JP2011248311A - Ferrite particle for electrostatically charging magnetic brush and manufacturing method of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide ferrite particles for electrostatically charging a magnetic brush in which electric resistance is not fluctuated or reduced even when it is used for a long period of time and stable electrostatic chargeability is obtained.SOLUTION: The ferrite particle contains as a principal component a material represented by the general formula: MnFeO(wherein 0≤x≤1), and has a surface roughness of 0.4 to 0.6 μm and a saturation magnetization of 60 emu/g or more. A difference between before crushing and after crushing of a peak intensity ratio of FeOto MnFeOobtained from X-ray diffraction is set 0.015 or less in the absolute value. Al is preferably 0.2 to 2.0 mass% in aluminum and dissolved. An electric resistance value at an applied voltage of 1000 V is preferably within the range from 1.0×10Ω to 9.0×10Ω.

Description

  The present invention relates to ferrite particles for charging a magnetic brush and a method for producing the same.

  In electrophotographic image forming apparatuses, corona charging devices such as corotrons and scorotrons that do not come into contact with photoreceptors have been widely used. However, in response to the recent increase in environmental awareness, contact-type charging devices that do not generate ozone have attracted attention in place of corona charging devices that inevitably generate ozone, and various devices are being developed and put into practical use.

  As the contact type charging device, there are a roller charging device, a fixed brush charging device, a magnetic brush charging device, etc. Among them, the magnetic brush charging device attracts attention from the viewpoints of long life and recovery of residual toner on the photoreceptor. ing. The magnetic brush charging device carries magnetic particles in the form of a brush on the surface of a carrier by magnetic force, and contacts the magnetic brush with a photoconductor and applies a voltage to charge the photoconductor (for example, Patent Document 1). See).

  The magnetic particles constituting the magnetic brush must have a predetermined magnetic force that does not separate from the magnetic brush and a predetermined electric resistance that charges the photosensitive member. For this reason, as the magnetic particles to be used, for example, the fired ferrite particles are oxidized or the surface is coated with a coating resin to adjust the electric resistance.

JP-A-8-254881

  However, when the oxidation-treated or surface-coated ferrite particles are used for a long period of time, there is a problem that the electric resistance fluctuates or decreases due to wear or chipping on the particle surface.

  The present invention has been made in view of such a conventional problem, and the object of the present invention is to provide a magnetic brush for charging, in which electrical resistance does not fluctuate or decrease even when used for a long period of time, and charging unevenness is suppressed. It is to provide ferrite particles.

  Another object of the present invention is to provide a method for efficiently producing ferrite particles for charging a magnetic brush having the above characteristics.

According to the present invention, ferrite particles comprising a material represented by the general formula Mn _x Fe _3-x O ₄ (where 0 ≦ x ≦ 1) as a main component and used for magnetic brush charging, Before and after pulverization of the peak intensity ratio of Fe ₂ O ₃ and MnFe ₂ O ₄ obtained by X-ray diffraction with a roughness in the range of 0.4 to 0.6 μm and a saturation magnetization of 60 emu / g or more. Ferrite particles characterized in that the subsequent difference is 0.015 or less in absolute value are provided.

  In addition, the surface roughness Ra of the particle in this specification shall mean the arithmetic average roughness prescribed | regulated by JIS B 0601. The measurement conditions of X-ray diffraction (“XRD”: X-ray diffraction) are shown in the examples described later.

  Here, from the viewpoint of setting the surface roughness of the particles in the above range, it is preferable to dissolve Al in an amount of 0.2 to 2.0% by weight in terms of Al.

In addition, from the viewpoint of effectively charging a member to be charged such as a photoreceptor, it is preferable that the electric resistance value of the ferrite particles when the applied voltage is 1000 V is in the range of 1 × 10 ⁶ to 1 × 10 ⁸ Ω.

According to the present invention, the Fe raw material and the Mn raw material whose components are adjusted so that ferrite particles having a composition represented by the general formula Mn _x Fe _3-x O ₄ (where 0 ≦ x ≦ 1) are generated, And a step of mixing an Al raw material in a medium solution to obtain a slurry, a step of spray-drying the slurry to obtain a granulated product, and the granulated product in an oxygen concentration range of 1.0 to 1.7%. There is provided a method for producing ferrite particles for charging a magnetic brush, characterized in that the method comprises a step of obtaining a fired product by firing.

