JP2007314412A - Black magnetic iron oxide particle - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a black magnetic iron oxide pigment forming a toner which exhibits high image density under high-temperature and high-humidity conditions, is improved in keeping property of the image density, and is inhibited from suffering from occurrence of fogging even under low-temperature and low-humidity conditions. <P>SOLUTION: A surface of the respective particles is covered with a compound of at least one alkaline earth metal element and an Al element, in which a content of the at least one alkaline earth metal element present in the surface of the particles is from 100 ppm to 1,000 ppm on the basis of a whole weight of the particles; a content of the Al element present in the surface of the particles is from 1,000 ppm to 20,000 ppm on the basis of a whole weight of the particles; a ratio [A/B] of the content [A] of the Al element to the content [B] of the at least one alkaline earth metal element present in the surface is from 1 to 100; and a molded product comprising the black magnetic iron oxide particles has a breakdown voltage of not less than 400 V/cm. The black magnetic iron oxide particles are used for toners. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  Since the black magnetic iron oxide particles according to the present invention are black, they can be used for paints, resins, black color pigments such as printing ink, magnetic materials for binder type carriers, and the like. In particular, when used as black magnetic particles for magnetic toner, the image density is high in a high temperature and high humidity environment, the image density maintenance is improved, and the fog is suppressed even in a low temperature and low humidity environment. Toner can be configured.

  Magnetite particle powder is a typical black pigment, and has been widely used as a colorant for paints, printing inks, cosmetics, rubber / resin compositions, etc. for a long time.

  In particular, the magnetite particle powder is frequently used in a one-component magnetic toner using, as a developing material, composite particles obtained by mixing and dispersing black magnetic iron oxide particles such as magnetite particles in a resin.

  Recently, along with the development of devices that can be used in various environments, in addition to increasing the speed and image quality of laser beam printers and digital copying machines, the characteristics of magnetic toner as a developer have been improved. There is a strong demand for toners that maintain good image density in low-temperature, low-humidity and high-temperature, high-humidity environments, and that suppress fogging.

  Therefore, further improvement in characteristics is strongly desired for the black magnetic iron oxide particle powder in order to satisfy the requirements for the magnetic toner.

  That is, the black magnetic iron oxide particle powder has a sufficient resistance value and a high dielectric breakdown voltage in order to obtain a toner excellent in environmental stability, particularly in image density maintenance under a high temperature and high humidity environment. It is required that the electrical characteristics are more excellent and these characteristics are excellent in environmental stability.

This is because in the process of forming a toner image, when the toner particles are blown to the latent image on the photoreceptor, a mirror image force, which is the combined force of electrostatic attraction and magnetic restraint force, acts on the toner particles, and this strength is subtly This is because the balance between the image density and the fog is controlled by controlling to the above.
That is, if the resistance value of the toner particles is high, the charging performance is improved and the image density is likely to fly onto the photoreceptor, and the image density is high. However, if the charging performance of the toner particles is too high, it causes fogging. On the other hand, if the charging performance of the toner particles is too low, fogging is difficult to occur, but a situation occurs in which the image density does not occur.

  In order to control the charging performance of the toner particles, the use of a charge control agent is usually raised, but as one of other means, the electric resistance value of the magnetic iron oxide particles which are pigment components exposed on the toner particle surface There is a way to control. That is, if the electric resistance value of the magnetic iron oxide particles exposed on the toner particle surface is high, the toner particles are easily charged, and conversely if the magnetic iron oxide particle has a low electric resistance value, it is charged by stirring in the toner hopper. As a result, the electrostatic charge on the surface of the toner particles escapes through the magnetic iron oxide particles exposed on the toner particle surface, and as a result, the charge amount of the toner particles decreases.

  These phenomena are particularly remarkable in an environmental atmosphere to which the developing device is exposed, particularly in a high temperature and high humidity environment or a low temperature and low humidity environment. That is, in general, the charging performance of the toner tends to be low in a high temperature and high humidity environment, and as a result, the image density tends to be low. In a low temperature and low humidity environment, the toner chargeability is excessive and fog is likely to occur. .

