JP2012076955A - Ferrite particle, and electrophotographic developing carrier and electrophotographic developer using the same - Google Patents

Ferrite particle, and electrophotographic developing carrier and electrophotographic developer using the same Download PDF

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JP2012076955A
JP2012076955A JP2010222343A JP2010222343A JP2012076955A JP 2012076955 A JP2012076955 A JP 2012076955A JP 2010222343 A JP2010222343 A JP 2010222343A JP 2010222343 A JP2010222343 A JP 2010222343A JP 2012076955 A JP2012076955 A JP 2012076955A
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ferrite particles
alkaline earth
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metal element
crystal structure
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JP5822377B2 (en
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Sho Ogawa
翔 小川
Tomohide Iida
智英 飯田
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Dowa Electronics Materials Co Ltd
Dowa IP Creation Co Ltd
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Abstract

PROBLEM TO BE SOLVED: To provide a ferrite particle having not only high resistance and a high magnetic characteristic but also high electro-static chargeability.SOLUTION: This ferrite particle contains, as a principal component, a material expressed by composition formula: MFeO(M is at least one kind of metal selected from the group comprising Mn, Mg, Ti, Cu, Zn and Ni, and 0≤x≤1), and contains an alkaline earth metal element. The alkaline earth metal element is formed not into magnetoplumbite type crystal structure but into solid solution to spinel crystal structure. At least one of Sr and Ba is preferable as the alkaline earth metal element, and Sr is more preferable. The content of the alkaline earth metal element is preferably 3 mol% or less.

Description

本発明はフェライト粒子並びにそれを用いた電子写真現像用キャリア及び電子写真用現像剤に関するものである。   The present invention relates to a ferrite particle, an electrophotographic developer carrier and an electrophotographic developer using the same.

近年の電子機器の高機能化に伴って、これらの機器の部品又は部品材料として使用されるフェライト粒子についても、高抵抗化や磁気特性の向上に加えて高帯電性が求められている。   As electronic devices become more sophisticated in recent years, ferrite particles used as parts or component materials of these devices are also required to have high chargeability in addition to higher resistance and improved magnetic properties.

例えば、電子写真方式を用いたファクシミリやプリンタ、複写機などの画像形成装置では、フェライト粒子の表面を絶縁性樹脂で被覆したいわゆるコーティングキャリアとトナーとを混合した二成分系現像剤によって、感光体表面に形成された静電潜像を可視像化している。   For example, in image forming apparatuses such as facsimiles, printers, and copiers using an electrophotographic method, a two-component developer in which a so-called coating carrier in which the surface of a ferrite particle is coated with an insulating resin and a toner are mixed is used as a photosensitive member. The electrostatic latent image formed on the surface is visualized.

近年、画像形成装置における画像形成速度の高速化及び高画質化の市場要求に対応するため、現像装置の現像スリーブや撹拌部材の回転速度を速めて、静電潜像への現像剤の供給量及びトナーの帯電速度を速めている。   In recent years, in order to respond to the market demand for higher image formation speed and higher image quality in image forming apparatuses, the rotation speed of the developing sleeve and the stirring member of the developing apparatus is increased to supply the developer to the electrostatic latent image. In addition, the charging speed of the toner is increased.

現像スリーブや撹拌部材の回転速度を速めると、遠心力によって現像スリーブから現像剤が飛散等しやすくなるため、キャリアの磁気特性をさらに向上させる必要がある。また、コーティングキャリア同士の衝突や、コーティングキャリアと現像装置内壁面との間の摩擦などが激しくなるため、フェライト粒子表面の絶縁性樹脂が使用と共に剥がれ落ちやすくなりフェライト粒子が露出しやすくなるが、このようなフェライト粒子の表面露出が生じた場合でも帯電性能が低下しないようにする必要がある。   When the rotation speed of the developing sleeve and the agitating member is increased, the developer is likely to be scattered from the developing sleeve due to the centrifugal force, so that it is necessary to further improve the magnetic characteristics of the carrier. In addition, since the collision between the coating carriers and the friction between the coating carrier and the developing device inner wall surface become intense, the insulating resin on the surface of the ferrite particles is easily peeled off with use and the ferrite particles are easily exposed. Even when such surface exposure of ferrite particles occurs, it is necessary to prevent the charging performance from deteriorating.

例えば特許文献1では、マグネタイト相とフェライト相の複合磁性酸化物であって、スピネル型とマグネトプランバイト型の結晶構造から構成され、スピネル型結晶構造のAサイト及びBサイトにおけるFe2+及びFe3+の含有割合を規定した強磁性材料粉が提案されている。 For example, in Patent Document 1, a composite magnetic oxide of a magnetite phase and a ferrite phase, which is composed of a spinel type and a magnetoplumbite type crystal structure, Fe 2+ and Fe 3+ at the A site and B site of the spinel type crystal structure is disclosed. Ferromagnetic material powders with a specified content ratio have been proposed.

特開2007-273505号公報JP 2007-273505 A

前記提案の強磁性材料粉をキャリアとして用いた場合、飛散防止や高抵抗化、高強度化は図れると思われるものの、帯電性能の向上は図れないと考えられる。   When the proposed ferromagnetic material powder is used as a carrier, it is thought that the prevention of scattering, high resistance, and high strength can be achieved, but the charging performance cannot be improved.

本発明はこのような従来の問題に鑑みてなされたものであり、その目的は、高抵抗化と高磁気特性を有するのみならず高帯電性をも有するフェライト粒子を提供することにある。   The present invention has been made in view of such conventional problems, and an object of the present invention is to provide ferrite particles having not only high resistance and high magnetic properties but also high chargeability.

また本発明の目的は、画像形成速度の高速化及び高画質化に対応し得るキャリア及び現像剤を提供することにある。   Another object of the present invention is to provide a carrier and a developer that can cope with an increase in image formation speed and an increase in image quality.

本発明によれば、組成式MFe3−X(但し、MはMn,Mg,Ti,Cu,Zn,Niからなる群より選ばれる少なくとも1種の金属、0≦X≦1)で表される材料を主成分とし、アルカリ土類金属元素を含有するフェライト粒子であって、前記アルカリ土類金属元素がマグネトプランバイト型結晶構造をとらず、スピネル型結晶構造に固溶していることを特徴とするフェライト粒子が提供される。 According to the present invention, the composition formula M X Fe 3-X O 4 (where M is at least one metal selected from the group consisting of Mn, Mg, Ti, Cu, Zn, Ni, 0 ≦ X ≦ 1) Ferrite particles containing as a main component a material represented by and containing an alkaline earth metal element, wherein the alkaline earth metal element does not have a magnetoplumbite type crystal structure but is dissolved in a spinel type crystal structure. A ferrite particle is provided.

