JP6040471B2 - Ferrite carrier core material and ferrite carrier for electrophotographic developer, and electrophotographic developer using the ferrite carrier - Google Patents

Description

  The present invention relates to a ferrite carrier core material and ferrite carrier for an electrophotographic developer used in a two-component electrophotographic developer used in a copying machine, a printer, and the like, and an electrophotographic developer using the ferrite carrier.

  The electrophotographic development method is a method in which toner particles in a developer are attached to an electrostatic latent image formed on a photoreceptor and developed, and the developer used in this method is composed of toner particles and carrier particles. The two-component developer and the one-component developer using only toner particles.

  Among these developers, as a developing method using a two-component developer composed of toner particles and carrier particles, the cascade method has been used in the past, but at present, the magnetic brush method using a magnet roll is the mainstream. It is.

  In the two-component developer, the carrier particles are agitated together with the toner particles in the developing box filled with the developer, thereby imparting a desired charge to the toner particles, and thus being charged. A carrier material for transporting toner particles to the surface of the photoreceptor to form a toner image on the photoreceptor. The carrier particles remaining on the developing roll holding the magnet are returned to the developing box from the developing roll, mixed and stirred with new toner particles, and used repeatedly for a certain period.

  Unlike the one-component developer, the two-component developer has the function of mixing and stirring the carrier particles with the toner particles, charging the toner particles, and further transporting the toner particles. Good controllability. Therefore, the two-component developer is suitable for a full-color developing device that requires high image quality and a device that performs high-speed printing that requires image maintenance reliability and durability.

  In the two-component developer used in this manner, image characteristics such as image density, fog, vitiligo, gradation, and resolving power show predetermined values from the initial stage, and these characteristics are in the printing life period. It needs to be kept stable without fluctuating inside. In order to maintain these characteristics stably, it is necessary that the characteristics of the carrier particles contained in the two-component developer are stable.

  Conventionally, iron powder carriers such as iron powder whose surface is covered with an oxide film or iron powder whose surface is coated with a resin have been used as carrier particles for forming a two-component developer. Since such an iron powder carrier has high magnetization and high conductivity, there is an advantage that an image with a good reproducibility of the solid portion can be easily obtained.

  However, such an iron powder carrier has a heavy true specific gravity of about 7.8 and is too high in magnetization, so that the toner constituent components on the surface of the iron powder carrier are mixed by stirring and mixing with toner particles in the developing box. Fusing, so-called toner spent, is likely to occur. The generation of such toner spent reduces the effective carrier surface area and tends to reduce the triboelectric charging ability with the toner particles.

  Moreover, in the resin-coated iron powder carrier, the resin on the surface peels off due to stress during durability, and the core material (iron powder) with high conductivity and low dielectric breakdown voltage is exposed, which may cause charge leakage. . Due to such charge leakage, the electrostatic latent image formed on the photoconductor is destroyed, and a crack or the like is generated in the solid portion, so that it is difficult to obtain a uniform image. For these reasons, iron powder carriers such as oxide-coated iron powder and resin-coated iron powder are no longer used.

  In recent years, instead of iron powder carriers, ferrite particles, which are light as true specific gravity of about 5.0 and have low magnetization, are used as carriers, and resin coated ferrite carriers in which resin is coated on the surface of ferrite particles are often used. As a result, the developer life has been dramatically increased.

  As a method for producing such a ferrite carrier, a predetermined amount of ferrite raw materials are mixed, calcined, pulverized, and generally fired after granulation. Depending on conditions, calcining may be omitted. .

  Recently, environmental regulations have become stricter, and the use of metals such as Ni, Cu, and Zn has been avoided, and the use of metals suitable for environmental regulations has been demanded, and it is used as a carrier core material. The composition of the ferrite particles has shifted from Cu—Zn ferrite, Ni—Zn ferrite to manganese ferrite using Mn, Mn—Mg—Sr ferrite and the like.

  Patent Document 1 (Japanese Patent Application Laid-Open No. 2006-337828) discloses a ferrite carrier core material for electrophotography in which the surface is divided into regions of 2 to 50 per 10 μm square by grooves or streaks, and the main component is manganese ferrite. Have been described. This ferrite carrier core material has a uniform composition, constant surface properties, good fluidity, high magnetization, low resistance, and an electron using a ferrite carrier in which this ferrite carrier core material is coated with a resin. Photographic developers are said to have a fast charge rise and a stable charge over time.

  In Patent Document 1, in order to produce the ferrite carrier core material as described above, a composite oxide mainly composed of Fe and Mn having a molar ratio of Fe to Mn (Fe / Mn) of 4 to 16 is crushed. It has been shown that in a production method in which granulation, firing, and further pulverization and classification are performed after mixing, firing is performed in an atmosphere having an oxygen concentration of 5% by volume or less.

  However, Mn is also subject to various laws and regulations, and a new carrier core material that does not use Mn as well as the above various heavy metals is demanded.

As an alternative to a carrier core material containing Mn, a carrier core material containing Mg has also been proposed. Patent Document 2 (JP 2005-162597), wherein _{X a Mg b Fe c Ca d} O e (X is Li, Na, Ti, etc., or a combination thereof) Mg ferrite material (carrier core material represented by ), The saturation magnetization is 30 to 80 emu / g, and the dielectric breakdown voltage is 1.5 to 5.0 kV. With this Mg-based ferrite material, it is possible to achieve high image quality and comply with environmental regulations. It is supposed to be possible. Patent Document 3 (Japanese Patent Application Laid-Open No. 2009-237155) has (M _x Fe _3-x ) O ₄ (M is a metal such as Mg, and soft ferrite represented by 0 <x <3). There is described a carrier core material for electrophotographic development in which Al ₂ O ₃ is dissolved and 0.1 to 1% by mass of Al is contained. This electrophotographic developing carrier core material is said to be highly effective in suppressing carrier scattering that is the cause of image abnormalities and preventing the resin coated on the coating core material from peeling off. Is likely to cause local high resistance and low magnetization region of ferrite particles and is not necessarily effective in preventing carrier scattering.

  Patent Document 4 (Japanese Patent Laid-Open No. 2010-210975) has ferrite particles containing 1.0 to 14.0% by weight of magnesium element, and the average distribution ratio D of magnesium element in the ferrite particles is 1. A carrier for developing an electrostatic charge image of 1 to 2.0 is described. According to this electrostatic charge image developing carrier, the image density uniformity and the appearance of the printed matter are excellent, and it is said that the image density uniformity is excellent even when printed in a low temperature and low humidity environment and then left in a high temperature and high humidity environment. However, it does not intend to improve the carrier characteristics by intentionally controlling the magnesium average element distribution.

Further, Patent Document 5 (Japanese Patent Application Laid-Open No. 2012-25640) discloses a surface of a ferrite particle body represented by (M _x Fe _3-x ) O ₄ (M is a metal such as Mg, 0 ≦ x ≦ 1). Ferrite particles coated with alumina, and a carrier for electrophotographic development whose surface is coated with a resin. According to the ferrite particles, the apparent density is small and the fluidity is excellent.

  Thus, although the carrier core material using Mg is proposed, since magnetization and resistance are generally in a trade-off relationship, it is difficult to achieve both high magnetization and characteristics such as medium resistance to high resistance. Particularly in the case of ferrite particles having a composition that easily oxidizes and ferrite particles having a large specific surface area that are easily oxidized, the trade-off tendency is remarkable. Therefore, by adding Mn, the trade-off relationship between magnetization and resistance is relaxed to realize high magnetization, medium resistance to high resistance, and it is currently used as a carrier core material for electrophotographic developer. However, as described above, it is becoming difficult to use Mn with the strengthening of various heavy metal regulations.

  In addition, in a Mg-based carrier core material in which Mn is not intentionally added, as a method of realizing high magnetization and medium resistance to high resistance even with a conventional firing method, a desired resistance can be obtained by surface oxidation after firing. Efforts to match the level have been made, but it cannot be said that the above trade-off relationship has been sufficiently solved.

JP 2006-337828 A Japanese Patent Laid-Open No. 2005-162597 JP 2009-237155 A JP 2010-210975 A JP 2012-25640 A

  Accordingly, an object of the present invention is to use a ferrite carrier core material and a ferrite carrier for an electronic developer that have any resistance and magnetization and excellent chargeability without using heavy metals and without performing surface oxidation treatment. Another object is to provide an electrophotographic developer using the ferrite carrier.

