JP2012144401A - Ferrite particle, and carrier for developing electrophotograph using it, and developer for electrophotograph - Google Patents
Ferrite particle, and carrier for developing electrophotograph using it, and developer for electrophotograph Download PDFInfo
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- Developing Agents For Electrophotography (AREA)
- Compounds Of Iron (AREA)
Abstract
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.
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 ferrite particles 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速度及びトナーの帯電速度を速めている。 In recent years, in order to meet market demands for higher image formation speed and higher image quality in image forming apparatuses, the rotation speed of the developing sleeve and stirring member of the developing apparatus is increased, and the developer supply speed to the electrostatic latent image is increased. 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、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、コーティングキャリアの芯材に欠けや割れが発生しやすくなる。欠けや割れが生じたコーティングキャリアは飛散して感光体に付着し画質低下の原因の一つとなっていた。 Increasing the rotation speed of the developing sleeve and the stirring member increases the collision between the coating carriers and the friction between the coating carrier and the inner wall surface of the developing device, so that the core material of the coating carrier is likely to be chipped or cracked. Become. The coating carrier in which chipping or cracking has occurred scatters and adheres to the photoreceptor, which is one of the causes of image quality degradation.
そこで、例えば特許文献１では、キャリア芯材の強度を高めるため、フェライト原料を粉砕、混合、ペレット化した後、９００〜１２００℃で仮焼成し、次いで、粉砕、スラリー化し、スラリーの粒径Ｄ５０およびＤ９０を小さくした後、１１５０〜１２３０℃で本焼成して電子写真用キャリア芯材を製造する方法が提案されている。 Therefore, in Patent Document 1, for example, in order to increase the strength of the carrier core material, the ferrite raw material is pulverized, mixed, and pelletized, and then calcined at 900 to 1200 ° C., and then pulverized and slurried. after reducing the 50 and D 90, a method of manufacturing the electrophotographic carrier core material and the firing at 1150-1230 ° C. has been proposed.
しかしながら、前記提案の製造方法では、キャリア芯材の製造工程での焼成温度、焼成雰囲気、原料組成などによって結晶粒界の成長が大きな影響を受けるため、得られるキャリア芯材の粒子強度は必ずしも満足できるものではなかった。 However, in the proposed manufacturing method, since the grain boundary growth is greatly affected by the firing temperature, firing atmosphere, raw material composition, etc. in the carrier core manufacturing process, the particle strength of the obtained carrier core is not always satisfactory. It wasn't possible.
本発明は、このような従来の問題点に鑑みなされたものであり、その目的は、高帯電性と高強度と備えた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 thereof is to provide ferrite particles having high chargeability and high strength.
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電子写真用の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 an electrophotographic carrier and a developer that can cope with an increase in image forming speed and high image quality.
本発明によれば、組成式（ＭＸＦｅ３−Ｘ）Ｏ４（ただし、ＭはＦｅ，Ｍｇ，Ｍｎ，Ｔｉ，Ｃｕ，Ｚｎ，Ｓｒ，Ｎｉからなる群より選ばれる少なくとも１種の金属元素、０≦Ｘ＜１）で表される材料を主成分とし、Ｃａ元素とＰ元素とを含有するフェライト粒子であって、Ｃａ元素の含有量がＰ元素の含有量に対して重量比で０．４５〜１．０の範囲であ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 element selected from the group consisting of Fe, Mg, Mn, Ti, Cu, Zn, Sr, Ni) , 0 ≦ X <1) as a main component, and ferrite particles containing Ca element and P element, and the content of Ca element is 0 by weight with respect to the content of P element. Ferrite particles are provided that are in the range of .45 to 1.0.
ここで、高帯電性と高強度とを一層向上させる観点からは、Ｃａ元素及びＰ元素の総含有量を５０００ｐｐｍ以下の範囲とするのが好ましい。 Here, from the viewpoint of further improving high chargeability and high strength, the total content of Ca element and P element is preferably in the range of 5000 ppm or less.
また、Ｃａ元素とＰ元素とは主として同一箇所に存在しているのが好ましい。 Moreover, it is preferable that Ca element and P element exist mainly in the same place.
そしてまた、Ｃａ元素とＰ元素とは主として結晶粒界に存在しているのが好ましい。 In addition, it is preferable that the Ca element and the P element exist mainly at the crystal grain boundaries.