  Therefore, controlling the electrical characteristics of the black magnetic iron oxide particle powder is very important for obtaining an image with high image density and no fogging when the black magnetic iron oxide particle powder is used as a pigment of toner particles. It has meaning.

  The resistance value of black magnetic iron oxide particle powder is high or low resistance component (high resistance oxide / hydroxide / dielectric) on the surface of black magnetic iron oxide particles because magnetite generally has electrical characteristics of semiconductor. It is generally known that a powder having a high resistance value can be obtained by coating or adhering an organic or hydrophobic organic substance).

  Conventionally, attempts have been made to improve various characteristics by incorporating different elements other than iron into the black magnetic iron oxide particles and coating the surface of the black magnetic iron oxide particles with an inorganic substance or an organic substance.

For example, Patent Document 1 (Japanese Patent Laid-Open No. 5-213620) discloses black magnetic iron oxide having a high electrical resistance value by exposing the Si component to the inside and the surface of the particle. 2 (Japanese Patent Laid-Open No. 8-208236) discloses black magnetic iron oxide covered with an oxide layer of Fe and Zn.
Patent Document 3 (Japanese Patent Laid-Open No. 2000-272924) discloses black magnetic iron oxide having a high electrical resistance value coated with a hydrophobizing agent.
Patent Document 4 (Japanese Patent Laid-Open No. 2003-192350) discloses black magnetic iron oxide coated with a composite iron oxide layer containing an Al component and an Mg component.
Patent Document 5 (Japanese Patent Laid-Open No. 2004-161551) discloses black magnetic iron oxide covered with a composite iron oxide layer of Ti and Fe.

JP-A-5-213620 JP-A-8-208236 JP 2000-272924 A JP 2003-192350 A JP 2004-161551 A

  Black magnetic iron oxide particles having a high resistance in the high voltage region are currently most demanded, but have not yet been obtained.

  That is, the prior art described in the above-mentioned Patent Documents 1 to 5 is a technique focusing on the electric resistance value of the powder, and the electric resistance value in the low voltage region has been mainly studied. However, the electric field applied to the toner particles inside the printer in which the toner is actually used varies depending on the apparatus, but is generally an electric field in the region of several hundred volts.

  In terms of image density and image density maintainability, not only the electrical resistance value of the pigment used in the toner is high, but also the electrical resistance value at a high voltage is important. That is, even if a pigment with a high resistance value is obtained at a low voltage, if the resistance value is low in the electric field actually used, the static electricity on the toner surface escapes as a leak site from the pigment exposed on the toner surface. Since the charge amount of the toner is reduced, the image density is significantly reduced.

  Therefore, the black magnetic iron oxide particle powders disclosed in the aforementioned Patent Documents 1 to 5 are all techniques for increasing the electrical resistance value in the low voltage region, and are currently in the most necessary high voltage region. From the viewpoint of increasing the electrical resistance value, the requirements have not been met.

  Accordingly, the present invention provides a black magnetic iron oxide pigment capable of constituting a toner having a high image density in a high temperature and high humidity environment, improving the image density maintenance property, and suppressing fogging in a low temperature and low humidity environment. Doing this is a technical issue.

  As a result of investigations in view of the above technical problems, the present inventors have been able to obtain black magnetic iron oxide particle powder having a high electric resistance value at a high voltage, leading to the present invention.

  The technical problem can be achieved by the present invention as follows.

  That is, according to the present invention, the particle surface of the core particle is covered with a surface layer composed of a compound of Al element and at least one of alkaline earth metal elements (Mg, Ca, Sr, Ba). It is iron particles, and the content of at least one of the alkaline earth metal elements present in the surface layer is 100 ppm or more and 1000 ppm or less with respect to the entire black magnetic iron oxide particles, and the Al element present in the surface layer The content of Al is 1000 ppm or more and 20000 ppm or less with respect to the entire black magnetic iron oxide particles, and the Al element content [A (ppm)] present in the surface layer and the alkaline earth metal elements (Mg, Ca, The ratio [A / B] to the content [B (ppm)] of Sr, Ba) is 1 or more and 100 or less, and the dielectric breakdown voltage of the black magnetic iron oxide particle powder is 40 A black magnetic iron oxide particles, characterized in that it is V / cm or more (the present invention 1).