  As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention have found that the core of the ferrite particles is coated with composite oxide particles containing Fe and Mg, and the ferrite carrier in which the resin is coated. Has found that the above object can be achieved, and has led to the present invention. The present invention has been made based on these findings.

That is, the present invention comprises ferrite particles in which composite oxide particles containing Fe and Mg are solid-dissolved near the particle surface, and the content of the composite oxide particles is 1.96 to 10.7 wt%.
The ferrite particles is to provide an electrophotographic developer ferrite carrier core material is Fe and Mg content at the grain inside and the grain near the surface, characterized the different of Turkey.

  In the ferrite carrier core material for an electrophotographic developer according to the present invention, the crystal structure of the composite oxide particles preferably has a spinel phase and a corundum structure.

  In the ferrite carrier core material for an electrophotographic developer according to the present invention, the composite oxide particles preferably contain Ti and / or Sr.

  The present invention provides a ferrite carrier for an electrophotographic developer obtained by coating the surface of the ferrite carrier core material with a resin.

  The present invention provides an electrophotographic developer comprising the above ferrite carrier and a toner.

  The electrophotographic developer according to the present invention is also used as a replenishment developer.

  The ferrite carrier core material for an electrophotographic developer according to the present invention has an arbitrary resistance and magnetization without using a heavy metal and without performing surface oxidation treatment, and is excellent in chargeability. Therefore, an electrophotographic developer composed of a ferrite carrier and a toner obtained by coating the ferrite carrier core material with a resin is excellent in charging stability in each environment.

Hereinafter, modes for carrying out the present invention will be described.
<Ferrite carrier core material and ferrite carrier for electrophotographic developer according to the present invention>
In the ferrite particles used as the ferrite carrier core material for an electrophotographic developer according to the present invention, composite oxide particles are dissolved in the vicinity of the surface. Further, the Fe and Mg contents are different between the inside of the particle and the vicinity of the particle surface. The ferrite carrier core material having the above characteristics has appropriate resistance and magnetization, is excellent in chargeability, can maintain high charge particularly under high temperature and high humidity, and has good environmental dependency. In the present invention, the term “ferrite particles” means an aggregate of individual ferrite particles unless otherwise specified, and the term simply refers to individual ferrite particles.

The increase in resistance by the surface oxidation treatment of conventional ferrite particles is achieved mainly by oxidation of Fe ²⁺ . This treatment is characterized by the fact that it can be easily implemented as a post-process after the main firing, but in the Fe-rich ferrite composition, the magnetite composition part mainly responsible for the development of magnetization is a non-stoichiometric compound, and the crystal structure depends on the degree of oxidation. This recombination easily spreads over the entire ferrite particles, so that the decrease in magnetization becomes extremely large. Therefore, it is not easy to balance high resistance and magnetization.

  On the other hand, in the ferrite particles used as the ferrite carrier core material according to the present invention, composite oxide particles (calcined powder) having a high resistance and having a certain degree of magnetization are preliminarily formed into ferrite core material particles (calcined calcined powder). A high resistance layer is realized by forming a high resistance layer on the surface of the ferrite particles by adhering to a powder granulated product) and then performing a main firing. In addition, since the surface oxidation treatment is not performed after the main firing and the use of the composite oxide particles having magnetization, the decrease in magnetization is overwhelmingly small compared to the ferrite particles obtained by conventional surface oxidation treatment. Is the feature.

  The ferrite particles used as the ferrite carrier core material for an electrophotographic developer according to the present invention preferably contain 0.9 to 3.5% by weight of Mg and 66 to 71% by weight of Fe.

  When the ferrite particles used as the ferrite carrier core material contain Mg, it is possible to obtain a developer having a good rise in charge, which is composed of a ferrite carrier and a full color toner. Also, the resistance can be increased. If the Mg content is less than 0.9% by weight, a sufficient content effect cannot be obtained, the resistance becomes low, and the image quality deteriorates, such as generation of fogging and deterioration of gradation. In addition, since the magnetization becomes too high, the ears of the magnetic brush become hard, causing image defects such as scissors. On the other hand, when the Mg content exceeds 3.5% by weight, not only carrier scattering occurs due to a decrease in magnetization, but when the firing temperature is low, the amount of moisture adsorbed is affected by the hydroxyl group caused by Mg. It becomes large and causes the environmental dependence of electrical characteristics such as charge amount and resistance to deteriorate.

  When the content of Fe in the ferrite particles is less than 66% by weight, when the content of Mg and / or Ti is relatively increased, it means that the nonmagnetic component and / or the low magnetization component is increased. Not only can the desired magnetic properties not be obtained, but also the difference between the surface resistance and the resistance inside the ferrite particles becomes too wide, causing breakdown of the resistance on the high electric field side. Causes scattering. If the Fe content exceeds 71% by weight, the Mg and / or Ti content effect cannot be obtained, and ferrite particles substantially equivalent to magnetite are obtained.

  The ferrite particles used as the ferrite carrier core material for an electrophotographic developer according to the present invention preferably contain 0.3 to 2.0% by weight of Ti. Ti has the effect of lowering the firing temperature and can not only reduce aggregated particles but also obtain a uniform and wrinkled surface property. When the content of Ti in the ferrite particles is less than 0.3% by weight, the effect of containing Ti cannot be obtained, the BET specific surface area tends to be high, and sufficient chargeability cannot be obtained. On the other hand, when the Ti content exceeds 2.0% by weight, the rise of magnetization is deteriorated, which causes carrier scattering.

  The ferrite particles used as the ferrite carrier core material for an electrophotographic developer according to the present invention preferably contains 0.1 to 1.0% by weight of Sr. Sr contributes to the adjustment of resistance and surface properties, and has the effect of maintaining high magnetization, but also contains the effect of increasing the charging ability of the ferrite particles, and the effect is particularly great in the presence of Ti. When the Sr content in the ferrite particles is less than 0.1% by weight, the effect of containing Sr is not obtained, and the magnetization is greatly reduced when firing is performed under a high oxygen concentration. When the Sr content exceeds 1.0% by weight, the residual magnetization and coercive force increase, and when used as a developer, image defects such as scissors occur and image quality deteriorates.

(Contents of Fe, Mg, Ti and Sr)
The contents of these Fe, Mg, Ti and Sr are measured by the following.
Weigh 0.2 g of ferrite particles (ferrite carrier core material), heat 60 ml of pure water plus 20 ml of 1N hydrochloric acid and 20 ml of 1N nitric acid to prepare an aqueous solution in which ferrite particles are completely dissolved, and perform ICP analysis The content of Fe, Mg, Ti and Sr was measured using an apparatus (ICPS-1000IV manufactured by Shimadzu Corporation).

  The crystal structure of the composite oxide particles contained on the surface of the ferrite particles used as the ferrite carrier core material for an electrophotographic developer according to the present invention desirably has a spinel phase and a corundum structure.

The composite oxide particles preferably contain magnesium ferrite and are fired in an air atmosphere. Further, the composite oxide particles preferably have a higher Mg content than the ferrite particle body. A corundum structure mainly composed of Fe and O is generated in addition to the spinel phase by firing Fe-excess magnesium ferrite in the air. In any crystal structure, since there is almost no Fe ²⁺ responsible for electrical conduction, the composite oxide particles themselves tend to have high resistance. Further, when these composite oxide particles conduct the sintering by attaching the ferrite particle surface, excess Fe ²⁺ becomes ferrite particle body integrally are moderately oxidized by a moderately Fe ³⁺ spinel on the entire ferrite particles Can be promoted.

  Furthermore, not only may the effect of improving the rise of magnetization of the ferrite particles be obtained by the diffusion effect of Mg contained in the composite oxide particles, but these composite oxide particles have a magnetization that is not so high. Therefore, it has a feature that the magnetization is not easily lowered as compared with the ferrite carrier core material particles subjected to the surface oxidation treatment.

MgFe ₂ O ₄ is a typical spinel structure included in the ferrite particle main body and the composite oxide particles, but the Fe content is too _high as shown in the elemental composition ratio. A part of which is replaced by Fe, and a crystal structure that is formally expressed by Mg _x Fe _y-x O ₄ , (Mg _x Fe _1-x ) (Mg _{x ′} Fe _{1-x ′} ) ₂ O _{4, and the} like Some of them were substituted with Ti, and those in which the spinel structure periodically contains lattice defects were also included in the spinel structure.