  The addition amount of the Al raw material is preferably in the range of 0.2 to 2.0% by weight in terms of Al.

  According to the ferrite particles for charging a magnetic brush according to the present invention, the electrical resistance does not fluctuate or decrease even when used for a long period of time, and charging unevenness is suppressed.

  Further, according to the method for producing ferrite particles according to the present invention, ferrite particles for charging a magnetic brush can be efficiently produced.

It is a schematic diagram which shows an example of a magnetic brush charging device. 4 is a SEM photograph of ferrite particles of Example 3. FIG. 3 is a diagram illustrating a change with time of the surface potential of the photosensitive drum in Embodiment 1. 4 is a graph showing the XRD measurement results of the ferrite particles of Example 1. 4 is a SEM photograph of ferrite particles of Comparative Example 4. FIG. 10 is a diagram showing a change with time in the surface potential of the photosensitive drum in Comparative Example 4;

  First, the magnetic brush charging device will be briefly described. FIG. 1 is a schematic diagram showing an example of a magnetic brush charging device. A magnetic brush charging device 1 shown in this figure includes a rotatable magnetic sleeve 11 made of a nonmagnetic material such as aluminum, and a magnet roll 12 fixedly arranged in the magnetic sleeve 11 and magnetized with different magnetic poles in the circumferential direction. And magnetic particles 13 that form a magnetic brush on the outer periphery of the magnetic sleeve 11 by the magnetic force of the magnet roll 12. The magnetic brush charging device 1 is arranged so that the magnetic brush contacts the surface of the photosensitive drum 2 as a member to be charged and a nip portion is formed. A voltage application power source 3 is connected to the magnetic sleeve 11. The magnetic sleeve 11 and the photosensitive drum 2 rotate clockwise. That is, the magnetic sleeve 11 rotates in the counter direction with respect to the rotation direction of the photosensitive drum 2 in the nip portion.

  In the magnetic brush charging device 1 having such a configuration, when charging the photosensitive drum 2, the magnetic sleeve 11 is rotated and a predetermined voltage is applied to the magnetic sleeve 11 from the voltage application power source 3. Then, the magnetic brush rotates in the same direction as the magnetic sleeve 11 rotates, and the magnetic brush rubs the surface of the photosensitive drum 2 at the nip portion, and the photosensitive drum 2 is contact-charged.

  Note that the magnetic brush charging device may be configured such that the magnet roll 12 is rotatable and the magnetic brush is formed on the surface thereof without providing the magnetic sleeve 11.

The ferrite particles according to the present invention are preferably used as the magnetic particles of the magnetic brush charging device 1 as described above. One of the major characteristics of the ferrite particles according to the present invention is that the main component is a material represented by the composition formula: Mn _x Fe _3-x O ₄ (where 0 ≦ x ≦ 1), and the surface roughness of the particles is It is in the range of 0.4 to 0.6 μm. By setting the surface roughness of the ferrite particles in the above range, it becomes possible to charge a charged body such as a photosensitive member without unevenness. When the surface roughness of the particles is less than 0.4 μm, the charged unevenness of the object to be charged becomes large. On the other hand, when it exceeds 0.6 μm, the ears of the magnetic brush become hard, and the convex portions on the surface are strong against the object to be charged. The surface may be damaged by rubbing.

In order to make the surface roughness of the ferrite particles within the above range, for example, an Al component may be added in the ferrite particle manufacturing process described later. By adding Al _component, replace the _{Mn x Fe 3-x O 4} Mn in the crystal structure is Al, it is uneven particle surface resulting crystal growth rate difference. In order to make the surface roughness of the ferrite particles in the above range, the solid solution amount of the Al component is preferably in the range of 0.2 to 2.0% by weight in terms of Al.

Further, it is important that the ferrite particles according to the present invention have a saturation magnetization σ _s of 60 emu / g or more. If the saturation magnetization σ _s is less than 60 emu / g, the ferrite particles may frequently adhere to the member to be charged. On the other hand, a suitable upper limit of saturation magnetization is 80 emu / g. When the saturation magnetization σ _s exceeds 80 emu / g, the ears of the magnetic brush become hard and there is a risk of damaging the charged body. The more preferable saturation magnetization σ _s of the ferrite particles is in the range of 60 to 80 emu / g.