  Further, according to the present invention, when the black magnetic iron oxide particle powder is stirred and mixed in a 0.002N-HCl aqueous solution at 40 ° C. for 10 minutes, the eluted Al amount (weak acid-soluble Al amount) is 500 ppm or less in terms of the weight of the particle powder. This is the black magnetic iron oxide particle powder of the present invention 1 (Invention 2).

In addition, the present invention is characterized in that the electric resistance value when a 500 V DC voltage is applied is 1 × 10 ⁶ Ωcm or more of a molded product having a molded body density of black magnetic iron oxide particles of 2.7 g / cm ^3. It is the black magnetic iron oxide particle powder of the present invention 1 or 2 (present invention 3).

Further, in the present invention, the average particle size of the black magnetic iron oxide particles is 0.10 to 0.30 μm, the BET specific surface area is 4 to ²⁰ m ² / g, and the average particle represented by the following formula The black magnetic iron oxide particle powder according to any one of the present inventions 1 to 3, wherein the product α of the diameter and the BET specific surface area value is 1.2 ≦ α ≦ 2.0 (Invention 4). .
α = BET specific surface area (m ² / g) × average particle diameter (μm)

  The black magnetic iron oxide particle powder of the present invention, particularly when used as a pigment for toner, provides a high image density, a high electric resistance value at a high voltage, and a high image density particularly in a high temperature and high humidity environment. It is suitable as an application for obtaining

  The configuration of the present invention will be described in more detail as follows.

  The particle shape of the black magnetic iron oxide particle powder according to the present invention is not particularly limited, and may be hexahedron, octahedron, polyhedron shape, granular shape, spherical shape, or the like.

  The black magnetic iron oxide particles constituting the black magnetic iron oxide particle powder according to the present invention are composed of core particles and a surface layer existing on the particle surface of the core particles. The surface layer refers to a portion excluding a portion containing Fe from the central portion of the particle toward the surface. The core particle refers to the inside of the particle excluding the surface layer portion.

  In the surface layer of the black magnetic iron oxide particles in the present invention, a compound composed of at least one of alkaline earth metal elements (Mg, Ca, Sr, Ba) and Al element forms a uniform layer on the particle surface. ing.

  In the black magnetic iron oxide particles according to the present invention, the content of Al element present in the surface layer of the black magnetic iron oxide particles is 1000 ppm or more and 20000 ppm or less with respect to the entire black magnetic iron oxide particles. When the Al content is less than 1000 ppm, the electrical resistance value is low and the dielectric breakdown voltage is also low. When it exceeds 20000 ppm, the hygroscopicity becomes high, and both the electric resistance value and the dielectric breakdown voltage become low. Preferably it is 1000-18000 ppm, More preferably, it is 1000-15000 ppm.

  In the black magnetic iron oxide particles according to the present invention, the content of at least one of the alkaline earth metal elements present in the surface layer of the black magnetic iron oxide particles is 100 ppm or more and 1000 ppm or less with respect to the entire black magnetic iron oxide particles. It is. When the content of the alkaline earth metal element is less than 100 ppm, a dielectric breakdown voltage of 400 V / cm or more cannot be obtained. Further, when the content of the alkaline earth metal element exceeds 1000 ppm, the surface becomes hygroscopic, so that not only the electric resistance value is low and the dielectric breakdown voltage is low, but also a resin that is a toner composition. The interaction with the component becomes strong, which is not preferable in terms of mixing and dispersibility. Preferably it is 120-990 ppm, More preferably, it is 130-980 ppm.