ここで、前記アルカリ土類金属元素としてはSr及びBaの少なくとも一方が好ましく、Srがより好ましい。   Here, as the alkaline earth metal element, at least one of Sr and Ba is preferable, and Sr is more preferable.

前記アルカリ土類金属元素の含有量としては、3mol%以下であるのが好ましい。なお、フェライト粒子中のアルカリ土類金属元素の特定及び定量は、フェライト粒子を酸溶液中で溶解し、ICP(Inductively Coupled Plasma)発光分析によって行えばよい。   The content of the alkaline earth metal element is preferably 3 mol% or less. In addition, the alkaline earth metal element in the ferrite particles may be identified and quantified by dissolving the ferrite particles in an acid solution and performing ICP (Inductively Coupled Plasma) emission analysis.

また本発明によれば、前記記載のフェライト粒子の表面を樹脂で被覆したことを特徴とする電子写真現像用キャリアが提供される。   According to the present invention, there is also provided an electrophotographic developing carrier characterized in that the surface of the ferrite particles described above is coated with a resin.

さらに本発明によれば、前記記載のキャリアとトナーとを含むことを特徴とする電子写真用現像剤が提供される。   Furthermore, according to the present invention, there is provided an electrophotographic developer comprising the carrier described above and a toner.

本発明のフェライト粒子では、組成式MFe3−X(但し、MはMn,Mg,Ti,Cu,Zn,Niからなる群より選ばれる少なくとも1種の金属、0≦X≦1)で表される材料を主成分とし、アルカリ土類金属元素をスピネル型結晶構造に固溶させているので、高抵抗化と高磁気特性を有するのみならず高帯電性をも有する。 In the ferrite particles of the present invention, the composition formula M X Fe 3-X O 4 (where M is at least one metal selected from the group consisting of Mn, Mg, Ti, Cu, Zn, Ni, 0 ≦ X ≦ 1) ) And the alkaline earth metal element is dissolved in the spinel crystal structure, so that it has not only high resistance and high magnetic properties but also high chargeability.

本発明のフェライト粒子を画像形成装置の電子写真現像用キャリアとして用いた場合には、高速化及び高画質化が達成される。   When the ferrite particles of the present invention are used as an electrophotographic developing carrier for an image forming apparatus, high speed and high image quality are achieved.

実施例1〜5及び比較例1,2のフェライト粒子のXRDパターンを示す図である。It is a figure which shows the XRD pattern of the ferrite particle of Examples 1-5 and Comparative Examples 1 and 2. FIG. Sr含有量と格子定数との関係を示すグラフである。It is a graph which shows the relationship between Sr content and a lattice constant. Sr含有量と帯電量比との関係を示すグラフである。It is a graph which shows the relationship between Sr content and charge amount ratio.

本発明に係るフェライト粒子の大きな特徴は、組成式MFe3−X(但し、MはMn,Mg,Ti,Cu,Zn,Niからなる群より選ばれる少なくとも1種の金属、0≦X≦1)で表される材料を主成分とし、アルカリ土類金属元素を含有するフェライト粒子であって、前記アルカリ土類金属元素がマグネトプランバイト型結晶構造をとらず、スピネル型結晶構造に固溶していることにある。これまでアルカリ土類金属元素を添加したフェライト粒子は提案もされているが、いずれもアルカリ土類金属元素の添加量が多く、スピネル型結晶構造のみならずマグネトプランバイト型結晶構造も有していた。本発明者等が鋭意検討したところ、フェライト粒子がマグネトプランバイト型結晶構造を有していると、帯電性能が格段に低下するという新たな知見が得られた。なお、本明細書においてアルカリ土類金属元素がマグネトプランバイト型結晶構造をとらず、スピネル型結晶構造に固溶しているとは、粉末X線回折分析において実施例に示す測定条件下でスピネル型結晶構造の強度ピークが見られ、マグネトプランバイト型結晶構造の強度ピークが実質的に見られないことをいうものとする。 The major feature of the ferrite particles according to the present invention is that the composition formula M X Fe 3 -X O 4 (where M is at least one metal selected from the group consisting of Mn, Mg, Ti, Cu, Zn, Ni, 0 ≦ X ≦ 1) as a main component, ferrite particles containing an alkaline earth metal element, wherein the alkaline earth metal element does not have a magnetoplumbite type crystal structure, but a spinel type crystal structure It is in a solid solution. So far, ferrite particles to which alkaline earth metal elements have been added have been proposed, but all of them have a large amount of alkaline earth metal elements added and have not only a spinel crystal structure but also a magnetoplumbite crystal structure. It was. As a result of intensive studies by the present inventors, there has been obtained a new finding that when the ferrite particles have a magnetoplumbite type crystal structure, the charging performance is remarkably lowered. In this specification, an alkaline earth metal element does not have a magnetoplumbite type crystal structure but is dissolved in a spinel type crystal structure in a powder X-ray diffraction analysis under the measurement conditions shown in the examples. An intensity peak of the type crystal structure is seen, and an intensity peak of the magnetoplumbite type crystal structure is substantially not seen.

アルカリ土類金属元素がマグネトプランバイト型結晶構造をとらずスピネル型結晶構造に固溶しているようにするには、アルカリ土類金属元素の含有量を調整すればよい。具体的には、アルカリ土類金属元素の含有量を3mol%以下とするのが望ましい。アルカリ土類金属元素の含有量が3mol%を超えると、アルカリ土類金属元素がスピネル型結晶構造に固溶しきれず、過剰なアルカリ土類金属元素がFeと反応しマグネトプランバイト型結晶構造をとり始める。アルカリ土類金属元素のより好ましい含有量は0.2mol%〜2mol%の範囲であり、より好ましくは0.5mol%〜1.5mol%の範囲である。   In order for the alkaline earth metal element not to have the magnetoplumbite type crystal structure but be dissolved in the spinel type crystal structure, the content of the alkaline earth metal element may be adjusted. Specifically, the content of the alkaline earth metal element is desirably 3 mol% or less. When the content of the alkaline earth metal element exceeds 3 mol%, the alkaline earth metal element cannot be completely dissolved in the spinel crystal structure, and the excess alkaline earth metal element reacts with Fe to form a magnetoplumbite crystal structure. Start taking. The more preferable content of the alkaline earth metal element is in the range of 0.2 mol% to 2 mol%, and more preferably in the range of 0.5 mol% to 1.5 mol%.

