WO2013014969A1 - Procédé de production de particules de ferrite - Google Patents

Procédé de production de particules de ferrite Download PDF

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Publication number
WO2013014969A1
WO2013014969A1 PCT/JP2012/056956 JP2012056956W WO2013014969A1 WO 2013014969 A1 WO2013014969 A1 WO 2013014969A1 JP 2012056956 W JP2012056956 W JP 2012056956W WO 2013014969 A1 WO2013014969 A1 WO 2013014969A1
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Prior art keywords
firing
ferrite particles
precursor
firing step
slurry
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PCT/JP2012/056956
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English (en)
Japanese (ja)
Inventor
智英 飯田
翔 小川
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Ｄｏｗａエレクトロニクス株式会社
Ｄｏｗａ Ｉｐクリエイション株式会社
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Publication of WO2013014969A1 publication Critical patent/WO2013014969A1/fr

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    • 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
    • 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
    • G03G9/1075—Structural characteristics of the carrier particles, e.g. shape or crystallographic structure

Definitions

  • the present invention relates to a method for producing ferrite particles, and more particularly to a method for producing ferrite particles having a concavo-convex surface and predetermined magnetic properties.
  • an electrostatic latent image formed on the surface of an electrostatic latent image carrier (hereinafter sometimes referred to as “photosensitive member”). Is visualized with a developer, and the visible image is transferred onto paper or the like, and then fixed by heating and pressing.
  • a so-called two-component developer including a carrier and a toner is widely used as a developer from the viewpoint of high image quality and colorization.
  • a developer carrier (hereinafter sometimes referred to as a “development sleeve”) that carries the developer on the surface and a photosensitive member are spaced at a predetermined interval.
  • a developing region a region where the photosensitive member and the developing sleeve face each other.
  • a developing bias voltage is applied between the photosensitive member and the developing sleeve, and toner is attached to the electrostatic latent image on the surface of the photosensitive member.
  • Patent Document 1 In order to improve the image quality, for example, in Patent Document 1, an alternating electric field is formed between the developing sleeve and the photosensitive member, and the electrostatic toner is held by the toner held on the magnetic brush and the toner carried on the developing sleeve. It has been proposed to develop the latent image. Further, Patent Document 2 proposes developing an electrostatic latent image using a carrier having a small particle diameter and low magnetization.
  • the rotational speed of the developing sleeve is increased to increase the supply amount of the developer per unit time to the developing region.
  • an object of the present invention is to provide a method capable of stably producing ferrite particles having a concavo-convex surface and having predetermined magnetic characteristics and resistance characteristics.
  • an Fe component raw material and a Mn component raw material whose components are adjusted so that ferrite particles having a composition represented by Mn X Fe 3-X O 4 (where 0 ⁇ X ⁇ 1) are generated are used as a medium liquid
  • a second firing step in which the precursor is further fired in a reducing atmosphere at a firing temperature in the range of 1050 ° C. to 1300 ° C. to obtain a fired product.
  • the firing temperature in the first firing step is preferably in the range of 1150 ° C. to 1300 ° C.
  • the firing time is preferably 1.5 hours or longer.
  • the firing time in the second firing step is preferably 0.5 hours or more.
  • the oxygen concentration in the second firing step is preferably 1% or less.
  • the surface can be formed into an uneven shape, and predetermined magnetic characteristics and resistance characteristics can be imparted.
  • a firing temperature in the second firing step is a graph showing the relationship between magnetization ⁇ 1k (Am 2 / kg) .
  • 2 is a SEM photograph of ferrite particles of Example 1.
  • 4 is a SEM photograph of ferrite particles of Example 2.
  • 4 is a SEM photograph of ferrite particles of Example 3.
  • 4 is a SEM photograph of ferrite particles of Example 4.
  • 6 is a SEM photograph of ferrite particles of Example 5.
  • 4 is a SEM photograph of ferrite particles of Example 6.
  • the inventors have baked the granulated material containing raw materials in an oxidizing atmosphere. Although the granulated product is once ferritized, it reacts with oxygen in the cooling process and decomposes into Fe oxide and Mn oxide. At this time, the crystal structure changes, and a plurality of angular grains are formed on the particle surface. The surface of the fired product was found to be uneven. However, desired magnetic characteristics such as saturation magnetization and coercive force cannot be obtained by firing in an oxidizing atmosphere.
  • the precursor having a concavo-convex shape which is fired in an oxidizing atmosphere, is sintered again in a reducing atmosphere to impart magnetic properties while maintaining the concavo-convex shape of the surface.