  In the black magnetic iron oxide particle powder according to the present invention, the content [A (ppm)] of the Al element present in the surface layer of the black magnetic iron oxide particle and the alkaline earth metal element (Mg, Ca, Sr, Ba) The ratio [A / B] with respect to the content [B (ppm)] is 1.0 or more and 100 or less. Ratio [A / B] of content [A (ppm)] of Al element and content [B (ppm)] of alkaline earth metal elements (Mg, Ca, Sr, Ba) is less than 1.0 In this case, an electrical resistance value in the low voltage region can be obtained to a certain degree, but the resistance value becomes low in the high voltage region. When the A / B ratio exceeds 100, the hygroscopicity increases, and as a result, the electric resistance value decreases in the high voltage region. Preferably it is 1.0-90, More preferably, it is 1.0-80.

  The dielectric breakdown voltage of the black magnetic iron oxide particles according to the present invention is 400 V / cm or more. When the dielectric breakdown voltage is less than 400 V / cm, it cannot be said that the electric resistance is high in the high voltage region. The dielectric breakdown voltage is preferably 500 V / cm or more, more preferably 600 V / cm or more. The upper limit is about 1.8 kV / cm in actuality because the measurement at the applied voltage of 1000 V is the limit in the measuring apparatus used this time.

  When the black magnetic iron oxide particle powder according to the present invention is stirred and mixed in a 0.002N HCl aqueous solution at 40 ° C. for 10 minutes, the eluted Al amount (weak acid-soluble Al amount) is 500 ppm or less in terms of the weight of the particle powder. Preferably there is. When the amount of weak acid-soluble Al exceeds 500 ppm, the electrical resistance value / dielectric breakdown voltage is low. This is because the layer of the compound composed of alkaline earth metal element and Al element formed on the surface of the particle is non-uniform, so that it is easy to elute when the powder is exposed to a weak acid aqueous solution. Because of the surface treatment, there is a portion where the surface treatment layer is thin or a portion where the surface treatment is not performed, and electricity easily flows in that portion, and the electric resistance value is low and the dielectric breakdown voltage is also low. The amount of eluted Al is more preferably 450 ppm or less, and still more preferably 400 ppm or less.

The electric resistance value when a 500 V DC voltage is applied to a molded product having a molded body density of 2.7 g / cm ³ of the black magnetic iron oxide particles according to the present invention is preferably 1 × 10 ⁶ Ωcm or more, more preferably 1 ×. It is preferable that it is 10 ⁷ Ωcm or more.

  The average particle size of the black magnetic iron oxide particles according to the present invention is preferably 0.10 to 0.30 μm. When the particle size is smaller than 0.10 μm, it is difficult to disperse the pigment in the toner particle when used for the toner particle, which is not preferable. In the case of particles larger than 0.30 μm, the number of magnetic particles in the toner particles decreases, so that the coloring power is low, which is not preferable.

The BET specific surface area value of the black magnetic iron oxide particle powder according to the present invention is preferably 4 to ²⁰ m ² / g. When the BET specific surface area value is less than 4 m ² / g, the BET specific surface area value is smaller than the theoretical calculation value, and particles may strongly aggregate and exist as coarse particles larger than the particle diameter. It is not preferable from the viewpoint. When the BET specific surface area value exceeds 20 m ² / g, the hygroscopicity becomes high, which is not preferable because it tends to cause a decrease in image density in a high temperature and high humidity environment.

  In the black magnetic iron oxide particles according to the present invention, the product α of the average particle diameter and the BET specific surface area represented by the following formula is preferably 1.2 to 2.0, more preferably 1.3 to 1.9. It is.

<Equation 1>
α = BET specific surface area (m ² / g) × average particle diameter (μm)

  When α exceeds 2.0, the BET specific surface area value at the same particle diameter is high and the hygroscopicity is high, so that the electric resistance value is low and the dielectric breakdown voltage tends to be low. The reason why the BET specific surface area value increases is that the compound of the alkaline earth metal element and Al element present on the surface is not uniformly surface-treated, or is a compound other than the magnetic particle at a portion other than the surface of the core particle Can be caused by precipitation. When α is 1.2, it is a case where the BET specific surface area value is the smallest possible assuming that the particles are spherical, and means that the most uniform and smooth surface layer is formed. It is theoretically impossible to obtain particles having a BET specific surface area value lower than this value in the particle diameter range described above.