本発明で使用するアルカリ土類金属元素としては、Sr,Ba,Ca,Raが挙げられ、これらの中でもSr及びBaがより好適に用いられ、さらにはSrが好適に用いられる。   Examples of the alkaline earth metal element used in the present invention include Sr, Ba, Ca, and Ra. Among these, Sr and Ba are more preferably used, and Sr is more preferably used.

本発明のフェライト粒子の粒径に特に限定はないが、平均粒径で数十μm〜数百μm程度が好ましく、粒度分布はシャープであるのが好ましい。   The particle size of the ferrite particles of the present invention is not particularly limited, but the average particle size is preferably about several tens of μm to several hundreds of μm, and the particle size distribution is preferably sharp.

本発明のフェライト粒子は各種用途に用いることができ、例えば、電子写真現像用キャリアや電磁波吸収材、電磁波シールド材用材料粉末、ゴム、プラスチック用充填材・補強材、ペンキ、絵具・接着剤用艶消材、充填材、補強材等として用いることができる。これらの中でも特に電子写真現像用キャリアとして好適に用いられる。   The ferrite particles of the present invention can be used in various applications, for example, electrophotographic developer carriers, electromagnetic wave absorbing materials, electromagnetic shielding material powders, rubber, fillers / reinforcing materials for plastics, paints, paints / adhesives It can be used as a matting material, filler, reinforcing material and the like. Among these, it is particularly preferably used as a carrier for electrophotographic development.

本発明のフェライト粒子の製造方法に特に限定はないが、以下に説明する製造方法が好適である。   Although the manufacturing method of the ferrite particle of the present invention is not particularly limited, the manufacturing method described below is preferable.

まず、Fe原料とM成分の原料、アルカリ土類金属元素原料とを秤量して分散媒中に投入し混合してスラリーを作製する。Fe原料としては、Fe等が好適に使用される。M成分の原料としては、Mn,Mg,Ti,Cu,Zn,Ni及びこれら2価の金属を任意に組み合わせたものが好適に使用できる。例えば、MnであればMnCO、Mn等が使用でき、MgであればMgO、Mg(OH)、MgCO等が好適に使用できる。 First, an Fe raw material, an M component raw material, and an alkaline earth metal element raw material are weighed, put into a dispersion medium, and mixed to prepare a slurry. Fe 2 O 3 or the like is preferably used as the Fe raw material. As the raw material for the M component, Mn, Mg, Ti, Cu, Zn, Ni and any combination of these divalent metals can be suitably used. For example, Mn can be MnCO 3 , Mn 3 O 4 or the like, and Mg can be suitably used MgO, Mg (OH) 2 , MgCO 3 or the like.

アルカリ土類金属元素原料としては、例えばアルカリ土類金属元素としてSrを用いる場合には、SrSiOやSrCO,Sr(NO等から選択される少なくとも1種の化合物が好適に用いられる。アルカリ土類金属元素原料の平均粒径としては5μm以下が好ましく、より好ましくは3μm以下、さらに好ましくは1μm以下である。この範囲の平均粒径のアルカリ土類金属元素原料を用いることにより、フェライト粒子のスピネル型結晶構造にアルカリ土類金属元素を効率的に固溶させることができる。 As the alkaline earth metal element raw material, for example, when Sr is used as the alkaline earth metal element, at least one compound selected from Sr 2 SiO 4 , SrCO 3 , Sr (NO 3 ) 2 and the like is preferably used. Used. The average particle size of the alkaline earth metal element raw material is preferably 5 μm or less, more preferably 3 μm or less, and even more preferably 1 μm or less. By using an alkaline earth metal element raw material having an average particle diameter in this range, the alkaline earth metal element can be efficiently dissolved in the spinel crystal structure of the ferrite particles.

アルカリ土類金属元素の添加量としては、前述のように、アルカリ土類金属元素の含有量が3mol%以下となるように添加するのがよい。   As described above, the alkaline earth metal element is preferably added so that the content of the alkaline earth metal element is 3 mol% or less.

本発明で使用する分散媒としては水が好適である。分散媒には、前記Fe原料、M成分の原料、アルカリ土類金属元素原料の他、必要によりバインダー、分散剤等を配合してもよい。バインダーとしては、例えば、ポリビニルアルコールが好適に使用できる。バインダーの配合量としてはスラリー中の濃度が0.5〜2wt%程度とするのが好ましい。また、分散剤としては、例えば、ポリカルボン酸アンモニウム等が好適に使用できる。分散剤の配合量としてはスラリー中の濃度が0.5〜2wt%程度とするのが好ましい。その他、潤滑剤や焼結促進剤等を配合してもよい。   Water is preferred as the dispersion medium used in the present invention. In addition to the Fe raw material, the M component raw material, and the alkaline earth metal element raw material, a binder, a dispersing agent, and the like may be added to the dispersion medium as necessary. For example, polyvinyl alcohol can be suitably used as the binder. The blending amount of the binder is preferably about 0.5 to 2 wt% in the slurry. Moreover, as a dispersing agent, polycarboxylate ammonium etc. can be used conveniently, for example. As the blending amount of the dispersant, the concentration in the slurry is preferably about 0.5 to 2 wt%. In addition, you may mix | blend a lubricant, a sintering accelerator, etc.

スラリーの固形分濃度は50〜90wt%の範囲が望ましい。なお、アルカリ土類金属元素原料の添加量が、Fe原料及びM成分の原料の総重量に対し微量であるので、アルカリ土類金属元素原料を先に分散媒中に分散させ、その後、Fe原料及びM成分の原料を分散媒に分散させてもよい。これにより、分散媒に原料を均一に分散できるようになる。また、原材料であるFe原料、M成分の原料、アルカリ土類金属元素原料を分散媒に投入する前に、必要により、粉砕混合の処理をしておいてもよい。   The solid content concentration of the slurry is desirably in the range of 50 to 90 wt%. Since the addition amount of the alkaline earth metal element raw material is a small amount with respect to the total weight of the Fe raw material and the M component raw material, the alkaline earth metal element raw material is first dispersed in the dispersion medium, and then the Fe raw material is added. In addition, the raw materials of the M component may be dispersed in a dispersion medium. Thereby, the raw material can be uniformly dispersed in the dispersion medium. In addition, before the raw materials Fe raw material, M component raw material, and alkaline earth metal element raw material are added to the dispersion medium, a pulverization and mixing process may be performed if necessary.