また本発明によれば、前記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が提供される。 In addition, according to the present invention, there is 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、前記記載の電子写真現像用キャリアとトナーとを含む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 electrophotographic developer carrier described above and a toner.
本発明のフェライト粒子は、Ｃａ元素とＰ元素とを含有し、Ｃａ元素の含有量がＰ元素の含有量に対して重量比で０．４５〜１．０の範囲であるので、高い帯電性を有しながら高い強度をも有する。 The ferrite particles of the present invention contain Ca element and P element, and the content of Ca element is in the range of 0.45 to 1.0 by weight ratio with respect to the content of P element. It has high strength while having.
また、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。 Further, when the ferrite particles of the present invention are used as an electrophotographic developing carrier of an image forming apparatus, high speed and high image quality are achieved.
本発明者等は、高い帯電性を有しながら高い強度をも有するフェライト粒子を得るべく種々検討を行った結果、Ｃａ成分を添加すると、フェライト粒子の帯電性は上がるものの粒子強度が低下すること、そしてＰ成分を添加すると焼結時に結晶成長が促進されて粒子強度が向上することを見出した。そこで、Ｃａ成分とＰ成分とを所定の割合で添加することによって、フェライト粒子の帯電性の向上を図りながら強度の低下を防止できることを見出し本発明をなすに至った。 As a result of various studies conducted by the present inventors to obtain ferrite particles having high chargeability while having high chargeability, the addition of Ca component increases the chargeability of ferrite particles but decreases the particle strength. Further, it has been found that the addition of the P component promotes crystal growth during sintering and improves the particle strength. Accordingly, the inventors have found that by adding the Ca component and the P component at a predetermined ratio, a decrease in strength can be prevented while improving the charging property of the ferrite particles, and the present invention has been made.
すなわち、本発明に係るフェライト粒子の大きな特徴は、組成式（ＭＸＦｅ３−Ｘ）Ｏ４（ただし、ＭはＦｅ，Ｍｇ，Ｍｎ，Ｔｉ，Ｃｕ，Ｚｎ，Ｓｒ，Ｎｉからなる群より選ばれる少なくとも１種の金属元素、０≦Ｘ＜１）で表される材料を主成分とし、Ｃａ元素とＰ元素とを含有するとともに、Ｃａ元素の含有量をＰ元素の含有量に対して重量比で０．４５〜１．０の範囲としたことにある。Ｃａ／Ｐが重量比で０．４５未満であると充分な帯電性が得られない一方、Ｃａ／Ｐが重量比で１．０を超えると充分な粒子強度が得られない。より好ましいＣａ／Ｐが重量比は０．６〜０．８の範囲である。 That is, 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 selected from the group consisting of Fe, Mg, Mn, Ti, Cu, Zn, Sr, Ni). At least one kind of metal element, 0 ≦ X <1) as a main component, containing Ca element and P element, and the content of Ca element with respect to the content of P element by weight The ratio is in the range of 0.45 to 1.0. When Ca / P is less than 0.45 by weight, sufficient chargeability cannot be obtained, whereas when Ca / P exceeds 1.0 by weight, sufficient particle strength cannot be obtained. More preferable Ca / P has a weight ratio in the range of 0.6 to 0.8.
また、フェライト粒子の帯電性及び粒子強度の一層の向上を図る観点からはＣａ元素及びＰ元素の総含有量を５０００ｐｐｍ以下とするのが好ましい。より好ましくは４５００ｐｐｍ以下である。一方、Ｃａ元素及びＰ元素の総含有量の好ましい下限値は３５００ｐｐｍである。 Further, from the viewpoint of further improving the chargeability and particle strength of the ferrite particles, the total content of Ca element and P element is preferably 5000 ppm or less. More preferably, it is 4500 ppm or less. On the other hand, the preferable lower limit of the total content of Ca element and P element is 3500 ppm.