Further, as composite oxides containing Fe and Ti, FeTiO ₃ and Fe ₂ TiO ₅ are typical, but Fe is overwhelmingly present as abundance compared to Ti, and other than Fe _x TiO _y (FeTiO 3). _{3) x (Fe 2 O 3} ) y, Fe (Fe x Ti y) O 4, (Fe x Ti 1-x) (Fe x 'Ti 1-x') of the substance represented by _{O 4} or the like, If the crystal structure is a spinel structure, it shall be included as a substance having a spinel structure, and the crystal structure and a part of the crystal structure may be replaced with Mg, and the crystal structure may include lattice defects periodically. Included. On the other hand, among the above substances, those having the same crystal structure as Fe ₂ O ₃ were treated as a corundum structure as a part of Fe ₂ O ₃ .

The materials exemplified above may be measured as a spinel structure similar to Fe ₃ O _{4 for} convenience, depending on the length of lattice constant and the composition ratio instead of magnesium ferrite. The term “Fe ₃ O ₄ ” as used in the present invention includes those in which part of Fe is substituted with Mg and Ti, and also includes those in which lattice defects are periodically present in the spinel structure. The method for measuring the crystal structure is as follows.

(Measurement of crystal structure: X-ray diffraction measurement)
“X′PertPRO MPD” manufactured by Panalical Co., Ltd. was used as a measuring apparatus. Measurement was performed by continuous scanning at 0.2 ° / sec using a Co tube (CoKα ray) as an X-ray source and a concentrated optical system and a high-speed detector “X'Celarator” as an optical system. The measurement results are processed using data for analysis “X'Pert HighScore” in the same way as the crystal structure analysis of ordinary powders, the crystal structure is identified, and the resulting crystal structure is refined to determine the weight abundance ratio. Was calculated. When calculating the abundance ratio, it was difficult to separate the peaks of magnesium ferrite and Fe ₃ O ₄ , so that it was treated as a spinel phase, and the abundance ratios of the other crystal structures were calculated. In identifying the crystal structure, Fe and O are essential elements, and Mg, Ti, and Sr are elements that may be contained. In addition, the X-ray source can be measured without problems even with a Cu tube, but in the case of a sample containing a large amount of Fe, the background becomes larger than the peak to be measured, so it is better to use a Co tube. preferable. The same result can be obtained even when the optical system is a parallel method, but measurement with a concentrated optical system is preferable because the X-ray intensity is low and measurement takes time. Further, the speed of continuous scanning is not particularly limited, but in order to obtain a sufficient S / N ratio when analyzing the crystal structure, the peak intensity of the (311) plane which is the main peak of the spinel structure is about 50000 cps. Thus, the measurement was performed with the carrier core material set in the sample cell so that the particles were not oriented in a specific preferred direction.

The Sr compound is represented by Sr ₂ Fe ₂ O ₅ which is a precursor of Sr ferrite or strontium ferrite, Sr-Fe compound represented by Sr _x Fe _y O _z , SrTiO ₃ or the like, Sr _x Ti _y O _z There are Sr—Ti compounds, Sr—Fe—Ti compounds in which a part of Sr _x Fe _y O _z is substituted with Ti, and the like. Further, in addition to the above crystal structure, the crystal structure periodically includes lattice defects by being fired in a non-oxidizing atmosphere.

The ferrite particles used as the ferrite carrier core material for an electrophotographic developer according to the present invention desirably have an electric resistance of 5 × 10 ^{6 to} 5 × 10 ⁹ Ω at a 1 mm Gap applied voltage of 250V.

When the electrical resistance of the ferrite particles is less than 5 × 10 ^{6 at a 1} mm Gap applied voltage of 250 V, the resistance is too low, and when used as a carrier, the image density becomes higher than necessary and the toner consumption may increase. When the electrical resistance of the ferrite particles is higher than 5 × 10 ⁹ Ω, image density is difficult to be obtained when used as a carrier, and it may not be used as a carrier.

The ferrite particles used as the ferrite carrier core material for an electrophotographic developer according to the present invention preferably have an electric resistance of 5 × 10 ⁷ to 1 × 10 ¹¹ Ω at a voltage of 6.5 mm Gap applied.

When the electrical resistance of the ferrite particles is smaller than 5 × 10 ⁷ when the applied voltage of 6.5 mm Gap is 500 V, the resistance is too low and white spots may be generated or carriers may be scattered when used as a carrier. When the electrical resistance of the ferrite particles is higher than 1 × 10 ¹¹ Ω, an image with an excessively effective edge may be obtained when used as a carrier.

(Electrical resistance)
This electrical resistance is measured by:
A non-magnetic parallel plate electrode (10 mm × 40 mm) is opposed to each other with a distance of 1 mm or 6.5 mm between the electrodes, and 200 mg of a sample (ferrite particles) is weighed and filled therebetween. A sample is held between the electrodes by attaching a magnet (surface magnetic flux density: 1500 Gauss, area of the magnet in contact with the electrode: 10 mm × 30 mm) to the parallel plate electrodes, a voltage of 250 V or 500 V is applied, and an applied voltage of 250 V or 500 V The resistance was measured with an insulation resistance meter (SM-8210, manufactured by Toa Decay Co., Ltd.).

Ferrite particles used as a ferrite carrier core material for an electrophotographic developer according to the present invention have a magnetization of 40 to 60 Am ² / kg measured by VSM when a magnetic field of 1 K · 1000 / 4π · A / m is applied. Is desirable. When the magnetization of the ferrite particles at 1 K · 1000 / 4π · A / m is less than 40 Am ² / g, the scattered matter magnetization is deteriorated, causing image defects due to carrier adhesion. On the other hand, in the composition range of the present invention, the ferrite particles do not exceed 60 Am ² / g. This magnetic property is measured by:

(Magnetic properties)
A vibrating sample type magnetometer (model: VSM-C7-10A (manufactured by Toei Kogyo Co., Ltd.)) was used. The measurement sample (ferrite particles) was packed in a cell having an inner diameter of 5 mm and a height of 2 mm and set in the above apparatus. The measurement was performed by applying an applied magnetic field and sweeping to 1K · 1000 / 4π · A / m. Next, the applied magnetic field was decreased to create a hysteresis curve on the recording paper. From this curve data, the magnetization at an applied magnetic field of 1 K · 1000 / 4π · A / m was read.

The ferrite particles used as the ferrite carrier core material for an electrophotographic developer according to the present invention preferably have a BET specific surface area of 0.06 to 0.25 m ² / g, and 0.08 to 0.22 m ² / g. Is more desirable.

  When the BET specific surface area is smaller than the above range, the resin anchor effect may not be sufficiently obtained even if the resin coating is performed, and the ferrite particles may be aggregated by the uncoated resin. . For this reason, the amount of the coating resin is substantially reduced, the life as a carrier is shortened, or the aggregated ferrite particles are unraveled in the developing device, so that the surface of the ferrite particles is greatly exposed and the resistance is reduced to reduce carrier scattering. Cause the occurrence. When the BET specific surface area is larger than the above range, the coating resin does not stay on the ferrite particle surface and soaks too much, so that a desired resistance and charge amount as a carrier may not be obtained. When measuring the BET specific surface area, the measurement result may be affected by the moisture on the surface of the ferrite particles as the measurement sample, so pretreatment to remove moisture adhering to the sample surface as much as possible It is preferable to carry out.

(BET specific surface area)
The BET specific surface area was measured using a specific surface area measuring device (model: Macsorb HM model-1208 (manufactured by Mountec)). About 5 to 7 g of the measurement sample was put in a standard sample cell dedicated to a specific surface area measurement device, accurately weighed with a precision balance, the sample (ferrite particles) was set in the measurement port, and measurement was started. The measurement is performed by a one-point method, and the BET specific surface area is automatically calculated when the weight of the sample is input at the end of the measurement. In addition, as a pretreatment before the measurement, about 20 g of the measurement sample was placed on the medicine wrapping paper, and then deaerated to −0.1 MPa with a vacuum dryer, and it was confirmed that the degree of vacuum had reached −0.1 MPa or less. Then, it heated at 200 degreeC for 2 hours.
Environment: temperature; 10-30 ° C, humidity; 20-80% relative humidity, non-condensing

  The ferrite particles used as the carrier core material for an electrophotographic developer according to the present invention preferably have a volume average particle size measured by a laser diffraction particle size distribution measuring device of 15 to 60 μm, more preferably 15 to 50 μm, and most preferably. Is 20 to 45 μm. If the volume average particle size of the ferrite particles is less than 15 μm, carrier adhesion tends to occur, which is not preferable. If the volume average particle diameter of the ferrite particles exceeds 60 μm, the image quality tends to deteriorate, which is not preferable.