次に、以上のようにして作製されたスラリーを湿式粉砕する。例えば、ボールミルや振動ミルを用いて所定時間湿式粉砕する。粉砕後の原材料の平均粒径は50μm以下が好ましく、より好ましくは10μm以下である。振動ミルやボールミルには、所定粒径のメディアを内在させるのがよい。メディアの材質としては、鉄系のクロム鋼や酸化物系のジルコニア、チタニア、アルミナなどが挙げられる。粉砕工程の形態としては連続式及び回分式のいずれであってもよい。粉砕物の粒径は、粉砕時間や回転速度、使用するメディアの材質・粒径などによって調整される。   Next, the slurry produced as described above is wet pulverized. For example, wet grinding is performed for a predetermined time using a ball mill or a vibration mill. The average particle diameter of the raw material after pulverization is preferably 50 μm or less, more preferably 10 μm or less. The vibration mill or ball mill preferably contains a medium having a predetermined particle diameter. Examples of the material of the media include iron-based chromium steel and oxide-based zirconia, titania, and alumina. As a form of a grinding | pulverization process, any of a continuous type and a batch type may be sufficient. The particle size of the pulverized product is adjusted depending on the pulverization time and rotation speed, the material and particle size of the media used, and the like.

そして、粉砕されたスラリーを噴霧乾燥させて造粒する。具体的には、スプレードライヤーなどの噴霧乾燥機にスラリーを導入し、雰囲気中へ噴霧することによって球状に造粒する。噴霧乾燥時の雰囲気温度は100〜300℃の範囲が好ましい。これにより、粒径10〜200μmの球状の造粒物が得られる。なお、得られた造粒物は、振動ふるい等を用いて、粗大粒子や微粉を除去し粒度分布をシャープなものとするのが望ましい。   Then, the pulverized slurry is spray-dried and granulated. Specifically, the slurry is introduced into a spray dryer such as a spray dryer, and granulated into a spherical shape by spraying into the atmosphere. The atmospheric temperature during spray drying is preferably in the range of 100 to 300 ° C. Thereby, a spherical granulated product having a particle size of 10 to 200 μm is obtained. In addition, it is desirable that the obtained granulated product has a sharp particle size distribution by removing coarse particles and fine powder using a vibration sieve or the like.

次に、造粒物を800℃以上に加熱した炉に投入して、フェライト粒子を合成するための一般的な手法で焼成することにより、フェライト粒子を生成させる。焼成温度が800℃以上であれば焼結は進み、生成したフェライト粒子の形状が維持される。焼結温度の好ましい上限値は1500℃である。焼結温度が1500℃以下であると、フェライト粒子同士の過剰焼結が起こらず、異形粒子の発生が抑制されるからである。したがって、焼結温度としては800〜1500℃の範囲が好ましい。   Next, the granulated material is put into a furnace heated to 800 ° C. or higher and fired by a general method for synthesizing ferrite particles, thereby generating ferrite particles. If the firing temperature is 800 ° C. or higher, sintering proceeds and the shape of the generated ferrite particles is maintained. A preferable upper limit of the sintering temperature is 1500 ° C. This is because when the sintering temperature is 1500 ° C. or lower, the ferrite particles are not excessively sintered and the generation of irregularly shaped particles is suppressed. Therefore, the sintering temperature is preferably in the range of 800 to 1500 ° C.

次に、得られた焼成物を解砕する。具体的には、例えば、ハンマーミル等によって焼成物を解砕する。解砕工程の形態としては連続式及び回分式のいずれであってもよい。そして、必要により、粒径を所定範囲に揃えるため分級を行ってもよい。分級方法としては、風力分級や篩分級など従来公知の方法を用いることができる。また、風力分級機で1次分級した後、振動篩や超音波篩で粒径を所定範囲に揃えるようにしてもよい。さらに、分級工程後に、磁場選鉱機によって非磁性粒子を除去するようにしてもよい。   Next, the obtained fired product is crushed. Specifically, for example, the fired product is crushed by a hammer mill or the like. As a form of a crushing process, any of a continuous type and a batch type may be sufficient. And if necessary, classification may be performed in order to make the particle size in a predetermined range. As a classification method, a conventionally known method such as air classification or sieve classification can be used. In addition, after primary classification with an air classifier, the particle size may be aligned within a predetermined range with a vibration sieve or an ultrasonic sieve. Furthermore, you may make it remove a nonmagnetic particle with a magnetic field separator after a classification process.

その後、必要に応じて、分級後の粉末(焼成物)を酸化性雰囲気中で加熱して、粒子表面に酸化被膜を形成させて高抵抗化を図ってもよい。酸化性雰囲気としては大気雰囲気又は酸素と窒素の混合雰囲気のいずれでもよい。また、加熱温度は、200〜800℃の範囲が好ましく、250〜600℃の範囲がさらに好ましい。加熱時間は30分〜5時間の範囲が好ましい。   Thereafter, if necessary, the classified powder (baked product) may be heated in an oxidizing atmosphere to form an oxide film on the particle surface to increase the resistance. The oxidizing atmosphere may be either an air atmosphere or a mixed atmosphere of oxygen and nitrogen. The heating temperature is preferably in the range of 200 to 800 ° C, more preferably in the range of 250 to 600 ° C. The heating time is preferably in the range of 30 minutes to 5 hours.

以上のようにして作製した本発明のフェライト粒子を、電子写真現像用キャリアとして用いる場合、フェライト粒子をそのまま電子写真現像用キャリアとして用いることもできるが、帯電性等の観点からは、フェライト粒子の表面を樹脂で被覆して用いるのが好ましい。   When the ferrite particles of the present invention produced as described above are used as a carrier for electrophotographic development, the ferrite particles can be used as they are as a carrier for electrophotographic development. However, from the viewpoint of chargeability and the like, It is preferable to coat the surface with a resin.