Ｃａ元素とＰ元素とは、主として同一箇所に存在しているのが好ましい。図１に、後述する実施例１におけるフェライト粒子断面のＥＤＳによるＣａ元素のピークカウントマップ画像を、図２に、Ｐ元素のピークカウントマップ画像をそれぞれ示す。図１と図２のピークカウントマップ画像を重ね合わせると、Ｃａ元素とＰ元素の存在箇所がほぼ一致していることがわかる。このような、ＥＤＳのピークカウントマップ画像結果から、本発明者等は、フェライト粒子には、粒子中にＣａ（ＰＯ３）２が析出しているのではないかと推測している。また、Ｃａ元素とＰ元素とが存在している箇所は結晶粒界である。Ｃａ元素とＰ元素とが粒子粒界に存在することによって、フェライト粒子の帯電性及び粒子強度の向上が一層図られる。 It is preferable that the Ca element and the P element exist mainly at the same location. FIG. 1 shows a peak count map image of Ca element by EDS of a ferrite particle cross section in Example 1 described later, and FIG. 2 shows a peak count map image of P element. When the peak count map images of FIG. 1 and FIG. 2 are overlapped, it can be seen that the locations where the Ca element and the P element exist are almost the same. From these EDS peak count map image results, the present inventors presume that Ca (PO 3 ) 2 is precipitated in the ferrite particles. Moreover, the place where Ca element and P element exist is a crystal grain boundary. The presence of the Ca element and the P element at the grain boundary further improves the chargeability and particle strength of the ferrite particles.
フェライト粒子の主として同一箇所、特に結晶粒界にＣａ元素とＰ元素とを存在させるには、フェライト粒子の製造工程において出発原料としてのＣａ成分原料とＰ成分原料とを別原料として添加することが推奨される。フェライト粒子の具体的製造方法は後段で詳述するが、造粒後の焼結工程において、初めにＰ成分が溶融して粘着性を奏し、造粒物の結晶粒子同士を融着し、そこにＣａ成分が付着して結果的にＣａとＰとが結晶粒界に存在するようになるのではないかと今のところ推測している。 In order to allow Ca element and P element to exist mainly at the same location of the ferrite particle, particularly at the grain boundary, Ca component raw material and P component raw material as starting materials may be added as separate raw materials in the ferrite particle manufacturing process. Recommended. The specific method for producing the ferrite particles will be described in detail later. In the sintering step after granulation, the P component first melts to exhibit adhesiveness, and the crystal grains of the granulated material are fused to each other. At present, it is speculated that the Ca component may adhere to the surface and Ca and P will eventually exist at the grain boundaries.
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成分原料とＭ成分原料、そして添加剤としてＣａ成分原料とＰ成分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。なお、ＭはＦｅ、Ｍｇ、Ｍｎ、Ｔｉ、Ｃｕ、Ｚｎ、Ｓｒ、Ｎｉ等の２価の金属元素から選ばれる少なくとも１種の金属元素である。Ｆｅ成分原料としては、Ｆｅ２Ｏ３等が好適に使用される。Ｍ成分原料としては、ＭｎであればＭｎＣＯ３、Ｍｎ３Ｏ４等が使用でき、ＭｇであればＭｇＯ、Ｍｇ（ＯＨ）２、ＭｇＣＯ３が好適に使用できる。また、Ｃａ成分原料としては、ＣａＯ、Ｃａ（ＯＨ）２、ＣａＣＯ３等から選択される少なくとも１種の化合物が好適に使用される。Ｐ成分原料としてはＰ（赤リン）、Ｐ２Ｏ４等が好適に使用される。 First, an Fe component raw material, an M component raw material, and Ca component raw material and P component raw material as additives are weighed and charged into a dispersion medium to prepare a slurry. M is at least one metal element selected from divalent metal elements such as Fe, Mg, Mn, Ti, Cu, Zn, Sr, and Ni. As the Fe component material, Fe 2 O 3 or the like is preferably used. As the M component raw material, MnCO 3 , Mn 3 O 4 and the like can be used for Mn, and MgO, Mg (OH) 2 and MgCO 3 can be suitably used for Mg. As the Ca component raw material, at least one compound selected from CaO, Ca (OH) 2 , CaCO 3 and the like is preferably used. P (red phosphorus), P 2 O 4 or the like is preferably used as the P component raw material.