(Volume average particle size)
This volume average particle diameter was measured by a laser diffraction scattering method. As a device, a Nikkiso Co., Ltd. Microtrac particle size analyzer (Model 9320-X100) was used. The refractive index was 2.42, and the measurement was performed in an environment of 25 ± 5 ° C. and humidity 55 ± 15%. The volume average particle diameter (median diameter) referred to here is the cumulative 50% particle diameter in the volume distribution mode and under the sieve display. Water was used as the dispersion medium.

(Volume resistivity)
The volume resistivity is measured as follows. That is, in an N / N environment, a fluororesin cylinder having a cross-sectional area of 4 cm ² is filled with a sample so as to have a height of 4 mm, electrodes are attached to both ends, and a 1 kg weight is further placed thereon to provide resistance. Measure. Connect an electrometer (insulation resistance meter model 6517A manufactured by KEITHLEY) to the electrode, measure the current value while changing the applied voltage, and apply the volume resistance from the measured voltage and the applied voltage immediately before the rated output of the electrometer exceeds 1 mA. Was calculated. In addition, the measurement conditions used the STIRCASE mode of the electrometer, started voltage application from 2.5V, and made it change in steps to 1000V in 2.5V increments. Further, it was maintained for 2.5 seconds at each applied voltage.

  In the ferrite carrier for an electrophotographic developer according to the present invention, the surface of the ferrite carrier core material (ferrite particles) is coated with a resin. The number of times of resin coating may be only once, or two or more times of resin coating may be performed, and the number of times of coating can be determined according to desired characteristics. Further, the composition of the coating resin, the coating amount, and the apparatus used for resin coating may be changed or may not be changed when the number of times of coating is two times or more.

  The ferrite carrier for an electrophotographic developer according to the present invention desirably has a resin coating amount of 0.1 to 10% by weight with respect to the ferrite carrier core material. If the resin coating amount is less than 0.1% by weight, it is difficult to form a uniform coating layer on the carrier surface. If the resin coating amount exceeds 10% by weight, the ferrite carriers agglomerate with each other, resulting in a decrease in yield. As a result, the developer characteristics such as fluidity or charge amount in the actual machine are changed.

  The coating resin used here can be appropriately selected depending on the toner to be combined, the environment in which it is used, and the like. The type is not particularly limited, for example, fluorine resin, acrylic resin, epoxy resin, polyamide resin, polyamideimide resin, polyester resin, unsaturated polyester resin, urea resin, melamine resin, alkyd resin, phenol resin, fluorine acrylic resin, Examples thereof include acrylic-styrene resins, silicone resins, or modified silicone resins modified with resins such as acrylic resins, polyester resins, epoxy resins, polyamide resins, polyamideimide resins, alkyd resins, urethane resins, and fluororesins. In the present invention, acrylic resin, silicone resin or modified silicone resin is most preferably used.

  In addition, a conductive agent can be contained in the coating resin for the purpose of controlling the electrical resistance, charge amount, and charging speed of the carrier. Since the conductive agent has a low electric resistance, if the content is too large, it is likely to cause a rapid charge leak. Accordingly, the content is 0.25 to 20.0% by weight, preferably 0.5 to 15.0% by weight, particularly preferably 1.0 to 10.0% by weight, based on the solid content of the coating resin. It is. Examples of the conductive agent include conductive carbon, oxides such as titanium oxide and tin oxide, and various organic conductive agents.

  Further, the coating resin can contain a charge control agent. Examples of the charge control agent include various charge control agents generally used for toners, various silane coupling agents, and inorganic fine particles. This is because, when the core exposed area is controlled to be relatively small by forming a coating layer, the charge imparting ability may be reduced, but it can be controlled by adding various charge control agents and silane coupling agents. This is because it can. The types of charge control agents and coupling agents that can be used are not particularly limited, but charge control agents such as nigrosine dyes, quaternary ammonium salts, organometallic complexes, and metal-containing monoazo dyes, aminosilane coupling agents, and fluorine-based silane couplings. An agent or the like is preferable. As the inorganic fine particles that can be used for charge control, a substance having a biased electronegativity may be used, and silica or the like is preferably used.

<Ferrite carrier core material for electrophotographic developer and method for producing ferrite carrier according to the present invention>
Next, the carrier core material for an electrophotographic developer and the method for producing the carrier according to the present invention will be described.

  The method for producing ferrite particles used as a ferrite carrier core material for an electrophotographic developer according to the present invention is performed, for example, as follows.

(Preparation of ferrite core particles)
Each compound of Fe and Mg and, if necessary, a compound such as Ti are pulverized, mixed, and calcined, and then pulverized by a rod mill to obtain a calcined powder (particles) for a ferrite core material.

  An example of a preferable composition of the calcined powder for a ferrite core material is Fe 65 to 72% by weight, Mg 0.9 to 2% by weight, Ti 0.3 to 2% by weight, and Sr 0.1 to 1% by weight.

  By satisfying the composition range of the calcined powder for ferrite core material described above, various characteristics necessary and sufficient as a ferrite carrier core material for an electrophotographic developer can be obtained after coating the composite oxide fine particles.

  When the ferrite particles used as the ferrite carrier core material contain Mg, it is possible to obtain a developer having a good rise in charge, which is composed of a ferrite carrier and a full color toner. Also, the resistance can be increased. If the Mg content of the calcined powder for ferrite core material is less than 0.9% by weight, a sufficient content effect cannot be obtained, the resistance becomes low, and the image quality deteriorates, such as generation of fog and deterioration of gradation. . In addition, since the magnetization becomes too high, the ears of the magnetic brush become hard, causing image defects such as scissors. On the other hand, when the Mg content of the calcined powder for ferrite core material exceeds 2% by weight, the magnetization of the core material for ferrite carrier after the composite oxide coating is lowered, and carrier scattering is likely to occur.

  When the Fe content of the calcined powder for ferrite core material is less than 65% by weight, the content of one or more elements selected from Mg, Ti, and Sr is relatively increased, and nonmagnetic components and / or This means that the low magnetization component increases, and desired magnetic properties cannot be obtained. When the Fe content of the calcined powder for ferrite core material exceeds 72% by weight, the effect of containing one or more elements selected from Mg, Ti, and Sr cannot be obtained, and is substantially equivalent to magnetite. It becomes ferrite particles.

  As described above, the calcined powder for ferrite core material desirably contains 0.3 to 2.0% by weight of Ti. Ti has the effect of lowering the firing temperature and can not only reduce aggregated particles but also obtain a uniform and wrinkled surface property. When the Ti content of the calcined powder for ferrite core material is less than 0.3% by weight, the Ti content effect cannot be obtained.

  As described above, the calcined powder for ferrite core material desirably contains 0.1 to 1.0% by weight of Sr. Sr contributes to the adjustment of resistance and surface properties, and has the effect of maintaining high magnetization, but also contains the effect of increasing the charging ability of the ferrite particles, and the effect is particularly great in the presence of Ti. When the Sr content of the calcined powder for ferrite core material is less than 0.1% by weight, the effect of containing Sr cannot be obtained.

  The above-mentioned calcined powder for ferrite core material is added with water and, if necessary, a dispersant, a binder, etc. to make a slurry, after adjusting the viscosity, granulated with a spray dryer, granulated, and further debindered to give ferrite Core particles are obtained. The binder removal treatment is performed at 600 to 1000 ° C.

It is desirable that the slurry has a slurry particle size D ₅₀ of 0.5 to 4.5 μm. By setting the slurry particle size within the above range, ferrite particles having a desired BET specific surface area can be obtained. When the slurry particle size D ₅₀ is less than 0.5 μm, the specific surface area of the calcined powder after pulverization becomes too large, and the ferrite particles having a desired BET specific surface area cannot be obtained due to excessive firing of the ferrite particles. If the thickness exceeds 4.5 μm, not only the desired carrier characteristics cannot be obtained when the resin is coated, but also the strength of the obtained ferrite carrier core material (ferrite particles) and / or ferrite carrier deteriorates, Debris can cause image defects.

  In order to make the slurry particle size within the above range, it is necessary to control the pulverization time when preparing the slurry for this granulation, or to select the pulverization media so as to achieve the target slurry particle size and particle size distribution, or wet cyclone. The raw material particles present in the slurry may be classified using When a wet cyclone is used, the solid content of the slurry after classification is different, so it is necessary to adjust the solid content again, but the target slurry particle size can be achieved in a short time, combined with control of the grinding time May be used.