フェライト粒子の表面を被覆する樹脂としては、従来公知のものが使用でき、例えば、ポリエチレン、ポリプロピレン、ポリ塩化ビニル、ポリ−4−メチルペンテン−1、ポリ塩化ビニリデン、ABS(アクリロニトリル−ブタジエン−スチレン)樹脂、ポリスチレン、(メタ)アクリル系樹脂、ポリビニルアルコール系樹脂、並びにポリ塩化ビニル系やポリウレタン系、ポリエステル系、ポリアミド系、ポリブタジエン系等の熱可塑性エストラマー、フッ素シリコーン系樹脂などが挙げられる。   As the resin for covering the surface of the ferrite particles, conventionally known resins can be used, for example, polyethylene, polypropylene, polyvinyl chloride, poly-4-methylpentene-1, polyvinylidene chloride, ABS (acrylonitrile-butadiene-styrene). Examples thereof include resins, polystyrene, (meth) acrylic resins, polyvinyl alcohol resins, polyvinyl chloride-based, polyurethane-based, polyester-based, polyamide-based, polybutadiene-based thermoplastic elastomers, fluorine silicone-based resins, and the like.

フェライト粒子の表面を樹脂で被覆するには、樹脂の溶液又は分散液をフェライト粒子に施せばよい。塗布溶液用の溶媒としては、トルエン、キシレン等の芳香族炭化水素系溶媒;アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン系溶媒;テトラヒドロフラン、ジオキサン等の環状エーテル類溶媒;エタノール、プロパノール、ブタノール等のアルコール系溶媒;エチルセロソルブ、ブチルセロソルブ等のセロソルブ系溶媒;酢酸エチル、酢酸ブチル等のエステル系溶媒;ジメチルホルムアミド、ジメチルアセトアミド等のアミド系溶媒などの1種又は2種以上を用いることができる。塗布溶液中の樹脂成分濃度は、一般に0.001〜30wt%、特に0.001〜2wt%の範囲内にあるのがよい。   In order to coat the surface of the ferrite particles with a resin, a resin solution or dispersion may be applied to the ferrite particles. Solvents for the coating solution include aromatic hydrocarbon solvents such as toluene and xylene; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; cyclic ether solvents such as tetrahydrofuran and dioxane; ethanol, propanol, and butanol Alcohol solvents such as ethyl cellosolve, cellosolve solvents such as butyl cellosolve; ester solvents such as ethyl acetate and butyl acetate; amide solvents such as dimethylformamide and dimethylacetamide, etc. . The concentration of the resin component in the coating solution is generally in the range of 0.001 to 30 wt%, particularly 0.001 to 2 wt%.

フェライト粒子への樹脂の被覆方法としては、例えばスプレードライ法や流動床法あるいは流動床を用いたスプレードライ法、浸漬法等を用いることができる。これらの中でも、少ない樹脂量で効率的に塗布できる点で流動床法が特に好ましい。樹脂被覆量は、例えば流動床法の場合には吹き付ける樹脂溶液量や吹き付け時間によって調整することができる。   As a method for coating the resin on the ferrite particles, for example, a spray drying method, a fluidized bed method, a spray drying method using a fluidized bed, an immersion method, or the like can be used. Among these, the fluidized bed method is particularly preferable in that it can be efficiently applied with a small amount of resin. For example, in the case of the fluidized bed method, the resin coating amount can be adjusted by the amount of resin solution sprayed and the spraying time.

キャリアの粒子径は、一般に体積平均粒子径で20〜200μm、特に30〜150μmのものが好ましい。また、本発明のキャリアをトナーと混合し現像剤として使用する場合には、キャリアの体積平均粒子径は100μm以上とするのが好ましい。キャリアの見掛け密度は、磁性材料を主体とする場合は磁性体の組成や表面構造等によっても相違するが、一般に2.4〜3.0g/cmの範囲が好ましい。 The particle diameter of the carrier is generally 20 to 200 μm, particularly preferably 30 to 150 μm in volume average particle diameter. When the carrier of the present invention is mixed with toner and used as a developer, the carrier preferably has a volume average particle diameter of 100 μm or more. When the carrier material is mainly composed of a magnetic material, the apparent density of the carrier varies depending on the composition of the magnetic material, the surface structure, and the like, but is generally preferably in the range of 2.4 to 3.0 g / cm 3 .

本発明に係る電子写真用現像剤は、以上のようにして作製したキャリアとトナーとを混合してなる。キャリアとトナーとの混合比に特に限定はなく、使用する現像装置の現像条件などから適宜決定すればよい。一般に現像剤中のトナー濃度は1〜20wt%の範囲が好ましい。トナー濃度が1wt%未満の場合、画像濃度が薄くなりすぎ、他方トナー濃度が20wt%を超える場合、現像装置内でトナー飛散が発生し機内汚れや転写紙などの背景部分にトナーが付着する不具合が生じるおそれがあるからである。より好ましいトナー濃度は3〜15wt%の範囲である。   The electrophotographic developer according to the present invention is obtained by mixing the carrier prepared as described above and a toner. The mixing ratio of the carrier and the toner is not particularly limited, and may be determined as appropriate based on the developing conditions of the developing device to be used. In general, the toner concentration in the developer is preferably in the range of 1 to 20 wt%. When the toner density is less than 1 wt%, the image density becomes too low, and when the toner density exceeds 20 wt%, the toner scatters in the developing device, and the toner adheres to the background portion such as internal dirt or transfer paper. This is because there is a risk of occurrence. A more preferable toner concentration is in the range of 3 to 15 wt%.

キャリアとトナーとの混合は、従来公知の混合装置を用いることができる。例えばヘンシェルミキサー、V型混合機、タンブラーミキサー、ハイブリタイザー等を用いることができる。   A known mixing device can be used for mixing the carrier and the toner. For example, a Henschel mixer, a V-type mixer, a tumbler mixer, a hybridizer, or the like can be used.

以下、本発明を実施例によりさらに詳しく説明するが本発明はこれらの例に何ら限定されるものではない。   EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these examples at all.

