JP2007033485A - Image forming method and image forming apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an image forming method by which good images can be obtained over a prolonged period of time, with respect to an image forming method using a cleaning system simultaneous with development. <P>SOLUTION: An electrostatic latent image carrier is an electrophotographic photoreceptor having an organic photosensitive layer and has a hardened surface layer. A toner contains inorganic fine particles on the surface of toner particles containing a binder resin and a colorant, where the inorganic fine particles are strontium titanate, and the strontium titanate is particles having an average particle diameter of primary particles of 30-300 nm, a cubic particle shape and/or a cuboidal particle shape and perovskite type crystals. Particles of the toner having a circle-equivalent diameter (number basis) of ≥2 μm have an average circularity of 0.920-0.970, and UV transmittance of the toner to an aqueous solution containing 45 vol.% methanol is 10-80%. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  In the electrophotographic method, the electrostatic latent image formed on an electrostatic latent image carrier such as an electrophotographic photosensitive member or an electrostatic recording derivative is developed with a developer, and the electrostatic latent image carrier is obtained. A developing and collecting step for collecting toner remaining on the latent electrostatic image bearing member after transfer, and a toner image on the latent electrostatic image bearing member on the intermediate transfer member or transfer material. The present invention relates to an image forming method including at least a transfer step of transferring.

  Conventionally, a number of methods are known as electrophotographic methods. Generally, a photoconductive material is used to form an electrostatic latent image on an electrostatic latent image carrier (photoconductor) by various means. Next, the electrostatic latent image is developed with a developer to be visualized, and the toner image is transferred to a transfer material such as paper as necessary, and then the toner image is fixed on the transfer material by heat and pressure. To obtain a copy. At this time, the toner remaining on the photosensitive member without being transferred to the transfer material after transfer (transfer residual toner) is cleaned by various methods, and the above-described steps are repeated.

  As the cleaning method, an elastic rubber blade is pressed on the photoconductor to mechanically remove the transfer residual toner, or a brush roller planted with fine fibers is rotated at high speed to attach the toner to the brush tip. For example, a brush cleaning method for removing residual toner after transfer is known.

  In the case of an image forming method using such a cleaning method, it is necessary to provide a unit for cleaning, and work for collecting waste toner after cleaning occurs, or usable transfer residual toner is collected. Therefore, there is a problem that the printing cost per page increases. In addition, since the cleaning member directly contacts the photoconductor, depending on the long-term durability, the photoconductor may be scratched or worn, and the surface of the photoconductor may be deteriorated. In some cases, a good image cannot be obtained over a long period of time, such as a decrease in image density.

  Therefore, in recent years, the entire image forming apparatus has been made compact and compatible with ecology by eliminating waste toner. To reduce the amount of toner consumed per page, the transfer residual toner is collected and reused without using the cleaning method described above. A cleanerless system has been widely proposed (Patent Document 1, Patent Document 2, etc.). Among them, copiers and printers employing a so-called simultaneous development cleaning system that collects transfer residual toner in a developing device simultaneously with development have been put into practical use. In particular, since this simultaneous development cleaning system does not use a cleaning unit, dramatic progress can be seen with respect to ecology by making the apparatus compact and eliminating waste toner.

  However, when such a simultaneous development cleaning method is used, problems such as suppression and removal of deposits on the surface of the photoreceptor remain.

  From the standpoint of suppressing deposits on the surface of the photoconductor, a cleaning unit is not used in the image forming process, and therefore, in the long-term durability, phenomena such as toner fusing and filming on the photoconductor do not occur. desired. However, when the cleaning unit is not used, since there is no stripping means, if a phenomenon such as fusion or filming occurs even partly, these phenomena tend to be promoted. Therefore, in the conventional toner, in order to further reduce the transfer residual toner, a toner having high transfer efficiency and suppressing the adhesion of the toner to the surface of the photoreceptor is desired.

  In addition, when carried out over a long period of time, particularly in a high humidity environment, not only toner fusion and filming, but also ozone generated in the charging process for charging the photoreceptor reacts with nitrogen in the air to produce nitrogen oxides ( NOx), and these nitrogen oxides may react with moisture in the air to form nitric acid and adhere to the surface of the photoconductor, thereby reducing the resistance of the surface of the photoconductor. For this reason, an image flow due to a charged product on the surface of the photoreceptor is generated during image formation.

  Therefore, in the charging process, instead of the conventional charging method using corona discharge that generates a large amount of ozone, a charging member such as a roller or a blade is brought into contact with the surface of the photosensitive member to form a discharge near the contact portion. Therefore, a charging system that suppresses generation of ozone as much as possible is widely used. Among them, a roller charging method using a charging roller as a charging member is particularly preferably used from the viewpoint of charging stability. However, even in such a charging method, the essential charging mechanism uses a discharge phenomenon from the charging member to the photoconductor, so that the above-described image flow due to the charged product on the surface of the photoconductor is sufficient. It can not be said.