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成分原料、Ｍ成分原料、Ｃａ成分原料、Ｐ成分原料の他、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 component raw material, the M component raw material, the Ca component raw material, and the P component raw material, a binder, a dispersant, and the like may be blended in 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、Ｃａ成分原料とＰ成分原料の添加量が、Ｆｅ成分原料とＭ成分原料との総重量に対し微量であるので、Ｃａ成分原料及びＰ成分原料を先に分散媒中に分散させ、その後、Ｆｅ成分原料とＭ成分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、Ｆｅ成分原料、Ｍ成分原料、Ｃａ成分原料、Ｐ成分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%. In addition, since the addition amount of Ca component raw material and P component raw material is a very small amount with respect to the total weight of Fe component raw material and M component raw material, Ca component raw material and P component raw material are first dispersed in a dispersion medium, and then The Fe component raw material and the M component raw material may be dispersed in a dispersion medium. Thereby, the raw material can be uniformly dispersed in the dispersion medium. Further, before the Fe component raw material, the M component raw material, the Ca component raw material, and the P component raw material are added to the dispersion medium, a pulverization and mixing process may be performed as 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負帯電性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／ｃｍ３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 a negatively chargeable 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１ｗｔ％〜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 used. Generally, the toner concentration in the developer is preferably in the range of 1 wt% 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実施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
Ｃｕ−Ｚｎ系フェライト粒子を下記方法で作製した。出発原料として、Ｆｅ２Ｏ３を５０００ｇと、ＣｕＯを９７０ｇと、ＺｎＯを８００ｇと、ＣａＣＯ３を３５ｇと、Ｐを３０ｇとを水２３００ｇ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６０ｇ添加して混合物とした。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
Cu-Zn ferrite particles were prepared by the following method. As a starting material, Fe 2 O 3 is dispersed in 5000 g, CuO 970 g, ZnO 800 g, CaCO 3 35 g, P 30 g in 2300 g of water, and an ammonium polycarboxylate dispersant as a dispersant. Was added to make a mixture. 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１８０℃の熱風中に噴霧し（ディスク回転数２０，０００ｒｐｍ）、粒径１０〜２００μｍの乾燥造粒物を得た。この造粒物から、網目９１μｍの篩網を用いて粗粒を分離し、網目３７μｍの篩網を用いて微粒を分離した。 This mixed slurry was sprayed into hot air at about 180 ° C. with a spray dryer (disk rotation speed: 20,000 rpm) 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 size of 91 μm, and fine particles were separated using a sieve mesh having a mesh size of 37 μm.
この造粒粉を、大気雰囲気下の電気炉に投入し１２００℃で３時間焼成した。得られた焼成物をハンマーミルで解砕した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。図１及び図２に、フェライト粒子断面のＥＤＳによるＣａ元素及びＰ元素のピークカウントマップ画像を示す。また、得られたフェライト粒子のＣａ元素及びＰ元素の含有量、Ｃａ／Ｐ、見掛け密度、磁気特性、微粉発生量（粒子強度）、帯電量を下記に示す方法で測定した。表１に測定結果をまとめて示す。 This granulated powder was put into an electric furnace in an air atmosphere and fired at 1200 ° C. for 3 hours. The obtained fired product was crushed with a hammer mill and then classified using a vibration sieve to obtain ferrite particles having an average particle diameter of 25 μm. FIG. 1 and FIG. 2 show peak count map images of Ca element and P element by EDS of a ferrite particle cross section. Further, the content of Ca element and P element, Ca / P, apparent density, magnetic properties, fine powder generation amount (particle strength), and charge amount of the obtained ferrite particles were measured by the following methods. Table 1 summarizes the measurement results.
（ＥＤＳ分析）
フェライト粒子断面のＥＤＳ分析には、日本電子社製のＳＥＭ−ＥＤＳ測定装置（ＳＥＭ：ＪＳＭ−６５１０ＬＡ型，ＥＤＳ：２０３１０ＢＵ型）を用いた。ピークカウントマップ画像の測定条件は、加速電圧：１５ｋＶ、照射電流：１．０ｎＡ、スポットサイズ：７０、解像度：５１２×３１４、デュエルタイム：０．２ｍｓｅｃ、スイーブ回数：１０回である。
(EDS analysis)
An SEM-EDS measuring device (SEM: JSM-6510LA type, EDS: 20310BU type) manufactured by JEOL Ltd. was used for EDS analysis of the ferrite particle cross section. The measurement conditions of the peak count map image are acceleration voltage: 15 kV, irradiation current: 1.0 nA, spot size: 70, resolution: 512 × 314, duel time: 0.2 msec, and number of sweeps: 10 times.
（Ｃａ元素及びＰ元素の含有量）
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」）によってＣａ濃度及びＰ濃度を測定し、さらに酸化物換算を行って求めた。
(Ca element and P element content)
The ferrite particles were dissolved in an acid solution, and the Ca concentration and the P concentration were measured by an ICP emission analyzer (“ICPS-7510” manufactured by Shimadzu Corporation).