  • the manufacturing method of this invention is demonstrated in order for every process.
  • a Fe component raw material and a Mn component 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 component raw material.
  • Mn component raw material MnCO 3 , Mn 3 O 4 or the like can be suitably used.
  • Water is preferred as the dispersion medium used in the present invention.
  • a binder, a dispersant and the like may be blended in the dispersion medium as necessary.
  • polyvinyl alcohol can be suitably used as the binder.
  • the binder content is preferably about 0.5 to 2 wt% in the slurry.
  • a dispersing agent polycarboxylate ammonium etc. can be used conveniently, for example.
  • the blending amount of the dispersant is preferably about 0.5 to 2 wt% in the slurry.
  • the solid content concentration of the slurry is desirably in the range of 50 to 90 wt%.
  • pulverization and mixing may be performed before introducing the Fe component raw material and the Mn component raw material into the dispersion medium.
  • the slurry prepared as described above is wet-pulverized as necessary.
  • wet grinding is performed for a predetermined time using a ball mill or a vibration mill.
  • the average particle size of the raw material after pulverization is preferably 3 ⁇ m or less, more preferably 1 ⁇ m or less.
  • the vibration mill or ball mill preferably contains a medium having a predetermined particle diameter.
  • the material of the media include iron-based chromium steel and oxide-based zirconia, titania, and alumina.
  • 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.
  • the pulverized slurry is spray-dried and granulated.
  • 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.
  • a spherical granulated product having a particle size of 10 to 200 ⁇ m is obtained.
  • the obtained granulated product has a sharp particle size distribution by removing coarse particles and fine powder using a vibration sieve or the like.
  • the granulated material is put into a furnace heated to a predetermined temperature or higher and fired to produce a precursor (first firing step).
  • the granulated product is fired in an oxidizing atmosphere.
  • the granulated material may be fired in an air atmosphere.
  • the granulated material becomes ferrite and becomes Mn ferrite particles, but reacts with oxygen and decomposes into iron oxide and manganese oxide in the cooling process.
  • the firing temperature in the first firing step is preferably in the range of 1150 ° C. to 1300 ° C., and the firing time is preferably 1.5 hours or more.
  • FIG. 1 shows SEM photographs and peak count map images by EDS analysis of particles before, during and after firing in the first firing step.
  • FIG. 2 shows a diagram showing an XDR pattern.
  • FIGS. 1 and 2 it can be seen that by heating the granulated product, Fe and Mn dispersed in the particles react and ferritization proceeds. In addition, grains are exposed as they become ferritic and are exposed on the surface at the same time, and irregularities are formed on the surface of the particles.
  • the formed ferrite reacts with oxygen and decomposes into iron oxide ( ⁇ -Fe 2 O 3 ) and manganese oxide (Mn 3 O 4 ).
  • the crystal structure of the particles changes from the spinel structure of Mn ferrite to the trigonal system of iron oxide ( ⁇ -Fe 2 O 3 ), and the grain angulation on the particle surface further develops.
  • the precursor thus obtained is agglomerated by sintering, it may be pulverized if necessary.
  • the pulverization of the precursor can be performed by, for example, a hammer mill.
  • the form of the granulation step may be either a continuous type or a batch type.
  • pulverization of the precursor is sufficient to eliminate adhesion between particles, and it is important that the particles themselves are not pulverized.
  • this precursor is put into a furnace heated to a temperature of 1050 ° C. to 1300 ° C. and fired again (second firing step).
  • the precursor can be made ferrite while maintaining the uneven shape on the surface, and predetermined magnetic properties can be imparted.
  • FIG. 3 the SEM photograph of the particle
  • FIG. 4 is a diagram showing XDR patterns of particles before firing and after firing when firing at a temperature of 1200 ° C. in a nitrogen atmosphere in the second firing step.
  • the fired product after the second firing step had spinel structure Mn ferrite particles with an uneven surface.
  • the oxygen concentration in the reducing atmosphere is preferably 1% or less.
  • FIG. 5 shows the relationship between the firing temperature in the second firing step and the magnetization ⁇ 1k (Am 2 / kg) in a magnetic field of 1000 / (4 ⁇ ) kA / m (1 k Oersted).
  • the firing time was unified at 6 hours.
  • the magnetization ⁇ 1k is desirably larger than 50 Am 2 / kg from the viewpoint of preventing carrier scattering from the developing sleeve. Therefore, when Mn ferrite particles are used as a carrier for the developer, the firing temperature in the second firing step is preferably 1050 ° C. or higher.
  • the firing temperature is increased, the desired magnetic properties can be obtained, but the uneven shape on the surface disappears, so the upper limit of the firing temperature is preferably 1300 ° C.