  In Patent Documents 3 to 8, as a toner that can achieve both developability, transferability, and cleanability using a blade, a brush, or the like, the toner has an average circularity, a UV transmittance with respect to an aqueous solution of 45% by volume of methanol, and is contained in the toner. Proposals have been made for inorganic fine particles. However, these toners are good in terms of preventing toner fusion and filming on the photosensitive member in the simultaneous development cleaning system that does not use a cleaning unit, but are still improved in terms of removing charged products. There is room.

  Therefore, in addition to preventing toner fusing and filming, inorganic fine particles having an abrasive action are added to the image flow due to the charged product, and the charged product adhering to the surface of the photoreceptor is peeled off. There are known ways to improve by taking. However, conventionally used inorganic fine particles have a large particle size and a broad particle size distribution, and it has been difficult to uniformly polish the surface of the photoreceptor. Further, it was not sufficient from the viewpoint of scratches and scraping on the surface of the photoreceptor.

  As an improvement on this point, Patent Document 9 and Patent Document 10 propose a method of adding strontium titanate powder to toner particles. Since strontium titanate used in these methods has a fine particle size and few coarse particles, it has an excellent polishing effect. However, the strontium titanate powder used in these methods is effective for preventing filming and fusing by the toner on the surface of the photoreceptor, but for removing the charged product as described above. It was insufficient.

  Patent Document 11 proposes a method of using toner particles containing a polishing substance and a fatty acid metal salt. Patent Document 12 proposes a method of externally adding a fatty acid metal salt and a titanic acid compound to toner particles. Patent Document 13 proposes a method of externally adding a metal oxide surface-treated with a lubricant such as a fatty acid metal salt. However, none of these methods is sufficient for removing the charged product.

  As described above, in the simultaneous development cleaning method, the toner can be prevented from fusing and filming on the surface of the photosensitive member, and further, an effective polishing action that can suppress the image flow by removing the charged product. Toners containing inorganic fine particles are widely desired. At the same time, when using toner containing inorganic fine particles that have an effective polishing action, it has excellent wear resistance and releasability in order to suppress scratches and abrasions on the surface of the photoreceptor for a long period of time. A photoreceptor having a surface layer is also desired.

Japanese Patent Laid-Open No. 05-053482 JP-A-10-307456 JP 2004-271850 A JP 2004-271851 A JP 2004-271852 A JP 2004-271853 A JP 2004-295100 A JP 2004-295101 A Japanese Patent Laid-Open No. 10-10770 Japanese Patent No. 3047900 JP 2000-162812 A JP-A-8-272132 JP 2001-296688 A

  It is an object of the present invention to prevent toner fusing and filming on a photoreceptor and image flow due to a charged product in an image forming method using a simultaneous development cleaning method, particularly under high temperature and high humidity, and for a long time. An object is to provide an image forming method and an image forming apparatus capable of obtaining a good image.

  The above object is achieved by the following configurations of the present invention.

The present invention includes a charging step of charging the electrostatic latent image carrier, an electrostatic latent image forming step of forming an electrostatic latent image on the charged electrostatic latent image carrier, and the electrostatic latent image with a developer. Developing and forming a toner image on the electrostatic latent image carrier and developing and collecting the toner remaining on the electrostatic latent image carrier after transfer; In an image forming method including at least a transfer step of transferring a toner image to an intermediate transfer member or a transfer material,
The latent electrostatic image bearing member is an electrophotographic photosensitive member having an organic photosensitive layer, and has a curable surface layer,
The toner is a toner containing at least inorganic fine particles on the surface of toner particles containing at least a binder resin and a colorant, and the inorganic fine particles are strontium titanate, and the strontium titanate is a primary particle. Particles having an average particle size of 30 nm or more and 300 nm or less, a cubic particle shape and / or a rectangular parallelepiped particle shape, and a perovskite crystal, and an equivalent circle diameter (number basis) of the toner of 2 μm. The present invention relates to an image forming method, wherein the average circularity of the particles is 0.920 to 0.970, and the UV transmittance of the toner with respect to a 45 volume% methanol aqueous solution is 10 to 80%.

  According to the present invention, the developer is a two-component developer having at least a toner and a magnetic carrier, and the magnetic carrier has a coating layer on the surface of a magnetic fine particle-dispersed resin core containing at least magnetic fine particles and a binder resin. It is related with the image forming method characterized by having.