（見掛け密度）
フェライト粒子の見掛け密度はJIS Z 2504に準拠して測定した。
(Apparent density)
The apparent density of the ferrite particles was measured according to JIS Z 2504.
（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、７９．５８×１０３（Ａ／ｍ）の磁場における磁化σ１０００（Ａ・ｍ２／ｋｇ）及び飽和磁化σＳ（Ａ・ｍ２／ｋｇ）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 magnetization σ 1000 in a magnetic field of 79.58 × 10 3 (A / m) (A M 2 / kg) and saturation magnetization σ S (A · m 2 / kg) were measured respectively.
（微粉発生量（粒子強度））
作製したフェライト粒子から４０ｇ程度を採取し、網目２５μｍの篩を用いて、マイクロトラック粒度分析計（日機装社製）で測定したときの１４μｍ以下の累積粒子頻度が０．１０％以下となるように調整する。そして、調整した試料３０ｇをサンプルミルに投入し、回転数１２，５００ｒｐｍで１分間撹拌する。次いで、マイクロトラック粒度分析計を用いて１４μｍ以下の累積粒子頻度を測定する。サンプルミルによって処理した後の累積粒子頻度と処理する前の累積粒子頻度との差を算出し、これを微粉発生量として粒子強度の指標とした。
(Amount of fine powder generated (particle strength))
About 40 g is collected from the produced ferrite particles, and the cumulative particle frequency of 14 μm or less is 0.10% or less when measured with a microtrack particle size analyzer (manufactured by Nikkiso Co., Ltd.) using a sieve with a mesh of 25 μm. adjust. Then, 30 g of the adjusted sample is put into a sample mill and stirred for 1 minute at a rotational speed of 12,500 rpm. Next, the cumulative particle frequency of 14 μm or less is measured using a Microtrac particle size analyzer. The difference between the cumulative particle frequency after processing by the sample mill and the cumulative particle frequency before processing was calculated, and this was used as an index of particle strength as the amount of fine powder generated.
（帯電量）
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、下記式から重量当たりの帯電量を算出した。ただし、ｍはフェライト粒子の重量である。帯電量の測定は、日本パイオテク社製「STC-1-C1型」を用いて行った。
帯電量（μＣ／ｇ）＝Ｑ（μＣ）／ｍ（ｇ）
(Charge amount)
9.5 g of ferrite particles and 0.5 g of a commercially available full color toner are put into 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 charge amount was measured using “STC-1-C1 type” manufactured by Nippon Piotech.
Charge amount (μC / g) = Q (μC) / m (g)
実施例２
ＣａＣＯ３を３５ｇ、Ｐを３０ｇとし、焼成温度を１２５０℃とした以外は実施例１と同様にしてフェライト粒子を作製した。作製したフェライト粒子のＣａ元素及びＰ元素の含有量、Ｃａ／Ｐ、見掛け密度、磁気特性、微粉発生量（粒子強度）、帯電量を下記に示す方法で測定した。表１に測定結果をまとめて示す。
Example 2
Ferrite particles were produced in the same manner as in Example 1 except that 35 g of CaCO 3 and 30 g of P were used, and the firing temperature was 1250 ° C. The content of Ca element and P element, Ca / P, apparent density, magnetic property, fine powder generation amount (particle strength), and charge amount of the produced ferrite particles were measured by the following methods. Table 1 summarizes the measurement results.
実施例３
ＣａＣＯ３を４０ｇ、Ｐを３０ｇとし、焼成温度を１１５０℃とした以外は実施例１と同様にしてフェライト粒子を作製した。作製したフェライト粒子のＣａ元素及びＰ元素の含有量、Ｃａ／Ｐ、見掛け密度、磁気特性、微粉発生量（粒子強度）、帯電量を下記に示す方法で測定した。表１に測定結果をまとめて示す。また、図３にフェライト粒子のＳＥＭ写真を示す。
Example 3
Ferrite particles were produced in the same manner as in Example 1 except that CaCO 3 was 40 g, P was 30 g, and the firing temperature was 1150 ° C. The content of Ca element and P element, Ca / P, apparent density, magnetic property, fine powder generation amount (particle strength), and charge amount of the produced ferrite particles were measured by the following methods. Table 1 summarizes the measurement results. FIG. 3 shows an SEM photograph of the ferrite particles.