(Preparation of ferrite coating particles)
Similarly to the above, each compound of Fe and Mg and, if necessary, a compound such as Ti are pulverized and mixed, calcined in the air, and then pulverized with a rod mill to obtain a calcined powder for ferrite coating. The calcined powder for ferrite coating has a larger volume resistance than the calcined powder for ferrite core material.

  Next, a silane coupling agent is added to the acetic acid water, the homogenizer is mixed and stirred, the calcined powder for ferrite coating is added, the pH is adjusted with aqueous ammonia, and the resulting slurry is further solid-liquid separated. After drying, it is pulverized to obtain ferrite-coated particles.

  An example of a preferable composition of the ferrite coating particles is 55 to 65% by weight of Fe and 2 to 9% by weight of Mg.

  An example of a more preferable composition of the ferrite coating particles is Ti 0.3 to 2 wt% and Sr 0.1 to 1 wt% in addition to the above composition.

  By satisfying the composition range of the above-mentioned ferrite coating particles, various characteristics necessary and sufficient as a ferrite carrier core material for an electrophotographic developer can be obtained after coating the composite oxide fine particles.

  When the composite oxide fine particles used as the ferrite coating particles contain 2% by weight or more of Mg, the resistance of the ferrite carrier core material for an electrophotographic developer after coating the composite oxide fine particles can be increased. If the Mg content is less than 2% by weight, a sufficient content effect cannot be obtained, the resistance becomes low, and the image quality deteriorates, such as generation of fogging and deterioration of gradation. On the other hand, if the Mg content exceeds 9% by weight, carrier scattering is likely to occur because the magnetization of the carrier core material after the composite oxide coating is reduced.

  When the content of Fe in the ferrite coating particles is less than 55% by weight, the content of one or more elements selected from Mg, Ti, and Sr is relatively increased, and the nonmagnetic component and / or the content is low. This means that the magnetization component increases, and the desired magnetic properties cannot be obtained. When the Fe content exceeds 65% by weight, the effect of containing one or more elements selected from Mg, Ti, and Sr is not obtained, and the ferrite particles are substantially equivalent to the core particles before coating. Because it becomes, there is no meaning.

  The ferrite coating particles preferably contain 0.3 to 2.0% by weight of Ti as described above. Ti has the effect of lowering the firing temperature and can not only reduce aggregated particles but also obtain a uniform and wrinkled surface property. When the content of Ti in the ferrite particles is less than 0.3% by weight, the Ti content effect cannot be obtained.

  The ferrite coating particles preferably contain 0.1 to 1.0% by weight of Sr as described above. Sr contributes to the adjustment of resistance and surface properties, and has the effect of maintaining high magnetization, but also contains the effect of increasing the charging ability of the ferrite particles, and the effect is particularly great in the presence of Ti. When the Sr content in the ferrite particles is less than 0.1% by weight, the effect of containing Sr cannot be obtained.

  The ferrite coating particles preferably have a volume average particle size of 0.1 μm to 5 μm. When the surface treatment is smaller than 0.1 μm, it is difficult to disperse the particles when performing the surface treatment with the silane coupling agent, and the coated particles treated with the silane coupling agent become aggregates with a desired coating amount. Even if the ferrite core material particle surface is coated, the coating layer is likely to be uneven, and sufficient resistance as a carrier core material may not be obtained. If it exceeds 5 μm, gaps are likely to be formed between the coated particles, and after the main firing, a region having a low magnetization is partially formed on the surface of one carrier core particle, resulting in a decrease in scattered matter magnetization and a carrier used as a carrier. Causes scattering.

  The ferrite coating particles are preferably 2 to 12% by weight with respect to the ferrite core particles, though depending on the volume average particle diameter of each of the ferrite core particles. When the amount is less than 2% by weight, sufficient resistance cannot be obtained after the main baking. When the amount is more than 12% by weight, the ferrite coating particles that have not adhered to the ferrite core particles may aggregate to form low-magnetization particles, which causes carrier scattering when used as a carrier. .

  The ferrite coating particles are preferably charged with a silane coupling agent. The silane coupling agent preferably has a linear alkyl group having 8 to 10 carbon atoms and has a methoxy group or an ethoxy group. When the number of carbon atoms of the alkyl group is 7 or less, sufficient charge can be imparted even if the charge application is performed with an addition amount corresponding to the minimum coating area / the BET specific surface area of the ferrite coating particles × the weight of the ferrite coating particles. There is a possibility that the ferrite core material particles may adhere to the ferrite core particles as aggregates. In the case of 11 or more, since the hydrophobicity is too strong, it becomes difficult to treat the silane coupling agent in water. When it has reactive groups other than a methoxy group and an ethoxy group, the rate of hydrolysis of the silane coupling agent is too slow, so that it takes too much time for the silane coupling agent treatment and the productivity is inferior, so it cannot be used.

  When the silane coupling agent treatment is performed on the ferrite coating particles, the addition amount of the silane coupling agent is “BET specific surface area of the ferrite coating particles / silane coupling agent with respect to 100 wt% of the filler to be treated. A is performed in the range of 0.8 to 2 when the minimum coverage area of 100 × A ”wt%. If it is smaller than 0.8, the ferrite coating particles cannot be sufficiently charged, so the ferrite coating particles aggregate together and adhere to the ferrite core particles as aggregates. When a region with low magnetization is partially formed on the surface of the carrier core particle, the scattered matter magnetization is lowered, which may cause carrier scattering when used as a carrier. If it exceeds 2, the influence of charging imparted by an excessive silane coupling agent is large, and the ferrite coating particles do not adhere closely to the ferrite core particles, so that not only sufficient resistance cannot be obtained after the main firing, The ferrite coating particles that have not adhered to the ferrite core material particles may aggregate to form low-magnetization particles, which may cause carrier scattering when used as a carrier.

The ferrite coating particles used here preferably have a magnetization of 30 Am ² / kg or less as measured by VSM when a magnetic field of 1 K · 1000 / 4π · A / m is applied. When the magnetization of the ferrite coating particles at 1K · 1000 / 4π · A / m is larger than 30 Am ² / g, it means an increase in the magnetite component, and even if the coating particles are coated, the resistance tends to be low, and carrier scattering It can be a cause.

  The coating particles used here are more preferably calcined in the air. When calcination is performed in a non-oxidizing atmosphere, magnetite is likely to be generated, and even if the coating particles are coated, the resistance tends to be low, which may cause carrier scattering.

Here, it is desirable that the volume resistance of the obtained ferrite core material particles (calcined powder) and the volume resistance of the ferrite coating particles (calcined powder) are in the following ratio. That is, it is desirable that the volume resistance of the ferrite coating particles (calcined powder) / the volume resistance of the ferrite core particles (calcined powder)> 10. More preferably, the volume resistance of the ferrite coating particles (calcined powder) / the volume resistance of the ferrite core particles (calcined powder)> 50. When this ratio exceeds 10, Mg and Fe ³⁺ are diffused on the surface of the ferrite core material in the main firing step, and necessary resistance can be added while preventing a decrease in magnetization.

(Preparation of ferrite particles)
Ferrite coating particles were added to the ferrite core material particles obtained as described above, and mixed with a mixing mill to obtain a ferrite particle material. This raw material for ferrite particles is performed at 950 to 1230 ° C. in an inert atmosphere or a weakly oxidizing atmosphere such as a nitrogen atmosphere or a mixed gas atmosphere of nitrogen and oxygen having an oxygen concentration of 3% by volume or less.

  Thereafter, the fired product is crushed and classified to obtain ferrite particles. As a classification method, the particle size is adjusted to a desired particle size using an existing air classification, mesh filtration method, sedimentation method, or the like. When dry collection is performed, it can also be collected with a cyclone or the like.

  In this way, ferrite particles used as the ferrite carrier core material for an electrophotographic developer according to the present invention having the above characteristics can be obtained.

  The ratio of the Mg content of ferrite particles used as the ferrite carrier core material for an electrophotographic developer according to the present invention to the Mg content of uncoated ferrite particles (the ferrite core material particles described above) is 1.05 to 1.35. It is preferable that

  When the ratio of the Mg content is smaller than 1.05, since the coating amount of the composite oxide particles is small, sufficient resistance cannot be obtained as the ferrite core material particles after coating, and the effect cannot be obtained. When it exceeds 1.35, the magnetization tends to be low, which may cause carrier scattering.

  The method of performing the main firing after attaching the fine particles to the surface of the ferrite core material particles before the main firing has been proposed as described above, but the main firing is performed using fine particles that are dry and not subjected to pretreatment for charging. When adhering to the surface of the previous ferrite core particles, the fine particles to be adhered are intensely agglomerated or difficult to adhere to the ferrite core particles, or they adhere as large agglomerates, resulting in a large compositional bias and are obtained after firing. The properties of the ferrite particles are never good.