  • the firing time is preferably 0.5 hours or more.
  • the obtained fired product is pulverized.
  • the fired product is pulverized by a hammer mill or the like.
  • the form of the granulation step may be either a continuous type or a batch type.
  • classification may be performed in order to make the particle diameter in a predetermined range.
  • a classification method a conventionally known method such as air classification or sieve classification can be used.
  • the particle size may be aligned within a predetermined range with a vibration sieve or an ultrasonic sieve.
  • the Mn ferrite particles produced as described above can be used for various applications, for example, electrophotographic developing carriers and electromagnetic wave absorbing materials, electromagnetic shielding material powders, rubber, plastic fillers / reinforcing materials, paints, It can be used as a matting material, filler, reinforcing material, etc. for paints and adhesives. Among these, it is particularly preferably used as a carrier for electrophotographic development.
  • the ferrite particles of the present invention prepared 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.
  • the ferrite particles It is preferable that the surface is coated with a resin.
  • resins for coating the surface of the ferrite particles conventionally known resins can be used.
  • silicone resin polyethylene, polypropylene, polyvinyl chloride, poly-4-methylpentene-1, polyvinylidene chloride, ABS (acrylonitrile-butadiene) -Styrene) resin, polystyrene, (meth) acrylic resin, polyvinyl alcohol resin, polyvinyl chloride, polyurethane, polyester, polyamide, polybutadiene, and other thermoplastic elastomers, fluorosilicone resins, etc. .
  • Solvents for coating solutions 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 1 type, or 2 or more types, such as 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 can be used. .
  • the concentration of the resin component in the coating solution is generally in the range of 0.001 to 30 wt%, particularly 0.001
  • 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.
  • the fluidized bed method is particularly preferable in that it can be efficiently applied with a small amount of resin.
  • the resin coating amount can be adjusted by the amount of resin solution sprayed and the spraying time.
  • the particle diameter of the carrier is generally 10 to 110 ⁇ m, particularly 10 to 50 ⁇ m in terms of volume average particle diameter.
  • the apparent density of the carrier when mainly composed of a magnetic material, varies depending on the composition of the magnetic material, the surface structure, etc., but is generally preferably in the range of 1.0 to 2.5 g / cm 3 .
  • the electrophotographic developer 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.
  • the toner concentration in the developer is preferably in the range of 1 wt% to 15 wt%.
  • the toner density is less than 1 wt%, the image density becomes too thin, and when the toner density exceeds 15 wt%, the toner scatters in the developing device, and the toner adheres to the background portion such as in-machine 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 10 wt%.
  • the toner to be used can be produced by a method known per se such as a polymerization method, a pulverization classification method, a melt granulation method, a spray granulation method, and the like in a binder resin mainly composed of a thermoplastic resin. , A colorant, a release agent, a charge control agent, and the like.
  • the volume average particle diameter measured by a Coulter counter is in the range of 5 to 15 ⁇ m, particularly 7 to 12 ⁇ m.
  • a modifier can be added to the surface of the toner particles.
  • the modifier include silica, aluminum oxide, zinc oxide, titanium oxide, magnesium oxide, calcium carbonate, polymethyl methacrylate, and the like. These 1 type (s) or 2 or more types can be used in combination.
  • a known mixing device can be used for mixing the carrier and the toner.
  • a Henschel mixer, a V-type mixer, a tumbler mixer, a hybridizer, or the like can be used.
  • Example 1 Mn ferrite particles were produced by the following method. As starting materials, Fe 2 O 3 (average particle size 0.6 ⁇ m) 10.75 kg (67.3 mol), Mn 3 O 4 (average particle size: 2 ⁇ m) 4.25 kg (19.0 mol), water Dispersed in 5.0 kg, 90 g of ammonium polycarboxylate dispersant as dispersant, 45 g of carbon black as reducing agent, 30 g (0.25 mol) of colloidal silica (solid content concentration 50%) as SiO 2 raw material added To make a mixture. The solid content concentration of this mixture was 75% by weight. This mixture was pulverized by a wet ball mill (media diameter 2 mm) to obtain a mixed slurry.
  • This mixed slurry was sprayed into hot air of about 130 ° C. with a spray dryer (disk rotation speed: 17500 rpm) to obtain a dry granulated product having a particle size of 10 to 200 ⁇ m. From this granulated product, coarse particles were separated using a sieve mesh having a mesh size of 54 ⁇ m, and fine particles were separated using a sieve mesh having a mesh size of 33 ⁇ m.
  • This granulated powder was put into an electric furnace in an air atmosphere and fired at 1150 ° C. for 3 hours.
  • the magnetic properties, resistance properties, and circularity of the obtained precursor were measured by the methods shown below. Table 1 summarizes the measurement results.