実施例４
ＣａＣＯ３を３０ｇ、Ｐを３０ｇとした以外は実施例１と同様にしてフェライト粒子を作製した。作製したフェライト粒子のＣａ元素及びＰ元素の含有量、Ｃａ／Ｐ、見掛け密度、磁気特性、微粉発生量（粒子強度）、帯電量を下記に示す方法で測定した。表１に測定結果をまとめて示す。
Example 4
Ferrite particles were produced in the same manner as in Example 1 except that 30 g of CaCO 3 and 30 g of P were used. The content of Ca element and P element, Ca / P, apparent density, magnetic property, fine powder generation amount (particle strength), and charge amount of the produced ferrite particles were measured by the following methods. Table 1 summarizes the measurement results.
実施例５
ＣａＣＯ３を２０ｇ、Ｐを２８ｇとした以外は実施例１と同様にしてフェライト粒子を作製した。作製したフェライト粒子のＣａ元素及びＰ元素の含有量、Ｃａ／Ｐ、見掛け密度、磁気特性、微粉発生量（粒子強度）、帯電量を下記に示す方法で測定した。表１に測定結果をまとめて示す。
Example 5
Ferrite particles were produced in the same manner as in Example 1 except that 20 g of CaCO 3 and 28 g of P were used. The content of Ca element and P element, Ca / P, apparent density, magnetic property, fine powder generation amount (particle strength), and charge amount of the produced ferrite particles were measured by the following methods. Table 1 summarizes the measurement results.
比較例１
ＣａＣＯ３を６０ｇ、Ｐを２８ｇとした以外は実施例１と同様にしてフェライト粒子を作製した。作製したフェライト粒子のＣａ元素及びＰ元素の含有量、Ｃａ／Ｐ、見掛け密度、磁気特性、微粉発生量（粒子強度）、帯電量を下記に示す方法で測定した。表１に測定結果をまとめて示す。
Comparative Example 1
Ferrite particles were produced in the same manner as in Example 1 except that 60 g of CaCO 3 and 28 g of P were used. The content of Ca element and P element, Ca / P, apparent density, magnetic property, fine powder generation amount (particle strength), and charge amount of the produced ferrite particles were measured by the following methods. Table 1 summarizes the measurement results.
比較例２
ＣａＣＯ３を２０ｇ、Ｐを３ｇとした以外は実施例１と同様にしてフェライト粒子を作製した。作製したフェライト粒子のＣａ元素及びＰ元素の含有量、Ｃａ／Ｐ、見掛け密度、磁気特性、微粉発生量（粒子強度）、帯電量を下記に示す方法で測定した。表１に測定結果をまとめて示す。
Comparative Example 2
Ferrite particles were produced in the same manner as in Example 1 except that 20 g of CaCO 3 and 3 g of P were used. The content of Ca element and P element, Ca / P, apparent density, magnetic property, fine powder generation amount (particle strength), and charge amount of the produced ferrite particles were measured by the following methods. Table 1 summarizes the measurement results.
比較例３
ＣａＣＯ３を５ｇ、Ｐを３０ｇとした以外は実施例１と同様にしてフェライト粒子を作製した。作製したフェライト粒子のＣａ元素及びＰ元素の含有量、Ｃａ／Ｐ、見掛け密度、磁気特性、微粉発生量（粒子強度）、帯電量を下記に示す方法で測定した。表１に測定結果をまとめて示す。また、図４にフェライト粒子のＳＥＭ写真を示す。
Comparative Example 3
Ferrite particles were produced in the same manner as in Example 1 except that 5 g of CaCO 3 and 30 g of P were used. The content of Ca element and P element, Ca / P, apparent density, magnetic property, fine powder generation amount (particle strength), and charge amount of the produced ferrite particles were measured by the following methods. Table 1 summarizes the measurement results. FIG. 4 shows an SEM photograph of ferrite particles.
本発明に係るフェライト粒子は高帯電性と高強度とを備え有用である。 The ferrite particles according to the present invention are useful since they have high chargeability and high strength.
Claims (6)
Ｃａ元素の含有量がＰ元素の含有量に対して重量比で０．４５〜１．０の範囲であることを特徴とするフェライト粒子。 Composition formula (M X Fe 3-X ) O 4 (where M is at least one metal element selected from the group consisting of Fe, Mg, Mn, Ti, Cu, Zn, Sr, Ni, 0 ≦ X <1 ) And a ferrite particle containing a Ca element and a P element as a main component,
Ferrite particles characterized in that the content of Ca element is in the range of 0.45 to 1.0 by weight ratio with respect to the content of P element.
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