  The ferrite particles according to the present invention are characterized in that a surface treatment for charging is performed in order to obtain easy dispersibility with respect to the surface of the ferrite coating particles to be adhered. By performing the surface treatment for applying the charge, the aggregation of the particles decreases, and the particles easily adhere to the ferrite core material particles before the main firing. In addition, by using a surface treating agent having a polarity opposite to the charged polarity of the ferrite core material particles, an effect of preventing the ferrite coating particles attached to the ferrite core material particles before firing from being detached can be obtained.

  The surface coating of the fine particles on the ferrite core material particles before the main firing by wet processing requires the removal of the liquid as a solvent together with the ferrite particle raw material subjected to the surface coating, which increases the cost of the process. The coating of the fine particles on the ferrite core material particles by the dry method is only required to perform the surface treatment of the fine particles, and it is easy to carry out and the cost increase is small.

  In the ferrite carrier for an electrophotographic developer of the present invention, the above-mentioned resin is coated on the surface of the ferrite carrier core material (ferrite particles) to form a resin film. As a coating method, it can be coated by a known method such as a brush coating method, a spray drying method using a fluidized bed, a rotary drying method, an immersion drying method using a universal stirrer, or the like. In order to improve the coverage, a fluidized bed method is preferred.

  When the resin is coated on the ferrite carrier core and then baked, either an external heating method or an internal heating method may be used, for example, a fixed or fluid electric furnace, a rotary electric furnace, a burner furnace, or a microwave oven Baking by may be used. When a UV curable resin is used, a UV heater is used. Although the baking temperature varies depending on the resin to be used, a temperature equal to or higher than the melting point or the glass transition point is necessary. For a thermosetting resin or a condensation-crosslinking resin, it is necessary to raise the temperature to a point where the curing proceeds sufficiently.

<Electrophotographic developer according to the present invention>
Next, the electrophotographic developer according to the present invention will be described.
The electrophotographic developer according to the present invention comprises the above-described ferrite carrier for electrophotographic developer and toner.

  The toner particles constituting the electrophotographic developer of the present invention include pulverized toner particles produced by a pulverization method and polymerized toner particles produced by a polymerization method. In the present invention, toner particles obtained by any method can be used.

  The pulverized toner particles are, for example, a binder resin, a charge control agent, and a colorant are sufficiently mixed with a mixer such as a Henschel mixer, then melt-kneaded with a twin screw extruder or the like, cooled, pulverized, classified, After adding the external additive, it can be obtained by mixing with a mixer or the like.

  The binder resin constituting the pulverized toner particles is not particularly limited, but polystyrene, chloropolystyrene, styrene-chlorostyrene copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid copolymer, Furthermore, rosin modified maleic acid resin, epoxy resin, polyester resin, polyurethane resin and the like can be mentioned. These may be used alone or in combination.

  Any charge control agent can be used. For example, nigrosine dyes and quaternary ammonium salts can be used for positively charged toners, and metal-containing monoazo dyes can be used for negatively charged toners.

  As the colorant (coloring material), conventionally known dyes and pigments can be used. For example, carbon black, phthalocyanine blue, permanent red, chrome yellow, phthalocyanine green, etc. can be used. In addition, external additives such as silica powder and titania for improving the fluidity and aggregation resistance of the toner can be added according to the toner particles.

  The polymerized toner particles are toner particles produced by a known method such as a suspension polymerization method, an emulsion polymerization method, an emulsion aggregation method, an ester elongation polymerization method, or a phase inversion emulsification method. Such polymerized toner particles are prepared by, for example, mixing and stirring a colored dispersion in which a colorant is dispersed in water using a surfactant, a polymerizable monomer, a surfactant, and a polymerization initiator in an aqueous medium. Then, the polymerizable monomer is emulsified and dispersed in an aqueous medium, polymerized while stirring and mixing, and then a salting-out agent is added to salt out the polymer particles. Polymerized toner particles can be obtained by filtering, washing and drying the particles obtained by salting out. Thereafter, if necessary, an external additive may be added to the dried toner particles to provide a function.

  Further, in the production of the polymerized toner particles, in addition to the polymerizable monomer, the surfactant, the polymerization initiator, and the colorant, a fixability improving agent and a charge control agent can be blended and obtained. Various characteristics of the polymerized toner particles can be controlled and improved. A chain transfer agent can be used to improve the dispersibility of the polymerizable monomer in the aqueous medium and adjust the molecular weight of the resulting polymer.

  The polymerizable monomer used for the production of the polymerized toner particles is not particularly limited. For example, styrene and its derivatives, ethylene unsaturated monoolefins such as ethylene and propylene, vinyl halides such as vinyl chloride, Α-methylene aliphatic monocarboxylic acids such as vinyl esters such as vinyl acetate, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, 2-ethylhexyl methacrylate, dimethylamino acrylate and diethylaminoester methacrylate Examples include esters.

  Conventionally known dyes and pigments can be used as the colorant (coloring material) used in the preparation of the polymerized toner particles. For example, carbon black, phthalocyanine blue, permanent red, chrome yellow, phthalocyanine green, and the like can be used. Moreover, the surface of these colorants may be modified using a silane coupling agent, a titanium coupling agent, or the like.

  As the surfactant used in the production of the polymerized toner particles, an anionic surfactant, a cationic surfactant, an amphoteric surfactant and a nonionic surfactant can be used.

  Here, examples of the anionic surfactant include fatty acid salts such as sodium oleate and castor oil, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, alkyl benzene sulfonates such as sodium dodecyl benzene sulfonate, and alkyl naphthalene sulfonic acids. Salt, alkyl phosphate ester salt, naphthalene sulfonic acid formalin condensate, polyoxyethylene alkyl sulfate ester salt and the like. Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene alkylamine, glycerin, fatty acid ester, and oxyethylene-oxypropylene block polymer. . Furthermore, examples of the cationic surfactant include alkylamine salts such as laurylamine acetate, and quaternary ammonium salts such as lauryltrimethylammonium chloride and stearyltrimethylammonium chloride. Examples of amphoteric surfactants include aminocarboxylates and alkylamino acids.

  The surfactant as described above can be used usually in an amount in the range of 0.01 to 10% by weight with respect to the polymerizable monomer. Such a surfactant affects the dispersion stability of the monomer and also affects the environmental dependency of the obtained polymerized toner particles. Use in an amount within the above range is preferable from the viewpoint of ensuring the dispersion stability of the monomer and reducing the environmental dependency of the polymerized toner particles.

  For the production of polymerized toner particles, a polymerization initiator is usually used. The polymerization initiator includes a water-soluble polymerization initiator and an oil-soluble polymerization initiator, and any of them can be used in the present invention. Examples of the water-soluble polymerization initiator that can be used in the present invention include persulfates such as potassium persulfate and ammonium persulfate, water-soluble peroxide compounds, and oil-soluble polymerization initiators. Examples thereof include azo compounds such as azobisisobutyronitrile and oil-soluble peroxide compounds.

  When a chain transfer agent is used in the present invention, examples of the chain transfer agent include mercaptans such as octyl mercaptan, dodecyl mercaptan, tert-dodecyl mercaptan, carbon tetrabromide, and the like.

  Further, when the polymerized toner particles used in the present invention contain a fixability improver, a natural wax such as carnauba wax, an olefin wax such as polypropylene or polyethylene can be used as the fixability improver. .

  Further, when the polymerized toner particles used in the present invention contain a charge control agent, the charge control agent to be used is not particularly limited, and nigrosine dyes, quaternary ammonium salts, organometallic complexes, metal-containing monoazo dyes, etc. Can be used.

  Examples of the external additive used for improving the fluidity of polymerized toner particles include silica, titanium oxide, barium titanate, fluororesin fine particles, and acrylic resin fine particles. Can be used in combination.

  Furthermore, examples of the salting-out agent used for separating the polymer particles from the aqueous medium include metal salts such as magnesium sulfate, aluminum sulfate, barium chloride, magnesium chloride, calcium chloride, and sodium chloride.

  The volume average particle size of the toner particles produced as described above is in the range of 2 to 15 μm, preferably 3 to 10 μm, and the polymerized toner particles have higher particle uniformity than the pulverized toner particles. . If the toner particles are smaller than 2 μm, the charging ability is lowered, and it is easy to cause fogging and toner scattering, and if it exceeds 15 μm, the image quality is deteriorated.