The preferred electrical resistance of the ferrite particles according to the present invention is in the range of 1.0 × 10 ^{6 to} 9.0 × 10 ⁸ Ωcm at an applied voltage of 1000V. If the electrical resistance of the ferrite particles is lower than 1.0 × 10 ⁶ , charge leakage may occur, while if the electrical resistance exceeds 9.0 × 10 ⁸ Ωcm, the charge is uniformly injected into the uncharged body. It may not be possible. A more preferable electric resistance of the ferrite particles is in the range of 4.0 × 10 ^{6 to} 9.0 × 10 ⁷ Ωcm. Specific measurement conditions will be described in the examples described later.

In addition, it is important that the electrical resistance of the ferrite particles used in the magnetic brush charging device is small in change over time due to long-term use. The change in electrical resistance with time is reduced when the difference in the ratio of Fe ₂ O ₃ and MnFe ₂ O ₄ is small between the surface and the inside. In the ferrite particles according to the present invention, the absolute value of the difference between the peak intensity ratio of Fe ₂ O ₃ and MnFe ₂ O ₄ obtained by X-ray diffraction of the particles before and after pulverization is 0.015 or less. This is very important. When the difference between before and after pulverization is higher than 0.015 in absolute value, the composition ratio of Fe ₂ O ₃ and MnFe ₂ O ₄ is greatly different between the surface and the inside, and when the particle surface is worn or chipped, There is a risk that the resistance may fluctuate or decrease.

  The average particle diameter of the ferrite particles according to the present invention is preferably in the range of 10 μm to 100 μm. When the average particle diameter is 10 μm or more, a necessary magnetic force is reliably applied to each of the particles, and for example, adhesion of ferrite particles to a charged body such as a photoreceptor is suppressed. On the other hand, when the average particle size is 100 μm or less, uneven charging is further suppressed. In order to set the average particle diameter of the ferrite particles within the above range, classification may be performed using a sieve or the like during the manufacturing process of the ferrite particles or after the manufacturing process.

  Although the manufacturing method of the ferrite particle of the present invention is not particularly limited, the manufacturing method described below is preferable.

First, a Fe raw material, a Mn raw material, and an Al raw material are weighed, put into a dispersion medium, and mixed to prepare a slurry. As the Fe raw material, Fe ₂ O ₃ powder, Fe oxide, Fe hydroxide, etc. can be used. As the Mn raw material, MnFe ₂ O ₄ calcined powder, Mn oxide, Mn hydroxide, etc. are suitably used. it can. Al ₂ O ₃ can be suitably used as the Al raw material.

What is important here is to add an Al raw material. By adding the Al raw material, Mn in the Mn _x Fe _3-x O ₄ crystal structure is replaced with Al, and the grain growth is caused to have a difference in size, and the particle surface is uneven. In order to make the surface roughness of the ferrite particles in the range of 0.4 to 0.6 μm, it is preferable that the addition amount of the Al raw material is in the range of 0.2 to 2.0% by weight in terms of Al.

  Since the addition amount of the Al raw material is very small as described above, the Al raw material may be introduced into the dispersion medium and dispersed before the Fe raw material and the Mn raw material. The solid content concentration of the raw slurry is desirably in the range of 50 to 90 wt%. If necessary, the raw material Fe raw material, Mn raw material, and Al raw material may be pulverized and mixed before being introduced into the dispersion medium.

  Water is preferred as the dispersion medium used in the present invention. In addition to the Fe raw material, Mn raw material, and Al raw material, a binder, a dispersing agent, and the like may be blended in the dispersion medium as necessary. For example, polyvinyl alcohol can be suitably used as the binder. The blending amount of the binder is preferably about 0.5 to 2 wt% in the slurry. Moreover, as a dispersing agent, polycarboxylate ammonium etc. can be used conveniently, for example. As the blending amount of the dispersant, the concentration in the slurry is preferably about 0.5 to 2 wt%. In addition, you may mix | blend a lubricant, a sintering accelerator, etc.

  Next, the slurry prepared as described above is wet-pulverized as necessary. For example, wet grinding is performed for a predetermined time using a ball mill or a vibration mill. The average particle diameter of the raw material after pulverization is preferably 50 μm or less, more preferably 10 μm or less. The vibration mill or ball mill preferably contains a medium having a predetermined particle diameter. Examples of the material of the media include iron-based chromium steel and oxide-based zirconia, titania, and alumina. As a form of a grinding | pulverization process, any of a continuous type and a batch type may be sufficient. The particle size of the pulverized product is adjusted depending on the pulverization time and rotation speed, the material and particle size of the media used, and the like.