  The core particle of the black magnetic iron oxide particle powder according to the present invention contains various elemental components in the whole particle interior or in a specific part inside the particle in order to further improve various properties required for use. However, when Al is contained in the core particles, the weakly acid-soluble Al elution amount of the black magnetic iron oxide particle powder finally obtained after the surface treatment is at least black magnetic iron oxide for the reason described above. It must be 500 ppm or less in terms of the weight of the particle powder.

  Next, a method for producing black magnetic iron oxide particles according to the present invention will be described.

  The black magnetic iron oxide particles according to the present invention produce magnetite core particles according to a conventional method, and then add an aluminum salt and an alkaline earth metal salt to the slurry containing the core particles, It can be obtained by adjusting the pH.

  As described above, the core particles for obtaining the black magnetic iron oxide particle powder of the present invention can be selected in various shapes and particle sizes from the viewpoint of magnetic properties and dispersibility required as a black magnetic pigment. There are various production methods, but in order to achieve the object of the present invention more effectively, from the viewpoint of performing the surface treatment described later more uniformly, the core particle slurry contains an inhibitor of the surface treatment. For example, it is preferable that no unreacted iron hydroxide fine particles are mixed. From the same viewpoint, it is more preferable that the surface of the core particle is smoother.

As described above, there are various methods for obtaining the slurry containing the core particles. For example, by controlling the pH during the oxidation reaction of the Fe ²⁺ aqueous solution to a predetermined value, octahedron, polyhedron, hexahedron, spherical -An uneven shape can be obtained. Further, core particles having a desired particle diameter can be obtained by controlling the growth conditions of the particles during the oxidation reaction. In addition, the surface smoothness of the core particles controls the growth conditions at the end of the oxidation reaction, and as is generally known, components such as silica components and aluminum components and spinel ferrite crystal structures such as zinc, manganese and calcium are formed. It can also be controlled by adding an easy-to-use component.

As the Fe ²⁺ aqueous solution, for example, a general iron compound such as ferrous sulfate or ferrous chloride can be used. In order to obtain iron hydroxide or an alkaline solution as a pH adjuster, an aqueous solution such as sodium hydroxide or sodium carbonate can be used. Each raw material may be selected in consideration of economy and reaction efficiency.

  For example, if spherical core particles are taken as an example, they can be obtained by the following method.

A ferrous sulfate reaction aqueous solution containing ferrous hydroxide colloid obtained by reacting ferrous sulfate aqueous solution with 0.95 equivalent sodium hydroxide aqueous solution with Fe ^{2+ in} the ferrous sulfate aqueous solution. Then, oxygen gas is passed through, and an oxidation reaction is performed at 90 ° C. to generate magnetite particles. Then, an aqueous sodium hydroxide solution of 1 equivalent or more is added to the remaining Fe ²⁺ , followed by an oxidation reaction.
In the surface treatment described later, when Ca, Sr, or Ba is used as an alkaline earth metal element, a water-insoluble salt such as sulfate radical (SO ₄ ²⁻ ) is generated in the slurry containing the core particles. More preferably, there are few components to do.

  The pH of the slurry containing the core particles is 10 or more, preferably 11 or more. When the pH is less than 10, when the Al component is added to the slurry containing the core particles, aluminum hydroxide is generated simultaneously with the addition, and it is difficult to form a uniform layer on the core particle surface.

  The temperature range of the slurry containing the core particles is preferably 60 to 95 ° C. When the temperature of the slurry is less than 60 ° C., it is difficult to form a uniform layer composed of an Al component and an alkaline earth metal element component on the core particle surface. The upper limit of the temperature is not particularly limited, but since it is an aqueous slurry, the upper limit is about 95 ° C. in consideration of productivity and cost.

  The addition amount of the Al compound to the slurry containing the core particles may be added in an amount of 1000 ppm or more and 20000 ppm or less as the surface treatment particles finally obtained according to the amount of the core particles contained in the slurry. If it is less than 1000 ppm, a powder having the desired electrical characteristics cannot be obtained. In the case of 20000 ppm or more, the hygroscopicity becomes high and the electric resistance value becomes low.