Further, according to the present invention, the surface of the electrostatic latent image carrier is subjected to a hardness test using a Vickers square pyramid diamond indenter in an environment of 25 ° C. and 50% humidity, and the HU (universal hard disk) is pushed in with a maximum load of 6 mN. And an elastic deformation rate We of 45% or more and 65% or less. The present invention relates to an image forming method characterized in that the value is 150 N / mm ² or more and 220 N / mm ² or less.

  The charging step in the present invention also relates to an image forming method characterized by a contact charging method.

  The image forming method according to the present invention also relates to an image forming method characterized by further comprising a leveling step of leveling toner remaining on the electrostatic latent image carrier after transfer and before charging, and applying a bias. .

The present invention also provides a charging means for charging the electrostatic latent image carrier, an electrostatic latent image forming means for forming an electrostatic latent image on the charged electrostatic latent image carrier, and the electrostatic latent image as a developer. Developing and collecting means for collecting toner remaining on the electrostatic latent image carrier after the transfer, and at the same time forming a toner image on the electrostatic latent image carrier, An image forming apparatus having at least transfer means for transferring the toner image to an intermediate transfer member or transfer material,
The electrostatic latent image carrier is an electrophotographic photosensitive member having an organic photosensitive layer, and has a curable surface layer,
The toner is a toner containing at least inorganic fine particles on the surface of toner particles containing at least a binder resin and a colorant, and the inorganic fine particles are strontium titanate, and the strontium titanate is a primary particle. Particles having an average particle diameter of 30 nm or more and 300 nm or less, a cubic particle shape and / or a rectangular parallelepiped particle shape, and a perovskite crystal, and an equivalent circle diameter (number basis) of the toner of 2 μm. The present invention relates to an image forming apparatus characterized in that the average circularity of the particles is 0.920 to 0.970, and the UV transmittance of the toner with respect to a 45 volume% methanol aqueous solution is 10 to 80%.

  According to the present invention, in the image forming method according to claim 1, in the image forming method using the simultaneous development cleaning method, the toner is fused or filmed to the photoreceptor, particularly under high temperature and high humidity. It has an effect that an image can be prevented from flowing due to a charged product and a good image can be obtained over a long period of time.

  According to the present invention, the image forming method according to claim 2 prevents the magnetic brush of the two-component developer from becoming rigid, and the polishing action of the inorganic fine particles contained in the toner is effective. This prevents the toner from fusing and filming on the photoconductor, and can effectively remove the charged products that cause the image flow.

  According to the present invention, the image forming method according to claim 3 improves the releasability of the surface of the photoreceptor, improves the transferability of the toner, and improves the wear resistance of the surface of the photoreceptor. By drastically improving, it is possible to provide an image forming method with further excellent durability.

  According to the present invention, the image forming method according to claim 4 can suppress the generation of charged products particularly under high temperature and high humidity, and in the transfer residual toner in the contact area with the photoreceptor. Due to the polishing action of the contained inorganic fine particles, there is an effect that the charged product that causes the image flow can be efficiently removed.

  According to the present invention, in the image forming method according to claim 5, the charging polarity of the transfer residual toner collected at the time of development can be made uniform by the leveling step, so that the toner recovery rate at the time of development can be increased. In addition to the improvement, there is an effect that the charged product which is the cause of the image flow can be efficiently removed by the polishing action of the inorganic fine particles contained in the transfer residual toner at the contact portion with the photoreceptor.

  Furthermore, according to the present invention, in the image forming apparatus according to claim 6, in the image forming apparatus using the simultaneous development cleaning method, the toner is fused or filmed to the photosensitive member particularly under high temperature and high humidity. In addition, the image flow due to the charged product can be prevented, and a good image can be obtained over a long period of time.

  Hereinafter, the best mode for carrying out the present invention will be described in detail.

  First, the image forming method of the present invention will be described in detail.

  An example of a simultaneous development cleaning method using the image forming method of the present invention is shown in FIG. In FIG. 1, an electrophotographic photosensitive member 1 serving as an electrostatic latent image carrier rotates in the b direction. The photosensitive member 1 is charged by a charging device 2 as a charging unit, and a laser beam L is projected onto the charged surface of the photosensitive member 1 by an exposure device 3 as an electrostatic latent image forming unit to form an electrostatic latent image. . Thereafter, the electrostatic latent image is visualized as a toner image by the developing device 4 that is a developing unit, and is transferred to the transfer material P by the transfer device 5 that is a transfer unit. In this transfer unit, the untransferred toner remaining on the surface of the photosensitive member without being transferred passes through the above-described charging unit and electrostatic latent image forming unit, and is again used for development or collected by the developing device.

  Here, each step of the image forming method that can be used in the present invention will be described in more detail.