  Then, the pulverized slurry is spray-dried and granulated. Specifically, the slurry is introduced into a spray dryer such as a spray dryer, and granulated into a spherical shape by spraying into the atmosphere. The atmospheric temperature during spray drying is preferably in the range of 100 to 300 ° C. Thereby, a spherical granulated product having a particle size of 10 to 200 μm is obtained. In addition, it is desirable that the obtained granulated product has a sharp particle size distribution by removing coarse particles and fine powder using a vibration sieve or the like.

  Next, the obtained granulated product is put into a heated furnace and fired to obtain a fired product having a magnetic phase. The firing temperature may be set to a temperature range in which the target magnetic phase is generated. However, when producing the ferrite particles according to the present invention, firing is preferably performed in a temperature range of 1000 to 1400 ° C. More preferably, it is the temperature range of 1100 degreeC-1350 degreeC.

  What is important here is that the oxygen concentration in the sintering step is in the range of 1.0 to 1.7%. Conventionally, sintering was performed under a nitrogen atmosphere (oxygen concentration of about 200 to 300 ppm), and the inside of the particles was uniformly ferritized to improve magnetic characteristics such as saturation magnetization. On the other hand, when ferrite is uniformly formed into the inside of the particle, the electric resistance is lowered. Conventionally, the ferrite particles are oxidized in the final manufacturing process to obtain a predetermined electric resistance. However, when oxidized ferrite particles are used, the surface of the particles is worn or chipped due to deterioration over time, resulting in a problem that the electric resistance is lowered. Therefore, in the present invention, the oxygen concentration in the firing process is made higher than before, and a hematite layer is uniformly formed inside the particles, so that the stability of electrical resistance with time is achieved.

  If the oxygen concentration in the sintering process is less than 1.0%, a hematite layer is not uniformly formed inside the particles. On the other hand, if the oxygen concentration exceeds 1.7%, magnetic properties such as saturation magnetization are deteriorated. A more preferable oxygen concentration is in the range of 1.2 to 1.6%.

  Next, the obtained fired product is crushed. Specifically, for example, the fired product is crushed by a hammer mill or the like. As a form of a crushing process, any of a continuous type and a batch type may be sufficient. And if necessary, classification may be performed in order to make the particle size in a predetermined range. As a classification method, a conventionally known method such as air classification or sieve classification can be used. In addition, after primary classification with an air classifier, the particle size may be aligned within a predetermined range with a vibration sieve or an ultrasonic sieve. Furthermore, you may make it remove a nonmagnetic particle with a magnetic field separator after a classification process.

  The ferrite particles of the present invention produced as described above are used as they are as a charging magnetic brush. If necessary, the particle surface may be coated with a resin.

  As the resin for covering the surface of the ferrite particles, conventionally known resins can be used, for example, polyethylene, polypropylene, polyvinyl chloride, poly-4-methylpentene-1, polyvinylidene chloride, ABS (acrylonitrile-butadiene-styrene). Examples thereof include resins, polystyrene, (meth) acrylic resins, polyvinyl alcohol resins, polyvinyl chloride-based, polyurethane-based, polyester-based, polyamide-based, polybutadiene-based thermoplastic elastomers, fluorine silicone-based resins, and the like.

  In order to coat the surface of the ferrite particles with a resin, a resin solution or dispersion may be applied to the ferrite particles. Solvents for the coating solution include aromatic hydrocarbon solvents such as toluene and xylene; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; cyclic ether solvents such as tetrahydrofuran and dioxane; ethanol, propanol, and butanol Alcohol solvents such as ethyl cellosolve, cellosolve solvents such as butyl cellosolve; ester solvents such as ethyl acetate and butyl acetate; amide solvents such as dimethylformamide and dimethylacetamide, etc. . The concentration of the resin component in the coating solution is generally in the range of 0.001 to 30 wt%, particularly 0.001 to 2 wt%.