  The amount of the alkaline earth metal element compound added to the slurry containing the core particles is 100 ppm or more and 2000 ppm or less as the surface treatment particles finally obtained according to the amount of the core particles contained in the slurry. do it. If it is less than 100 ppm, a powder having the desired electrical characteristics cannot be obtained. In the case of 2000 ppm or more, the hygroscopicity is high and the electrical resistance value is low.

  The order of addition of the aqueous solution containing the Al element component and the aqueous solution containing the alkaline earth metal element component to the slurry containing the core particles should not be specified. A mixed aqueous solution may be prepared and added.

  After the addition of the Al compound and the alkaline earth metal salt, the pH of the slurry is preferably controlled in the range of 4 to 10, preferably 5 to 8. In the control, it is preferable that the mixed solution with the slurry is well stirred. The pH control is preferably performed by gradually reducing the pH of the core particle slurry having a pH of 10 or more containing the Al compound and the alkaline earth metal salt aqueous solution as much as possible. , Adjusting the pH to 8 to 10, uniformly mixing for 5 minutes or more, adding an acidic aqueous solution again to gradually lower the pH, and finally adjusting to pH 6.5 to 7.5. When the final pH of the slurry is less than 4, it is difficult to uniformly form the Al compound layer on the surface of the core particles. When the pH exceeds 10, it is difficult to produce an Al compound.

  After the addition of the Al compound and the alkaline earth metal salt, the temperature range of the slurry is preferably controlled at 60 to 95 ° C. When the temperature of the slurry is less than 60 ° C., it is difficult to form a uniform layer composed of an Al component and an alkaline earth metal element component on the core particle surface. The upper limit of the temperature is not particularly limited, but since it is an aqueous slurry, the upper limit is about 95 ° C. in consideration of productivity and cost.

  After the reaction, it may be washed with water and dried according to a conventional method.

<Action>
It is important that the Al compound present on the outside (surface layer) of the core particle of the black magnetic iron oxide particle powder according to the present invention is present on the surface of the core particle together with the alkaline earth metal element component. In addition, this Al component may be an Al component that is charged all at once during the oxidation reaction for the synthesis of black magnetic iron oxide particles and remains in the system after the Al component is taken into the core particles. In this case as well, it is essential that the Al component present on the surface of the core particle be present together with the alkaline earth metal element component. In fact, particle powders (Patent No. 3259744) obtained by surface treatment by adding an Al component after the synthesis of magnetite particles previously reported by the present inventors, and Al-doped magnetite particle synthesis as described in Comparative Examples described later. In the case where only the Al component was surface-treated on the subsequent particle surface, no improvement in electrical properties was observed. The reason for this is not clear, but the present inventors formed a film-like hydroxide phase uniformly on the surface of the core particle by forming an Al component and an alkaline earth metal element component and a compound present on the surface of the core particle. Or it is guessed that it will be for forming the insulating layer as an oxide hydroxide phase.

  Representative examples of the present invention are as follows.

<Measurement method>
The average particle size of the black magnetic iron oxide particle powder was measured with an image processing system for a field of view of 800 or more particles taken with a “transmission electron microscope JEM-1200EX” (manufactured by JEOL Ltd.). It is the value obtained from the Martin diameter.

  The particle shape of the black magnetic iron oxide particle powder was judged from a photograph observed with a transmission electron microscope and “scanning electron microscope S-4800” (manufactured by Hitachi High-Technologies Corporation).

  The BET specific surface area value was determined by the BET method using “Mono Sorb MS-II” (manufactured by Yuasa Ionics Co., Ltd.).

  The amount of alkaline earth metal elements (Mg, Ca, Sr, Ba) and Al contained in the black magnetic iron oxide particle powder was measured with a “fluorescence X-ray analyzer RIX-2100” (manufactured by Rigaku Corporation). The values obtained in terms of Mg, Ca, Sr, Ba, and Al with respect to the black magnetic iron oxide particle powder.