  • the obtained precursor was further put into an electric furnace in a nitrogen atmosphere and baked at 1050 ° C. for 6 hours.
  • the fired product obtained was pulverized with a hammer mill and then classified using a vibration sieve to obtain ferrite particles having an average particle size of 35 ⁇ m.
  • the magnetic properties, resistance properties, apparent density, and circularity of the obtained ferrite particles were measured in the same manner as described above. Table 2 summarizes the measurement results.
  • FIG. 6 shows an SEM photograph of the produced ferrite particles.
  • VSM-P7 vibration sample type magnetometer
  • 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.
  • a magnet having a cross-sectional area of 240 mm 2 (ferrite magnet having a surface magnetic flux density of 1500 gauss) is arranged behind each electrode to form a bridge of ferrite particles between the electrodes. It was. Then, a DC voltage of 50 V was applied between the electrodes, the current value flowing through the ferrite particles was measured, and the resistance value of the ferrite particles was calculated.
  • Example 2 A precursor and ferrite particles were produced in the same manner as in Example 1 except that the firing time in the first firing step was 1.5 hours, the firing temperature in the second firing step was 1100 ° C., and the firing time was 3 hours. Then, the magnetic properties, resistance properties, apparent density, and circularity of the obtained precursor and ferrite particles were measured in the same manner as in Example 1. Table 1 shows the measurement results of the precursor, and Table 2 shows the measurement results of the ferrite particles. FIG. 7 shows an SEM photograph of the produced ferrite particles.
  • Example 3 A precursor and ferrite particles were prepared in the same manner as in Example 1 except that the firing temperature in the second firing step was 1125 ° C. and the firing time was 1 hour. Then, the magnetic properties, resistance properties, apparent density, and circularity of the obtained precursor and ferrite particles were measured in the same manner as in Example 1. Table 1 shows the measurement results of the precursor, and Table 2 shows the measurement results of the ferrite particles. FIG. 8 shows an SEM photograph of the produced ferrite particles.
  • Example 4 A precursor and ferrite particles were produced in the same manner as in Example 1 except that the firing temperature in the second firing step was 1200 ° C. and the firing time was 0.5 hours. Then, the magnetic properties, resistance properties, apparent density, and circularity of the obtained precursor and ferrite particles were measured in the same manner as in Example 1. Table 1 shows the measurement results of the precursor, and Table 2 shows the measurement results of the ferrite particles. FIG. 9 shows an SEM photograph of the produced ferrite particles.
  • Example 5 A precursor and ferrite particles were produced in the same manner as in Example 1 except that the firing temperature in the first firing step was 1200 ° C., the firing temperature in the second firing step was 1150 ° C., and the firing time was 3 hours. Then, the magnetic properties, resistance properties, apparent density, and circularity of the obtained precursor and ferrite particles were measured in the same manner as in Example 1. Table 1 shows the measurement results of the precursor, and Table 2 shows the measurement results of the ferrite particles. FIG. 10 shows an SEM photograph of the produced ferrite particles.
  • Example 6 A precursor and ferrite particles were produced in the same manner as in Example 1 except that the firing temperature in the first firing step was 1275 ° C., the firing temperature in the second firing step was 1150 ° C., and the firing time was 3 hours. Then, the magnetic properties, resistance properties, apparent density, and circularity of the obtained precursor and ferrite particles were measured in the same manner as in Example 1. Table 1 shows the measurement results of the precursor, and Table 2 shows the measurement results of the ferrite particles. FIG. 11 shows an SEM photograph of the produced ferrite particles.
  • Comparative Example 1 The granulated powder produced in the same manner as in Example 1 was put into an electric furnace in a nitrogen atmosphere and fired at 1150 ° C. for 3 hours. The obtained fired product was pulverized with a hammer mill and then classified using a vibration sieve to obtain ferrite particles having an average particle size of 35 ⁇ m. Then, the magnetic properties, resistance properties, apparent density, and circularity of the obtained ferrite particles were measured in the same manner as in Example 1. The measurement results are shown in Table 2.
  • FIG. 12 shows an SEM photograph of the produced ferrite particles.
  • the Mn ferrite particles of Examples 1 to 6 prepared by the production method according to the present invention have a circularity of 0.58 or less, an uneven surface, and as a carrier for electrophotographic development. Even when it was used, it had magnetic properties that did not cause problems such as carrier scattering.
  • the surface can be formed into an uneven shape, and predetermined magnetic characteristics and resistance characteristics can be imparted, which is useful.