実施例1
原料としてのFe(平均粒径:0.6μm)10.75kg(67.3mol)と、Mn(平均粒径:2μm)4.25kg(19.0mol)とを水5.0kg中に分散し、分散剤としてポリカルボン酸アンモニウム系分散剤を90g、還元剤としてカーボンブラックを45g、SiO原料としてコロイダルシリカ(固形分濃度50%)を30g(0.25mol)、SrCOを22g(0.15mol)添加して混合物とした。このときの固形分濃度を測定したところ75重量%であった。この混合物を湿式ボールミル(メディア径2mm)により粉砕処理し、混合スラリーを得た。
Example 1
As a raw material, Fe 2 O 3 (average particle size: 0.6 μm) 10.75 kg (67.3 mol) and Mn 3 O 4 (average particle size: 2 μm) 4.25 kg (19.0 mol) were added to water 5. Dispersed in 0 kg, 90 g of an ammonium polycarboxylate dispersant as a dispersant, 45 g of carbon black as a reducing agent, 30 g (0.25 mol) of colloidal silica (solid content concentration 50%) as an SiO 2 raw material, SrCO 3 22 g (0.15 mol) was added to form a mixture. The solid concentration at this time was measured and found to be 75% by weight. This mixture was pulverized by a wet ball mill (media diameter 2 mm) to obtain a mixed slurry.

この混合スラリーをスプレードライヤーにて約130℃の熱風中に噴霧し、粒径10〜200μmの乾燥造粒物を得た。この造粒物から、網目156μmの篩網を用いて粗粒を分離し、網目63μmの篩網を用いて微粒を分離した。   This mixed slurry was sprayed into hot air at about 130 ° C. with a spray dryer to obtain a dry granulated product having a particle size of 10 to 200 μm. From this granulated product, coarse particles were separated using a sieve mesh having a mesh of 156 μm, and fine particles were separated using a sieve mesh having a mesh of 63 μm.

この造粒粉を、酸素濃度が8000ppmに調整された窒素雰囲気下の電気炉に投入し1130℃で3時間焼成した。得られた焼成物を解粒後に振動ふるいを用いて分級し、平均粒径25μmのフェライト粒子を得た。得られたフェライト粒子の磁気特性、電気抵抗、帯電量比、Sr含有量を下記に示す方法で測定すると共に、粉体X線回折(「XRD」X-ray diffraction)分析を行い結晶構造を分析し格子定数を算出した。表1に結果をまとめて示す。   This granulated powder was put into an electric furnace in a nitrogen atmosphere in which the oxygen concentration was adjusted to 8000 ppm and fired at 1130 ° C. for 3 hours. The obtained fired product was classified using a vibrating screen after pulverization to obtain ferrite particles having an average particle size of 25 μm. The magnetic properties, electrical resistance, charge ratio, and Sr content of the obtained ferrite particles are measured by the following methods, and the crystal structure is analyzed by powder X-ray diffraction (“XRD” X-ray diffraction) analysis. The lattice constant was calculated. Table 1 summarizes the results.

また、図1にXRDパターン、図2にSr含有量と格子定数との関係を示すグラフ、図3に、Sr含有量と帯電量比との関係を示すグラフをそれぞれ示す。   FIG. 1 shows an XRD pattern, FIG. 2 shows a graph showing the relationship between the Sr content and the lattice constant, and FIG. 3 shows a graph showing the relationship between the Sr content and the charge amount ratio.

(平均粒径)
日機装株式会社製のマイクロトラック、Model9320−X100を用いて測定した。
(Average particle size)
Measurement was performed using a Microtrack, Model 9320-X100 manufactured by Nikkiso Co., Ltd.

(電気抵抗)
表面を電解研磨した厚さ2mmの電極としての真鍮板2枚を、距離2mm離して対向するように配置した。電極間にフェライト粒子200mgを装入した後、それぞれの電極の背後に、断面積240mmの磁石(表面磁束密度が1500ガウスのフェライト磁石)を配置して、電極間にフェライト粒子のブリッジを形成させた。そして、50Vから1000Vまでの直流電圧を電極間に印加し、フェライト粒子に流れる電流値を測定し、フェライト粒子の電気抵抗を算出した。
(Electrical resistance)
Two brass plates as electrodes having a thickness of 2 mm whose surfaces were electropolished were arranged to face each other with a distance of 2 mm. After inserting 200 mg of ferrite particles between the electrodes, a magnet having a cross-sectional area of 240 mm 2 (ferrite magnet having a surface magnetic flux density of 1500 gauss) is placed behind each electrode to form a bridge of ferrite particles between the electrodes. I let you. And the direct-current voltage from 50V to 1000V was applied between electrodes, the value of the electric current which flows into a ferrite particle was measured, and the electrical resistance of the ferrite particle was computed.

(帯電量比)
フェライト粒子9.5gと市販のフルカラー機のトナー0.5gとを100mlの栓付きガラス瓶に入れ、温度25℃、相対湿度50%の環境下で12時間放置して調湿した後、フェライト粒子とトナーとを入れたガラス瓶を振とう機(ヤヨイ社製「NEW-YS型」)を用いて200回/min,角度60°の条件で30分間振とうさせた。
このサンプル500mgを測定試料として、795メッシュのSUS製篩網に載せ、吸引圧5.0kPaで1分間吸引することによりトナーを除去し、残ったフェライト粒子の電荷量(Q)を測定し、下記式から重量あたりの帯電量を算出した。但し、Mはフェライト粒子の重量である。帯電量の測定は、日本パイオテク(株)製、STC−1−C1型を用いて行った。
帯電量(μC/g)=Q(μC)/M(g)
一方、SrCOを添加しない以外は前記フェライト粒子と同様の方法でリファレンスフェライト粒子を作製し、上記測定方法で帯電量を測定した。そして、リファレンスフェライト粒子の帯電量に対するフェライト粒子の帯電量比を算出した。
(Charge amount ratio)
9.5 g of ferrite particles and 0.5 g of commercially available full color machine toner are placed in a 100 ml stoppered glass bottle and left to stand for 12 hours in an environment of a temperature of 25 ° C. and a relative humidity of 50%. Using a shaker (“NEW-YS type” manufactured by Yayoi Co., Ltd.), the glass bottle containing the toner was shaken for 30 minutes under the conditions of 200 times / min and an angle of 60 °.
Using 500 mg of this sample as a measurement sample, it was placed on a 795 mesh SUS sieve screen, and the toner was removed by suction for 1 minute at a suction pressure of 5.0 kPa, and the charge amount (Q) of the remaining ferrite particles was measured. The charge amount per weight was calculated from the equation. Where M is the weight of the ferrite particles. The measurement of the charge amount was performed using STC-1-C1 type manufactured by Nippon Piotech Co., Ltd.
Charge amount (μC / g) = Q (μC) / M (g)
On the other hand, reference ferrite particles were prepared in the same manner as the ferrite particles except that SrCO 3 was not added, and the charge amount was measured by the above measuring method. Then, the charge amount ratio of the ferrite particles to the charge amount of the reference ferrite particles was calculated.