  The amount of weakly acid-soluble Al in the black magnetic iron oxide particles was determined by ICP spectroscopy of the amount of Al element contained in the filtrate after the particle powder to be measured was stirred and mixed in a 0.002N-HCl aqueous solution at 40 ° C. for 10 min. Quantification was performed by analysis “inductively coupled high-frequency plasma spectrometer SPS-4000 type” (manufactured by Seiko Denshi Kogyo Co., Ltd.).

That is, 8 g of black magnetic iron oxide particle powder was added to water and the well stirred slurry was kept at 40 ° C.
A hydrochloric acid solution was added thereto to make an HCl concentration of 0.002N and a total amount of 800 ml, and then the slurry stirred for 10 minutes was collected, and the filtrate separated using a 0.1 μm membrane filter was quantified for Al by ICP spectroscopic analysis. The starting point of stirring for 10 min was set to 0 min when the HCl solution was added. Moreover, the quantitative value of Al was stabilized with good reproducibility by thoroughly peptizing the water slurry before adding the HCl solution using a homogenizer or the like.

  The electric resistance value of the black magnetic iron oxide particle powder was indicated by a value measured by the following measuring method.

That is, the electric resistance value of the black magnetic iron oxide particle powder at an applied voltage of 15 V was measured by weighing 0.5 g of the particle powder to be measured, and using a KBr tablet molding machine (manufactured by Shimadzu Corporation), using a hand press (SSP manufactured by Shimadzu Corporation). -10-type gauge reading at a pressure of 14 MPa for 10 seconds (under these conditions, a molded body having a density of about 2.7 g / cm ³ can be obtained, but other molding machines are used. In such a case, the conditions may be set as appropriate so that the density is about 2.7 g / cm ^3. If the density greatly exceeds 2.5 to 2.8 g / cm ³ , the electrical resistance value changes. And comparison of measured values becomes difficult.) Next, the pressure-formed sample is set between stainless steel electrodes. At that time, the electrodes are completely separated from the outside by a fluororesin holder. A resistance value R is measured by applying a voltage of 15 V to the set sample with a Wheatstone bridge (TYPE 2768 manufactured by Yokogawa Electric Corporation). For samples with high resistance values that cannot be measured by Wheatstone Bridge, apply a constant voltage of DC 15V or 500V to the same compacted body using “High Resistance Meter 4339B” (manufactured by Hewlett Packard). Then, the resistance value R (Ω) at that time, the electrode area A (cm ² ) and the thickness t (cm) of the sample are measured, and the volume specific resistance value X (Ωcm) is calculated by the following formula.
<Formula 2>
X = R / (A / t)

The dielectric breakdown voltage of the black magnetic iron oxide particle powder was determined as follows.
First, after measuring the electrical resistance value at 10 V on the compact of the particle powder 2.0 g to be measured with the same device as the electrical resistance measuring device, the current value flowing through the sample at each voltage with the applied voltage increased by 10 V Measure. The voltage application time was within 20 seconds. When the applied voltage becomes high, dielectric breakdown occurs at a certain applied voltage, and the current value flowing through the sample becomes extremely high, making it impossible to measure the current value. A voltage E (V) at which the current value cannot be measured was obtained, and a value obtained by dividing the voltage by the sample thickness was defined as a dielectric breakdown voltage (V / cm).

Example 1
<Method for producing core particle slurry>
23.75 l of ferrous sulfate aqueous solution containing 1.6 mol / l Fe ²⁺ was prepared in advance in a reactor, 26.25 l of 2.75 mol / l sodium hydroxide aqueous solution (0.95 equivalent to Fe ²⁺ In addition to the corresponding amount), at a pH of 6.5 to 7.5 and at a temperature of 90 ° C., 80 l of air is aerated to conduct an oxidation reaction (first-stage reaction), and when the oxidation-reduction potential rises (Fe ²⁺ 1.25 l of ferrous sulfate aqueous solution containing Fe ²⁺ 1.6 mol / l is added, and at this point, Fe ²⁺ (3.9 mol) remaining in the reactor is oxidized. For this purpose, an aqueous sodium hydroxide solution was added to adjust the pH of the slurry in the reactor to 10 to 12, followed by an oxidation reaction (second stage reaction) to complete the oxidation reaction and obtain a slurry containing core particles. .