  As a method for coating the resin on the ferrite particles, for example, a spray drying method, a fluidized bed method, a spray drying method using a fluidized bed, an immersion method, or the like can be used. Among these, the fluidized bed method is particularly preferable in that it can be efficiently applied with a small amount of resin. For example, in the case of the fluidized bed method, the resin coating amount can be adjusted by the amount of resin solution sprayed and the spraying time.

Example 1
Al ₂ O ₃ powder finely pulverized to an average particle diameter of about 1 μm, Fe ₂ O ₃ and Mn ₃ O ₄ were prepared. Then, 5000 ppm of _Al 2 _{O 3} powder in terms of Al, and _Fe 2 _{O 3,} the _Mn 3 _{O 4} 8: two were weighed such that the molar ratio. Weighed Al ₂ O ₃ , Fe ₂ O ₃ , and Mn ₃ O ₄ were dispersed in pure water to which ammonium polycarboxylate as a dispersant was added so that the concentration in the medium liquid was 1% to obtain a mixture. . This mixture was pulverized by a wet ball mill (media diameter: 2 mm) to obtain a slurry.

  The obtained slurry was sprayed into hot air at about 150 ° C. with a spray dryer to obtain a dry granulated product having a particle size of 10 to 100 μm. And the granulated material with a particle size exceeding 100 micrometers was removed using the sieve. The obtained dried granulated product was put into an electric furnace and fired at 1100 ° C. for 3 hours in a nitrogen atmosphere having an oxygen concentration of 1.6% to obtain a fired product. After the obtained fired product was pulverized, coarse particles and fine particles were removed using a sieve to obtain Mn ferrite particles having an average particle diameter of 45 μm. The average particle size of the ferrite particles is measured using a laser diffraction particle size distribution measuring device (Microtrack, Model 9320-X100 manufactured by Nikkiso Co., Ltd.).

  The surface roughness, saturation magnetization σs, chargeability, and X-ray diffraction of the obtained ferrite particles were measured by the following methods. The results are shown in Table 1. FIG. 3 shows the time-dependent change in the surface potential of the photosensitive drum, and FIG. 4 shows the XRD measurement results.

(Surface roughness)
The surface roughness Ra was measured with a laser microscope (OLYMPUS LEXT OLS3000). More specifically, a range of 10 μm square is set in the ferrite particles, the height is measured in the range to obtain an average line, and the absolute value of the deviation from the average line to the measurement curve in this range is synthesized, and the average It was calculated by converting.

(Saturation magnetization measurement)
The magnetic properties of the ferrite were measured for magnetic susceptibility using VSM (manufactured by Toei Kogyo Co., Ltd., VSM-P7), and the saturation magnetization σ _s (emu / g) in an applied magnetic field of 10 kOe was measured.

(Chargeability)
The photosensitive drum is charged using the magnetic brush charging device shown in FIG. 1, the surface potential is measured using a non-contact voltage measuring device (manufactured by Trek), and the change in the surface potential of the photosensitive drum with time is examined. It was.

(Electrical resistance measurement)
Two brass plates as electrodes having a thickness of 2 mm whose surfaces were electropolished were arranged to face each other with a distance of 2 mm. After inserting 200 mg of ferrite particles between the electrodes, a magnet having a cross-sectional area of 240 mm ² (ferrite magnet having a surface magnetic flux density of 1500 gauss) is placed behind each electrode to form a bridge of ferrite particles between the electrodes. I let you. A DC voltage of 10 V to 1000 V was applied between the electrodes, the value of the current flowing through the ferrite particles was measured, and the electrical resistance of the ferrite particles was calculated.

(X-ray diffraction measurement)
It measured using the X-ray-diffraction apparatus (Rigaku make, RINT2000). Cobalt was used as the X-ray source, and X-rays were generated at an acceleration voltage of 40 kV and a current of 30 mA. The measurement conditions of the powder X-ray are scanning mode: FT, divergence slit: 1/2 °, scattering speed: 1/2 °, light receiving slit: 0.15 mm, rotation speed: 5.000 rpm, measurement angle: 10 ° ≦ 2θ ≦ Measurement was performed at 90 °, measurement interval: 0.01 °, and counting time: 5 seconds.

(Example 2)
A fired product was obtained in the same manner as in Example 1 except that the firing temperature was 1150 ° C. After the obtained fired product was pulverized, coarse particles and fine particles were removed using a sieve to obtain Mn ferrite particles having an average particle diameter of 45 μm.
The surface roughness, saturation magnetization σs, chargeability, and X-ray diffraction of the obtained ferrite particles were measured in the same manner as in Example 1. The results are shown in Table 1.