(磁気特性)
室温専用振動試料型磁力計(VSM)(東英工業社製「VSM−P7」)を用いて磁化の測定を行い、79.58×10(A/m)及び39.79×10(A/m)の磁場における磁化σ1000(A・m/kg)及び磁化σ500(A・m/kg)、そして飽和磁化σ(A・m/kg),残留磁化σ(A・m/kg),保磁力H(A/m)をそれぞれ測定した。
(Magnetic properties)
Magnetization is measured using a vibration sample type magnetometer (VSM) dedicated to room temperature (“VSM-P7” manufactured by Toei Kogyo Co., Ltd.), and 79.58 × 10 3 (A / m) and 39.79 × 10 3 ( Magnetization σ 1000 (A · m 2 / kg) and magnetization σ 500 (A · m 2 / kg), saturation magnetization σ S (A · m 2 / kg), residual magnetization σ r ( A · m 2 / kg) and coercive force H C (A / m) were measured.

(粉体X線回折分析及び格子定数の算出)
X線回折分析装置(リガク社製「RINT2000」)を用いてXRDパターンを測定した。X線源はコバルトを使用し、加速電圧40kV、電流30mAでX線を発生させた。粉末X線の測定条件は走査モード:FT,発散スリット:1/2°、散乱スピード:1/2°、受光スリット:0.15mm、回転速度:5.000rpm、測定角度:10°≦2θ≦90°、測定間隔:0.01°、計測時間:5秒、積算回数3回で測定を行った。そして、得られたXRDパターンから格子定数を算出した。
(Powder X-ray diffraction analysis and calculation of lattice constant)
The XRD pattern was measured using an X-ray diffraction analyzer (“RINT2000” manufactured by Rigaku Corporation). Cobalt was used as the X-ray source, and X-rays were generated at an acceleration voltage of 40 kV and a current of 30 mA. The measurement conditions of the powder X-ray are scanning mode: FT, diverging slit: 1/2 °, scattering speed: 1/2 °, light receiving slit: 0.15 mm, rotation speed: 5.000 rpm, measurement angle: 10 ° ≦ 2θ ≦ The measurement was performed at 90 °, measurement interval: 0.01 °, measurement time: 5 seconds, and integration number of 3 times. And the lattice constant was computed from the obtained XRD pattern.

(Sr含有量)
フェライト粒子を酸溶液中で溶解しICP発光分析装置(島津製作所製「ICPS−7510」)による定量分析から算出した。なお、Srの含有量はフェライト粒子に対するmol%のことである。
(Sr content)
The ferrite particles were dissolved in an acid solution and calculated from quantitative analysis using an ICP emission analyzer (“ICPS-7510” manufactured by Shimadzu Corporation). In addition, content of Sr is mol% with respect to a ferrite particle.

実施例2
原料としてのSrCOを55g(0.38mol)添加した以外は実施例1と同様にしてフェライト粒子を得た。得られたフェライト粒子の磁気特性、電気抵抗、帯電量比、XRDパターン、格子定数を前記方法で測定した。測定結果を表1にまとめて示す。
Example 2
Ferrite particles were obtained in the same manner as in Example 1 except that 55 g (0.38 mol) of SrCO 3 as a raw material was added. The magnetic properties, electric resistance, charge amount ratio, XRD pattern, and lattice constant of the obtained ferrite particles were measured by the above methods. The measurement results are summarized in Table 1.

実施例3
原料としてのSrCOを111g(0.75mol)添加した以外は実施例1と同様にしてフェライト粒子を得た。得られたフェライト粒子の磁気特性、電気抵抗、帯電量比、XRDパターン、格子定数を前記方法で測定した。測定結果を表1にまとめて示す。
Example 3
Ferrite particles were obtained in the same manner as in Example 1 except that 111 g (0.75 mol) of SrCO 3 as a raw material was added. The magnetic properties, electric resistance, charge amount ratio, XRD pattern, and lattice constant of the obtained ferrite particles were measured by the above methods. The measurement results are summarized in Table 1.

実施例4
原料としてのSrCOを221g(1.50mol)添加した以外は実施例1と同様にしてフェライト粒子を得た。得られたフェライト粒子の磁気特性、電気抵抗、帯電量比、XRDパターン、格子定数を前記方法で測定した。測定結果を表1にまとめて示す。
Example 4
Ferrite particles were obtained in the same manner as in Example 1 except that 221 g (1.50 mol) of SrCO 3 as a raw material was added. The magnetic properties, electric resistance, charge amount ratio, XRD pattern, and lattice constant of the obtained ferrite particles were measured by the above methods. The measurement results are summarized in Table 1.

実施例5
原料としてのSrCOを368g(2.50mol)添加した以外は実施例1と同様にしてフェライト粒子を得た。得られたフェライト粒子の磁気特性、電気抵抗、帯電量比、XRDパターン、格子定数を前記方法で測定した。測定結果を表1にまとめて示す。
Example 5
Ferrite particles were obtained in the same manner as in Example 1 except that 368 g (2.50 mol) of SrCO 3 as a raw material was added. The magnetic properties, electric resistance, charge amount ratio, XRD pattern, and lattice constant of the obtained ferrite particles were measured by the above methods. The measurement results are summarized in Table 1.

比較例1
原料としてのSrCOを553g(3.75mol)添加した以外は実施例1と同様にしてフェライト粒子を得た。得られたフェライト粒子の磁気特性、電気抵抗、帯電量比、XRDパターン、格子定数を前記方法で測定した。測定結果を表1にまとめて示す。
Comparative Example 1
Ferrite particles were obtained in the same manner as in Example 1 except that 553 g (3.75 mol) of SrCO 3 as a raw material was added. The magnetic properties, electric resistance, charge amount ratio, XRD pattern, and lattice constant of the obtained ferrite particles were measured by the above methods. The measurement results are summarized in Table 1.