  The obtained core particles were collected, and as a result of observation of electron micrographs of the core particles filtered, washed and dried by a conventional method, the shape of the core particles was spherical.

<Surface treatment method for core particles>
After adding 0.5 l (corresponding to 10340 ppm with respect to the whole powder) of a 2.30 mol / l aluminum sulfate aqueous solution to the slurry containing the core particles obtained above and having a pH of 10 or more, and stirring at 75 to 85 ° C., 1 Add 0.05 l of 23 mol / l magnesium sulfate aqueous solution (corresponding to 498 ppm with respect to the whole powder), mix uniformly for at least 10 minutes, then add acidic aqueous solution, and adjust pH to 8-10 once. Mix for 5 minutes or more, add an acidic aqueous solution again to gradually lower the pH, and finally adjust to pH 6.5 to 7.5. The slurry is washed with water, filtered and dried to form magnetite. Black magnetic iron oxide particle powder was obtained.

Examples 2-11, Comparative Examples 1-10
A black magnetic iron oxide particle powder was obtained in the same manner as in Example 1 except that the production conditions of the black magnetic particle powder were variously changed.

  Table 1 shows the production conditions of the core particles, and Table 2 shows the characteristics of the obtained core particles. Table 3 shows the production conditions of the black magnetic iron oxide particle powder, and Table 4 shows the characteristics of the obtained black magnetic iron oxide particle powder.

  In addition, as shown in Table 2, all of the nuclear particles 1 to 6 were not measurable because the current value already exceeded the measurement range at the applied voltage of 500V.

  Further, the surface Al amounts of Examples 8 and 9 and Comparative Example 2 in Table 4 were obtained by subtracting the Al amount in the core particles from the Al amount of the finally obtained surface-treated product.

  As shown in Table 4, the black magnetic iron oxide particle powders of Comparative Examples 1 to 10 could not measure the electric resistance value at an applied voltage of 500V.

The black magnetic iron oxide particle powder having a high resistance value in the high voltage region obtained by the present invention is suitable as a pigment used in various fields. When this material is used for a toner, a high temperature and high humidity environment is used. This is particularly preferable because a high image density can be obtained at a lower level.

Claims (4)

The particle surface of the core particle is a black magnetic iron oxide particle covered with a surface layer made of a compound of at least one kind of alkaline earth metal element (Mg, Ca, Sr, Ba) and Al element, The content of at least one of the alkaline earth metal elements present in the surface layer is 100 ppm to 1000 ppm with respect to the entire black magnetic iron oxide particles, and the content of Al element present in the surface layer is black magnetic. It is 1000 ppm or more and 20000 ppm or less with respect to the whole iron oxide particles, and the content of Al element existing in the surface layer [A (ppm)] and the content of alkaline earth metal elements (Mg, Ca, Sr, Ba) The ratio [A / B] to the amount [B (ppm)] is 1 or more and 100 or less, and the dielectric breakdown voltage of the black magnetic iron oxide particle powder is 400 V / cm or more. The black magnetic iron oxide particles and said Rukoto. Elution Al amount (weak acid-soluble Al amount) when black magnetic iron oxide particle powder is stirred and mixed in 0.002 N HCl aqueous solution at 40 ° C. for 10 min is 500 ppm or less in terms of weight of particle powder. The black magnetic iron oxide particle powder according to claim 1. ^3. The electrical resistance value when a 500 V DC voltage is applied to a molded product having a molding density of black magnetic iron oxide particles of 2.7 g / cm ³ is 1 × 10 ⁶ Ωcm or more. The black magnetic iron oxide particle powder described. The average particle diameter of the black magnetic iron oxide particle powder is 0.10 to 0.30 μm, the BET specific surface area value is 4 to ²⁰ m ² / g, and the average particle diameter and the BET specific surface area value represented by the following formulas The black magnetic iron oxide particle powder according to any one of claims 1 to 3, wherein the product α is 1.2 ≦ α ≦ 2.0.
α = BET specific surface area (m ² / g) × average particle diameter (μm)