(Example 3)
A fired product was obtained in the same manner as in Example 1 except that the firing temperature was 1200 ° C. After the obtained fired product was pulverized, coarse particles and fine particles were removed using a sieve to obtain Mn ferrite particles having an average particle diameter of 45 μm. An electron microscope (SEM) photograph of the obtained ferrite particles is shown in FIG.
The surface roughness, saturation magnetization σs, chargeability, and X-ray diffraction of the obtained ferrite particles were measured in the same manner as in Example 1. The results are shown in Table 1.

Example 4
A fired product was obtained in the same manner as in Example 1 except that the oxygen concentration in the firing step was 1.0% and the firing temperature was 1200 ° C. After the obtained fired product was pulverized, coarse particles and fine particles were removed using a sieve to obtain Mn ferrite particles having an average particle diameter of 45 μm.
The surface roughness, saturation magnetization σs, chargeability, and X-ray diffraction of the obtained ferrite particles were measured in the same manner as in Example 1. The results are shown in Table 1.

(Example 5)
A fired product was obtained in the same manner as in Example 1 except that the oxygen concentration in the firing step was 1.2% and the firing temperature was 1200 ° C. After the obtained fired product was pulverized, coarse particles and fine particles were removed using a sieve to obtain Mn ferrite particles having an average particle diameter of 45 μm.
The surface roughness, saturation magnetization σs, chargeability, and X-ray diffraction of the obtained ferrite particles were measured in the same manner as in Example 1. The results are shown in Table 1.

(Example 6)
A fired product was obtained in the same manner as in Example 1 except that the oxygen concentration in the firing step was 1.4% and the firing temperature was 1200 ° C. After the obtained fired product was pulverized, coarse particles and fine particles were removed using a sieve to obtain Mn ferrite particles having an average particle diameter of 45 μm.
The surface roughness, saturation magnetization σs, chargeability, and X-ray diffraction of the obtained ferrite particles were measured in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 1)
A fired product was obtained in the same manner as in Example 1 except that the oxygen concentration in the firing step was 2.0% and the firing temperature was 1200 ° C. After the obtained fired product was pulverized, coarse particles and fine particles were removed using a sieve to obtain Mn ferrite particles having an average particle diameter of 45 μm.
The surface roughness, saturation magnetization σs, chargeability, and X-ray diffraction of the obtained ferrite particles were measured in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 2)
A fired product was obtained in the same manner as in Example 1 except that the oxygen concentration in the firing step was 2.5% and the firing temperature was 1200 ° C. After the obtained fired product was pulverized, coarse particles and fine particles were removed using a sieve to obtain Mn ferrite particles having an average particle diameter of 45 μm.
The surface roughness, saturation magnetization σs, chargeability, and X-ray diffraction of the obtained ferrite particles were measured in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 3)
A fired product was obtained in the same manner as in Example 1 except that Al ₂ O ₃ powder was not added and the firing temperature in the firing step was 1200 ° C. After the obtained fired product was pulverized, coarse particles and fine particles were removed using a sieve to obtain Mn ferrite particles having an average particle diameter of 45 μm.
The surface roughness, saturation magnetization σs, chargeability, and X-ray diffraction of the obtained ferrite particles were measured in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 4)
A fired product was obtained in the same manner as in Example 1 except that Al ₂ O ₃ powder was not added, the oxygen concentration in the firing step was 0.03%, and the firing temperature was 1200 ° C. After the obtained fired product was pulverized, coarse particles and fine particles were removed using a sieve to obtain Mn ferrite particles having an average particle diameter of 45 μm. The obtained ferrite particles were oxidized (450 ° C. × 1.5 hours in an air atmosphere).
The surface roughness, saturation magnetization σs, chargeability, and X-ray diffraction of the obtained ferrite particles were measured in the same manner as in Example 1. The results are shown in Table 1. Further, FIG. 5 shows an electron micrograph of the obtained ferrite particles, and FIG. 6 shows changes with time in the surface potential of the photosensitive drum.

