electrochemical Co Ltd | Process for manufacturing homogeneous magnetite. |
KR100327646B1 (en) * | 1993-08-31 | 2002-07-06 | 다쯔타 도키오 | Oxide magnetic material and manufacturing method |
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JPH0766026A (en) * | 1993-08-31 | 1995-03-10 | Fuji Elelctrochem Co Ltd | Oxide magnetic material and manufacture thereof |
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US5538656A (en) * | 1993-08-31 | 1996-07-23 | Fuji Electrochemical Co., Ltd. | Magnetic oxide and process for producing same |
JPH0766024A (en) * | 1993-08-31 | 1995-03-10 | Fuji Elelctrochem Co Ltd | Manufacture of oxide magnetic material |
WO1995006948A1 (en) * | 1993-08-31 | 1995-03-09 | Fuji Electrochemical Co., Ltd. | Magnetic oxide material and method of its manufacture |
WO2001067182A1 (en) * | 2000-03-10 | 2001-09-13 | Höganäs Ab | Method for preparation of iron-based powder and iron-based powder |
US6702870B2 (en) | 2000-03-10 | 2004-03-09 | Höganäs Ab | Method for preparation of iron-based powder and iron-based powder |
WO2004088680A3 (en) * | 2003-03-31 | 2005-03-31 | Kanto Denka Kogyo Kk | A mg-based ferrite, an electrophotographic development carrier containing the ferrite, and a developer containing the carrier |
US7470498B2 (en) | 2003-03-31 | 2008-12-30 | Kanto Denka Kogyo Co., Ltd. | Mg-based ferrite, an electrophotographic development carrier containing the ferrite, and a developer containing the carrier |
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