  An electrophotographic developer can be obtained by mixing the carrier and toner manufactured as described above. The mixing ratio of the carrier and the toner, that is, the toner concentration is preferably set to 3 to 15% by weight. If it is less than 3% by weight, it is difficult to obtain a desired image density. If it exceeds 15% by weight, toner scattering and fogging are likely to occur.

  The electrophotographic developer according to the present invention can also be used as a replenishment developer. At this time, the mixing ratio of the carrier and the toner, that is, the toner concentration is preferably set to 100 to 3000% by weight.

  The electrophotographic developer according to the present invention prepared as described above uses an electrostatic latent image formed on a latent image holding member having an organic photoconductor layer, while applying a bias electric field to the toner and the carrier. The present invention can be used in digital copiers, printers, fax machines, printers, and the like that use a developing method in which reversal development is performed using a two-component developer magnetic brush. Further, the present invention can also be applied to a full color machine using an alternating electric field, which is a method of superimposing an AC bias on a DC bias when a developing bias is applied from the magnetic brush to the electrostatic latent image side.

  Hereinafter, the present invention will be specifically described based on examples and the like.

[Preparation Example 1]
(Preparation of ferrite core particles)
Fe ₂ O ₃ was weighed to 85.54 mol, Mg (OH) ₂ to 9.55 mol, SrCO ₃ to 1.03 mol and TiO ₂ to 3.87 mol, and carbon black as a reducing agent. After adding and adding 1.25% by weight to the raw material weight, the mixture was pulverized and pelletized with a roller compactor. The obtained pellets were temporarily fired at 1000 ° C. in a rotary firing furnace in a nitrogen atmosphere with an oxygen concentration of 0% by volume. This was pulverized with a rod mill to obtain a calcined powder for a ferrite core material.

This calcined powder for ferrite core material is pulverized with a wet bead mill for 1 hour, PVA is added as a binder component so as to be 1.5% by weight with respect to the solid content of the slurry, and the polycarboxylic acid dispersant is added to the viscosity of the slurry. Was added to make 2 to 3 poise. The D ₅₀ of the slurry particle size at this time was 2.676 μm.

  The pulverized slurry thus obtained is granulated and dried with a spray dryer, and debindered at 850 ° C. using a rotary kiln in a nitrogen atmosphere with an oxygen concentration of 0% by volume to obtain ferrite core material particles. It was.

[Preparation Example 2]
(Preparation of ferrite coating particles)
Fe ₂ O ₃ was weighed to 75.49 mol, Mg (OH) ₂ to 19.87 mol, SrCO ₃ to 0.98 mol and TiO ₂ to 3.66 mol, and after pulverization, pelletized with a roller compactor Turned into. The obtained pellets were temporarily fired at 1000 ° C. in an air atmosphere in a rotary firing furnace. This was pulverized with a rod mill to obtain a calcined powder for ferrite coating.

  Decyltrimethoxysilane was added to 5% by weight of acetic acid water, mixed and stirred for 30 minutes with a homogenizer, and then the calcined powder for ferrite coating was added so that the solid content was 20% by weight. After further stirring for 15 minutes, aqueous ammonia was added to adjust the pH to 8.5, and then stirring was continued for 15 minutes. The obtained slurry was solid-liquid separated, dried with a hot air dryer at 150 ° C. for 6 hours to completely remove moisture, and then pulverized with a Henschel mixer to obtain ferrite-coated particles.

[Preparation Example 3]
(Preparation of ferrite coating particles)
The same method as in Preparation Example 2, except that Fe ₂ O ₃ was 66.45 mol, Mg (OH) ₂ was 29.15 mol, SrCO ₃ was 0.93 mol and TiO ₂ was 3.47 mol. Thus, particles for ferrite coating were obtained.

[Preparation Example 4]
(Preparation of ferrite coating particles)
The same method as in Preparation Example 2, except that 58.31 mol of Fe ₂ O ₃ , 37.51 mol of Mg (OH) ₂ , 0.88 mol of SrCO ₃ and 3.3 mol of TiO ₂ were used. Thus, particles for ferrite coating were obtained.

[Example 1]
The ferrite coating particles obtained in Preparation Example 2 were added in an amount of 7.5% by weight to the ferrite core particles obtained in Preparation Example 1 that had been subjected to binder removal treatment, and mixed and stirred for 15 minutes in a mixing mill. The obtained mixture was loosened with an 80-mesh vibrating screen to obtain a raw material for ferrite particles.

  The raw material for ferrite particles obtained above was held at 1100 ° C. for 4 hours in a nitrogen atmosphere with an oxygen concentration of 0% by volume using an electric furnace to perform main firing. Thereafter, it was crushed and further classified to obtain ferrite particles.

[Example 2]
Ferrite particles (ferrite carrier core material) were obtained in the same manner as in Example 1 except that the ferrite coating particles were obtained in Preparation Example 3.

[Example 3]
Ferrite particles (ferrite carrier core material) were obtained in the same manner as in Example 1 except that the ferrite coating particles were obtained in Preparation Example 4.

[Example 4]
Ferrite particles (ferrite carrier core material) were obtained in the same manner as in Example 2 except that the addition amount of the ferrite coating particles was changed to 5% by weight.

[Example 5]
Ferrite particles (ferrite carrier core material) were obtained in the same manner as in Example 2 except that the addition amount of the ferrite coating particles was 10% by weight.

[Example 6]
Ferrite particles (ferrite carrier core material) were obtained in the same manner as in Example 2 except that the main firing temperature was 1060 ° C.

[Example 7]
Ferrite particles (ferrite carrier core material) were obtained in the same manner as in Example 2 except that the main firing temperature was 1200 ° C.

[Example 8]
Ferrite particles (ferrite carrier core material) were obtained in the same manner as in Example 2 except that the grinding time of the bead mill was set to 2 hr.

[Example 9]
Ferrite particles (ferrite carrier core material) were obtained in the same manner as in Example 2 except that the bead mill grinding time was 0.5 hr.

[Comparative Example 1]
Ferrite particles (ferrite carrier core material) were obtained in the same manner as in Example 1 except that the ferrite-coated particles were not added.

[Comparative Example 2]
Ferrite particles (ferrite carrier core material) were obtained in the same manner as in Example 1 except that the addition amount of the ferrite coating particles was 15% by weight.

[Comparative Example 3]
Ferrite particles (ferrite carrier core material) were obtained in the same manner as in Example 1 except that the ferrite particles obtained in Comparative Example 1 were further surface oxidized at 540 ° C. in the air.

[Comparative Example 4]
Ferrite particles (ferrite carrier core material) were obtained in the same manner as in Example 1 except that the ferrite particles obtained in Comparative Example 1 were further surface oxidized at 650 ° C. in the air.

Table 1 shows the blending ratio (raw material ratio mole and carbon amount) of Preparation Examples 1 to 4, calcining conditions (calcining temperature and atmosphere), and the crystal structure of the obtained particles after calcining, and the obtained calcining Results of chemical analysis of powder, physical properties (average particle size after grinding, BET specific surface area, volume resistance, VSM magnetization) and silane coupling agent treatment conditions (treatment agent, minimum coating area, treatment amount, treatment temperature and treatment time) It shows in Table 2. In Examples 1 to 9 and Comparative Examples 1 to 4, the ferrite core material particles used (the ferrite core material particles used, the slurry particle size of this granulation and the binder removal treatment conditions (treatment temperature and atmosphere)). Table 3 shows the particle coating treatment conditions (the ferrite coating particles used, the mixing amount), the main firing conditions (firing temperature and atmosphere) and the oxidation treatment conditions (treatment temperature and atmosphere). The chemical analysis results of the obtained ferrite particles Table 4 shows the ratio to the pre-coated particles and the crystal structure. Furthermore, the powder characteristics (volume average particle diameter, apparent density, fluidity and BET specific surface area) of the ferrite particles obtained in Examples 1 to 9 and Comparative Examples 1 to 4, VSM magnetization (saturation magnetization, residual magnetization, and retention). Magnetic force) and scattering test (δ _{scattered matter} / δ _{main body} ) are shown in Table 5, and resistances (50V, 100V, 250V, 500V and 1000V) of 1 mmGap and 6.5 mmGap and the charge amount in each environment are shown in Table 6. . Here, the apparent density, fluidity and amount of scattered matter shown in Table 5 and the method for measuring the charge amount shown in Table 6 are as follows. The other measurement methods are as described above.