比較例2
原料としてのSrCOを1105g(7.50mol)添加した以外は実施例1と同様にしてフェライト粒子を得た。得られたフェライト粒子の磁気特性、電気抵抗、帯電量比、XRDパターン、格子定数を前記方法で測定した。測定結果を表1にまとめて示す。
Comparative Example 2
Ferrite particles were obtained in the same manner as in Example 1 except that 1105 g (7.50 mol) of SrCO 3 as a raw material was added. The magnetic properties, electric resistance, charge amount ratio, XRD pattern, and lattice constant of the obtained ferrite particles were measured by the above methods. The measurement results are summarized in Table 1.

図1に示すXRDパターンによれば、実施例1〜5のフェライト粒子ではスピネル型結晶構造のピークのみが検出され、マグネトプランバイト型結晶構造のピークは検出されなかった。これに対し、比較例1,2のフェライト粒子ではスピネル型結晶構造及びマグネトプランバイト型結晶構造のピークが検出された。   According to the XRD pattern shown in FIG. 1, only the peak of the spinel crystal structure was detected in the ferrite particles of Examples 1 to 5, and the peak of the magnetoplumbite crystal structure was not detected. On the other hand, in the ferrite particles of Comparative Examples 1 and 2, peaks of the spinel crystal structure and the magnetoplumbite crystal structure were detected.

また、図2に示す格子定数とSr含有量との関係からは、実施例1〜5のフェライト粒子では、Sr含有量が増えるにしたがって格子定数が大きくなる一方、Sr含有量が3mol%を超えた比較例1,2のフェライト粒子では格子定数はほぼ一定値となった。これは、Sr含有量が3mol%以下では、Srがスピネル型結晶構造に固溶してSr含有量の増加と共に結晶格子が大きくなるが、Sr含有量が3mol%を超えるとスピネル型結晶構造にSrがそれ以上固溶できなくなり結晶格子の大きさが一定となるからと考えられる。   Further, from the relationship between the lattice constant and the Sr content shown in FIG. 2, in the ferrite particles of Examples 1 to 5, the lattice constant increases as the Sr content increases, while the Sr content exceeds 3 mol%. In the ferrite particles of Comparative Examples 1 and 2, the lattice constant was almost constant. This is because when the Sr content is 3 mol% or less, Sr is dissolved in the spinel crystal structure and the crystal lattice becomes larger as the Sr content increases, but when the Sr content exceeds 3 mol%, the spinel crystal structure is obtained. This is probably because Sr cannot be further dissolved and the crystal lattice size becomes constant.

これらのことから、実施例1〜5のフェライト粒子ではSrがスピネル型結晶構造に固溶し、Sr含有量の多い比較例1,2のフェライト粒子では、Srのスピネル型結晶構造に固溶できる量が限界に達し、過剰なSrがマグネトプランバイト型結晶構造をとっていると考えられる。   From these facts, in the ferrite particles of Examples 1 to 5, Sr can be dissolved in the spinel crystal structure, and in the ferrite particles of Comparative Examples 1 and 2 having a large Sr content, Sr can be dissolved in the spinel crystal structure. The amount reaches the limit, and it is considered that excess Sr has a magnetoplumbite type crystal structure.

そして、Srがマグネトプランバイト型結晶構造をとらず、スピネル型結晶構造に固溶した実施例1〜5のフェライト粒子では、磁気特性および電気抵抗共に実使用上問題のない範囲であった。加えて、図3から明らかなように、実施例1〜5のフェライト粒子では、リファレンスフェライト粒子に対する帯電量比が1.5以上と高い値を示した。これに対し、比較例1,2のフェライト粒子では、前記帯電量比は0.9及び0.7とリファレンスフェライト粒子の帯電量未満であった。   And in the ferrite particles of Examples 1 to 5 in which Sr did not take the magnetoplumbite type crystal structure but was dissolved in the spinel type crystal structure, both the magnetic properties and the electric resistance were in the range where there was no problem in practical use. In addition, as is clear from FIG. 3, the ferrite particles of Examples 1 to 5 showed a high charge ratio of 1.5 or more with respect to the reference ferrite particles. On the other hand, in the ferrite particles of Comparative Examples 1 and 2, the charge amount ratio was 0.9 and 0.7, which was less than the charge amount of the reference ferrite particles.

本発明に係るフェライト粒子では、高抵抗化と高磁気特性を実現できるのみならず高帯電性をも実現でき有用である。また、本発明に係るフェライト粒子を、例えば、画像形成装置の電子写真現像用キャリアとして用いた場合には、高速化及び高画質化が達成される。   The ferrite particles according to the present invention are useful because they can realize not only high resistance and high magnetic properties, but also high chargeability. In addition, when the ferrite particles according to the present invention are used, for example, as an electrophotographic developing carrier of an image forming apparatus, high speed and high image quality are achieved.

Claims (5)

組成式MFe3−X(但し、MはMn,Mg,Ti,Cu,Zn,Niからなる群より選ばれる少なくとも1種の金属、0≦X≦1)で表される材料を主成分とし、アルカリ土類金属元素を含有するフェライト粒子であって、
前記アルカリ土類金属元素がマグネトプランバイト型結晶構造をとらず、スピネル型結晶構造に固溶していることを特徴とするフェライト粒子。
A material represented by a composition formula M X Fe 3-X O 4 (where M is at least one metal selected from the group consisting of Mn, Mg, Ti, Cu, Zn, and Ni, 0 ≦ X ≦ 1). Ferrite particles containing an alkaline earth metal element as a main component,
The ferrite particle, wherein the alkaline earth metal element does not have a magnetoplumbite type crystal structure but is dissolved in a spinel type crystal structure.
前記アルカリ土類金属元素がSr及びBaの少なくとも一方である請求項1記載のフェライト粒子。   The ferrite particle according to claim 1, wherein the alkaline earth metal element is at least one of Sr and Ba. 前記アルカリ土類金属元素の含有量が3mol%以下である請求項1又は2記載のフェライト粒子。   The ferrite particles according to claim 1 or 2, wherein the content of the alkaline earth metal element is 3 mol% or less. 請求項1〜3のいずれかに記載のフェライト粒子の表面を樹脂で被覆したことを特徴とする電子写真現像用キャリア。   A carrier for electrophotographic development, wherein the surface of the ferrite particles according to claim 1 is coated with a resin. 請求項4記載のキャリアとトナーとを含むことを特徴とする電子写真用現像剤。   An electrophotographic developer comprising the carrier according to claim 4 and a toner.
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