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  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Developing Agents For Electrophotography (AREA)

Abstract

Ce procédé de production de particules de ferrite est caractérisé en ce qu'il implique : une étape consistant à obtenir une bouillie par injection dans une solution de milieu d'une matière brute de composant Mn et d'une matière brute de composant Fe ajustée de manière à générer des particules de ferrite ayant une composition exprimée par MnXFe3-XO4 (dans laquelle 0≦X≦1) ; une étape consistant à obtenir des granulés par séchage par pulvérisation de ladite bouillie ; une première étape de cuisson consistant à obtenir un précurseur par cuisson desdits granulés dans une atmosphère oxydante ; et une seconde étape de cuisson consistant à obtenir un produit cuit par davantage de cuisson du précurseur obtenu dans une plage de température de cuisson de 1050-1300°C dans une atmosphère réductrice. Ici, du point de vue d'une rugosification davantage encouragée de la forme de surface des particules de ferrite, la température de cuisson dans la première étape de cuisson se situe idéalement dans la plage de 1150-1300°C et le temps de cuisson est idéalement d'au moins 1,5 heure.
PCT/JP2012/056956 2011-07-23 2012-03-19 Procédé de production de particules de ferrite WO2013014969A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014149464A (ja) * 2013-02-02 2014-08-21 Dowa Electronics Materials Co Ltd キャリア粒子
JP2015093817A (ja) * 2013-11-13 2015-05-18 Ｄｏｗａエレクトロニクス株式会社 Ｍｎフェライト粒子及びそれを用いた電子写真現像剤用キャリア、電子写真用現像剤
JP2016170224A (ja) * 2015-03-11 2016-09-23 パウダーテック株式会社 電子写真現像剤用フェライトキャリア芯材及びその製造方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5751688B1 (ja) 2015-03-02 2015-07-22 Ｄｏｗａエレクトロニクス株式会社 キャリア芯材並びにこ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
KR102353354B1 (ko) 2016-05-06 2022-01-18 파우더테크 컴퍼니 리미티드 페라이트 분말, 수지 조성물 및 성형체

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JPS6148430A (ja) * 1984-08-13 1986-03-10 Fuji Elelctrochem Co Ltd 静電複写用フエライトキヤリアの製造方法
JPH09269613A (ja) * 1996-03-29 1997-10-14 Fuji Elelctrochem Co Ltd 低電気抵抗率キャリアの製造方法
JP2009086545A (ja) * 2007-10-02 2009-04-23 Dowa Electronics Materials Co Ltd 電子写真現像剤用キャリア芯材およびその製造方法、並びに、電子写真現像剤用キャリア
JP2010108006A (ja) * 2010-02-15 2010-05-13 Dowa Holdings Co Ltd 電子写真現像用キャリアおよびその製造方法並びに電子写真用現像剤

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6148430A (ja) * 1984-08-13 1986-03-10 Fuji Elelctrochem Co Ltd 静電複写用フエライトキヤリアの製造方法
JPH09269613A (ja) * 1996-03-29 1997-10-14 Fuji Elelctrochem Co Ltd 低電気抵抗率キャリアの製造方法
JP2009086545A (ja) * 2007-10-02 2009-04-23 Dowa Electronics Materials Co Ltd 電子写真現像剤用キャリア芯材およびその製造方法、並びに、電子写真現像剤用キャリア
JP2010108006A (ja) * 2010-02-15 2010-05-13 Dowa Holdings Co Ltd 電子写真現像用キャリアおよびその製造方法並びに電子写真用現像剤

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014149464A (ja) * 2013-02-02 2014-08-21 Dowa Electronics Materials Co Ltd キャリア粒子
JP2015093817A (ja) * 2013-11-13 2015-05-18 Ｄｏｗａエレクトロニクス株式会社 Ｍｎフェライト粒子及びそれを用いた電子写真現像剤用キャリア、電子写真用現像剤
JP2016170224A (ja) * 2015-03-11 2016-09-23 パウダーテック株式会社 電子写真現像剤用フェライトキャリア芯材及びその製造方法

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