(Apparent density)
It measured based on JISZ2504. Details are as follows.
1. Apparatus The powder apparent density meter is composed of a funnel, a cup, a funnel support, a support bar and a support base. A balance with a weighing of 200 mg and a weighing of 50 mg is used.
2. Measuring method (1) The sample shall be at least 150 g or more.
(2) The sample is poured into a funnel having an orifice with a pore diameter of 2.5 ^{+ 0.2 / −0} mm, and poured until the sample that has flowed out fills the glass and overflows.
(3) Stop the inflow of the sample as soon as it begins to overflow, and scrape the sample raised on the cup flatly with a spatula along the top edge of the cup so as not to give vibration.
(4) Tap the side surface of the cup to sink the sample and remove the sample attached to the outside of the cup, and weigh the sample in the cup with an accuracy of 0.05 g.
3. Calculation The numerical value obtained by multiplying the measured value obtained in 2- (4) above by 0.04 is rounded to the second decimal place by JIS-Z8401 (how to round the numerical value), and the unit of “g / cm ³ ” appears. Density.

(Liquidity)
It is measured by JIS Z2502 (fluidity test method for metal powder).

(Scattering test: δ _{scattered matter} / δ _body )
On a cylindrical sleeve having a region having a peak magnetic flux density of 100 mT in a direction perpendicular to the axis, the magnetization of the ferrite particles when a magnetic field of 1 K · 1000 / 4π · A / m is applied is δ _{main body} Am ² / kg, The ferrite particles are held magnetically, only the magnetic pole region having the peak magnetic flux density is opened, the cylindrical sleeve is rotated for 10 minutes, and a detachment force that is three times the gravity is applied in a direction perpendicular to the rotation axis. Thus, the magnetization of the detached ferrite particles detached from the opening when a magnetic field of 1 K · 1000 / 4π · A / m was applied was δ _{scattered matter} Am ² / kg. The large δ _{scattered matter} / δ _{main body} means that the carrier is likely to be detached from the magnet roll in actual use, and causes problems such as scratching the photosensitive member or generating white spots due to carrier scattering.

(Charge amount of ferrite carrier core material)
Sample (ferrite particles) and commercially available negative polarity toner used in full-color printers with an average particle size of about 6 μm, toner concentration of 6.5% by weight (toner weight = 3.25 g, ferrite carrier core material) (Ferrite particles) Weight = 46.75 g). The weighed ferrite carrier core material and toner were exposed to each environment described later for 12 hours or more. Thereafter, the ferrite carrier core material and the toner were placed in a 50 cc glass bottle and stirred at a rotation speed of 100 rpm for 30 minutes.
As a charge quantity measuring device, magnets with a total of 8 poles (flux density 0.1T) are arranged alternately in the N and S poles inside a cylindrical aluminum tube (hereinafter referred to as sleeve) with a diameter of 31mm and a length of 76mm. The magnet roll, the sleeve, and a cylindrical electrode having a gap of 5.0 mm were disposed on the outer periphery of the sleeve.
After 0.5 g of developer is uniformly deposited on the sleeve, a DC voltage of 2000 V is applied between the outer electrode and the sleeve while rotating the inner magnet roll at 100 rpm while fixing the outer aluminum tube. Was applied for 60 seconds to transfer the toner to the outer electrode. At this time, an electrometer (insulation resistance meter model 6517A manufactured by KEITHLEY) was connected to the cylindrical electrode, and the charge amount of the transferred toner was measured.
After the elapse of 60 seconds, the applied voltage was turned off, the rotation of the magnet roll was stopped, the outer electrode was removed, and the weight of the toner transferred to the electrode was measured.
The charge amount was calculated from the measured charge amount and the transferred toner weight.

Here, the conditions under each environment are as follows.
Normal temperature and humidity (N / N) environment = temperature 20-25 ° C, relative humidity 50-60%
Low temperature and low humidity (L / L) environment = temperature 10-15 ° C, relative humidity 10-15%
High temperature and high humidity (H / H) environment = temperature 30-35 ° C, relative humidity 80-85%

  The ferrite particles of Examples 1 to 9 were ferrite carrier core materials having good magnetic properties, BET specific surface area, charge amount, electrical resistance, and high breakdown voltage.

  In contrast, the ferrite particles of Comparative Example 1 were high in magnetization but low in resistance, and could not be used as a ferrite carrier core material.

  The ferrite particles of Comparative Example 2 had a low scattered matter magnetization and an excessively high resistance, and could not be used as a ferrite carrier core material.

  Although the ferrite particles of Comparative Example 3 had higher resistance than Comparative Example 1, the magnetization decreased, and the ferrite particles could not be used as a ferrite carrier core material.

  The ferrite particles of Comparative Example 4 had higher resistance than the ferrite particles of Comparative Example 3, but had low magnetization, and could not be used as a ferrite carrier core material.

[Example 10]
3 parts by weight of an acrylic resin powder having a primary average particle size of 0.4 μm is added to 100 parts by weight of the ferrite carrier core material (ferrite particles) obtained in Example 1, and mixed for 10 minutes with a V-type mixer having a volume of 3 L. The obtained mixture was put in a hot air dryer set at 240 ° C. for 2 hours to melt the resin, and the ferrite carrier core material was coated with the resin. Thereafter, the aggregated particles were crushed to obtain a resin-coated ferrite carrier.

[Example 11]
A resin-coated ferrite carrier was obtained in the same manner as in Example 10, except that the ferrite carrier core material (ferrite particles) obtained in Example 2 was used.

[Example 12]
A resin-coated ferrite carrier was obtained in the same manner as in Example 10 except that the ferrite carrier core material (ferrite particles) obtained in Example 3 was used.

[Example 13]
A resin-coated ferrite carrier was obtained in the same manner as in Example 10 except that the ferrite carrier core material (ferrite particles) obtained in Example 4 was used.

[Example 14]
A resin-coated ferrite carrier was obtained in the same manner as in Example 10 except that the ferrite carrier core material (ferrite particles) obtained in Example 5 was used.

[Example 15]
A resin-coated ferrite carrier was obtained in the same manner as in Example 10 except that the ferrite carrier core material (ferrite particles) obtained in Example 6 was used.

[Example 16]
A resin-coated ferrite carrier was obtained in the same manner as in Example 10 except that the ferrite carrier core material (ferrite particles) obtained in Example 7 was used.

[Example 17]
A resin-coated ferrite carrier was obtained in the same manner as in Example 10 except that the ferrite carrier core material (ferrite particles) obtained in Example 8 was used.

[Example 18]
A resin-coated ferrite carrier was obtained in the same manner as in Example 10 except that the ferrite carrier core material (ferrite particles) obtained in Example 9 was used.

  Table 7 shows the ferrite carrier core material (ferrite particles) used in Examples 10 to 18, resin coating conditions (coating resin, coating amount, mixing method, mixing time, curing temperature, curing time) and carrier charge amount. . The method for measuring the charge amount is the same as the method for measuring the ferrite carrier core material described above.

  As is clear from the results in Table 7, the ferrite carriers of Examples 10 to 18 had good chargeability in each environment.

  The ferrite carrier core material for an electrophotographic developer according to the present invention has moderate unevenness, strength, resistance, and magnetization, and is excellent in chargeability, and particularly can maintain high charge and high resistance under high temperature and high humidity. Good dependency. Therefore, an electrophotographic developer composed of a ferrite carrier and a toner obtained by coating the ferrite carrier core material with a resin is excellent in charging stability in each environment. In addition, the ferrite carrier core material and the ferrite carrier can be stably obtained with productivity by the production method of the present invention.

  Therefore, the present invention can be widely used in the field of full-color machines that particularly require high image quality and high-speed machines that require image maintenance reliability and durability.

Claims (6)

The composite oxide particles containing Fe and Mg are dissolved in the vicinity of the particle surface, and the composite oxide particles are composed of ferrite particles having a content of 1.96 to 10.7% by weight,
The ferrite particles for an electrophotographic developer ferrite carrier core material is Fe and Mg content at the grain inside and the grain near the surface, it characterized the different of Turkey.   The ferrite carrier core material for an electrophotographic developer according to claim 1, wherein the crystal structure of the composite oxide particles has a spinel phase and a corundum structure.   The ferrite carrier core material for an electrophotographic developer according to claim 1 or 2, wherein the composite oxide particles contain Ti and / or Sr.   The ferrite carrier for electrophotographic developers formed by coat | covering the resin on the surface of the ferrite carrier core material in any one of Claims 1-3.   An electrophotographic developer comprising the ferrite carrier according to claim 4 and a toner.   6. The electrophotographic developer according to claim 5, which is used as a replenishing developer.