(Comparative Example 5)
A fired product was obtained in the same manner as in Example 1 except that the oxygen concentration in the firing step was 0.03% and the firing temperature was 1200 ° C. After the obtained fired product was pulverized, coarse particles and fine particles were removed using a sieve to obtain Mn ferrite particles having an average particle diameter of 45 μm. The obtained ferrite particles were oxidized (450 ° C. × 1.5 hours in an air atmosphere).
The surface roughness, saturation magnetization σs, chargeability, and X-ray diffraction of the obtained ferrite particles were measured in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 6)
A fired product was obtained in the same manner as in Example 1 except that Al ₂ O ₃ powder was not added and the oxygen concentration in the firing step was 0.03%. After the obtained fired product was pulverized, coarse particles and fine particles were removed using a sieve to obtain Mn ferrite particles having an average particle diameter of 45 μm.
The surface roughness, saturation magnetization σs, chargeability, and X-ray diffraction of the obtained ferrite particles were measured in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 7)
A fired product was obtained in the same manner as in Example 1 except that Al ₂ O ₃ powder was not added, the firing temperature in the firing step was 1150 ° C., and the oxygen concentration was 0.03%. After the obtained fired product was pulverized, coarse particles and fine particles were removed using a sieve to obtain Mn ferrite particles having an average particle diameter of 45 μm.
The surface roughness, saturation magnetization σs, chargeability, and X-ray diffraction of the obtained ferrite particles were measured in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 8)
A fired product was obtained in the same manner as in Example 1 except that Al ₂ O ₃ powder was not added, the firing temperature in the firing step was 1200 ° C., and the oxygen concentration was 0.03%. After the obtained fired product was pulverized, coarse particles and fine particles were removed using a sieve to obtain Mn ferrite particles having an average particle diameter of 45 μm.
The surface roughness, saturation magnetization σs, chargeability, and X-ray diffraction of the obtained ferrite particles were measured in the same manner as in Example 1. The results are shown in Table 1.

  As the evaluation of charging unevenness, when the charging level (difference between maximum value and minimum value) of Example 3 in FIG. 3 is 1, 1.5 is defined as “small”, and 1.5 or more is defined as “large”. . As is apparent from Table 1, the ferrite particles according to the present invention in Examples 1 to 6 had small charging unevenness.

Moreover, the XRD measurement peak intensity difference is small before and after the pulverization, indicating that the composition ratio of Fe ₂ O ₃ and MnFe ₂ O ₄ is uniform between the surface and the inside. Therefore, it is possible to reduce a problem that electric resistance fluctuates or decreases due to wear or chipping on the particle surface.

  The ferrite particles for charging a magnetic brush according to the present invention are useful because the electrical resistance does not fluctuate or decrease even when used for a long period of time, and a stable charging property is obtained.

DESCRIPTION OF SYMBOLS 1 Magnetic brush charging device 2 Photosensitive drum 3 Voltage supply power source 11 Magnetic sleeve 12 Magnet roll 13 Magnetic particle

Claims (5)

Formula _{Mn x Fe 3-x O 4} ( where, 0 ≦ x ≦ 1) as a main component a material represented by a ferrite particles used in the magnetic brush charging,
The surface roughness of the particles is in the range of 0.4 to 0.6 μm, the saturation magnetization is 60 emu / g or more,
A ferrite particle characterized in that the difference between the peak intensity ratio of Fe ₂ O ₃ and MnFe ₂ O ₄ obtained by X-ray diffraction before and after pulverization is 0.015 or less in absolute value.   The ferrite particle according to claim 1, wherein Al is dissolved in an amount of 0.2 to 2.0 wt% in terms of Al. 3. The ferrite particle according to claim 1, wherein an electric resistance value at an applied voltage of 1000 V is in a range of 1.0 × 10 ^{6 to} 9.0 × 10 ⁸ Ω. Mixing Fe raw material, Mn raw material, and Al raw material, which are component-adjusted so that ferrite particles having a composition represented by the general formula Mn _x Fe _3-x O ₄ (where 0 ≦ x ≦ 1) are generated, are mixed in the medium liquid. And obtaining a slurry by spray drying the slurry to obtain a granulated product, and firing the granulated product in an oxygen concentration range of 1.0 to 1.7% to obtain a calcined product. And a method for producing ferrite particles for charging a magnetic brush.   The method for producing ferrite particles according to claim 4, wherein the additive amount of the Al raw material is in the range of 0.2 to 2.0% by weight in terms of Al.