  The charging step is not particularly limited as long as it is a means for charging the surface of the photoconductor to charge the electrophotographic photoconductor. As the charging means, a device for charging the electrophotographic photosensitive member without contact with the electrophotographic photosensitive member, such as a corona charging means, or an electrophotographic photosensitive member by contacting a conductive roller or blade with the electrophotographic photosensitive member. Devices that charge the body can be used.

  In the present invention, the contact charging method is preferable from the viewpoint of the charged product. Corona discharge, which is a conventional non-contact charging method, generates a large amount of ozone that reacts with nitrogen in the air to form nitrogen oxides (NOx), and these nitrogen oxides react with moisture in the air to form nitric acid. It adheres to the surface of the photoreceptor and tends to reduce the resistance of the surface of the photoreceptor. On the other hand, in the contact charging method, the amount of ozone generated is remarkably small, and the change in the resistance of the photoreceptor surface due to the charged product is small. Further, the contact charging method is more preferable because the charged product that causes the image flow can be efficiently removed by the polishing action of the inorganic fine particles contained in the transfer residual toner in the contact area with the photoreceptor.

  The contact charging method includes a discharge charging mechanism such as a roller charging method and a direct injection charging mechanism such as a magnetic brush charging method.

  The discharge charging mechanism is a mechanism in which the surface of the member to be charged is charged by a discharge phenomenon that occurs in the gap between the contact charging member and the member to be charged. Since the discharge charging system has a constant discharge threshold value for the contact charging member and the member to be charged, it is necessary to apply a voltage larger than the potential of the member to be charged to the contact charging member. In addition, the amount of generation is much smaller than that of a corona charger, but in principle, a charged product is generated.

As a contact charging member by discharge, a roller charging method (roller charging device) using a conductive roller (charging roller) is preferable in terms of discharge stability and is widely used. The discharge charging roller may be formed in a roller shape using a conductive or medium resistance rubber material or foam as a base layer, and the surface thereof may be made of a high resistance layer. In this configuration, the discharge phenomenon occurs in a gap of several tens of μm that is slightly away from the contact portion between the roller and the member to be charged. Therefore, in order to stabilize the discharge phenomenon, a layer on the roller surface (hereinafter referred to as a surface layer) is flat, has an average surface roughness Ra of 1.0 μm or less, and has a surface with high roller hardness. Preferably it is. In addition, the roller charging due to the discharge has a high applied voltage, and if there is a pinhole (exposed substrate due to damage to the film to be charged), a voltage drop and a charging failure are likely to occur around it. Therefore, the surface resistance of the surface layer is preferably 10 ¹¹ Ω or more from the viewpoint of preventing a voltage drop.

  The direct injection charging mechanism is a charging mechanism that charges (charges) the surface of a member to be charged by directly transferring and receiving charges by contacting the contact charging member and the member to be charged at the molecular level. It is also called direct charging or injection charging.

  As the contact charging member by injection, a magnetic brush charging method (magnetic brush charging device) using a magnetic brush is preferably used. The magnetic brush charging uses a member having a magnetic brush portion formed in a brush shape by magnetically constraining conductive magnetic particles with a magnet roll or the like as a contact charging member, and the magnetic brush portion is contacted with a photosensitive member as a charged body. Then, a predetermined charging bias is applied to charge the photoreceptor surface to a predetermined polarity and potential.

  It is preferable to perform direct injection charging uniformly by using particles having an average particle diameter of 5 to 50 μm on a number basis as the conductive magnetic particles constituting the magnetic brush portion and providing a sufficient speed difference from the photoreceptor. Magnetic brush charging also has problems such as complicated equipment configuration and conductive magnetic particles constituting the magnetic brush portion falling off and adhering to the photoreceptor.

  The average particle size of the conductive magnetic particles is determined by randomly extracting 300 or more conductive magnetic particles having a particle size of 0.1 μm or more with a scanning electron microscope (100 to 5000 times), and using a digitizer as a particle size with a horizontal ferret diameter. Measure and calculate the number average particle diameter of the conductive magnetic particles.

  In the direct injection charging mechanism, the potential difference between the contact charging member and the member to be charged is about several volts to several tens of volts. The charging potential is equal to the applied voltage, and there is no voltage difference that causes discharge. In addition, the voltage required for charging can be kept low. Since this direct charging system does not involve the generation of ions, no adverse effects caused by the discharge products occur. That is, it is a charging method that is excellent in terms of low power without generating ozone.

  As the mechanism of the contact charging method, the above two methods can be mentioned, but neither of them generates a large amount of ozone in the conventional non-contact charging method using corona discharge, from the viewpoint of suppression of charged products and low power. Preferably used.

  In the electrostatic latent image forming step, a known exposure apparatus can be used as the exposure means. For example, a semiconductor laser or a light emitting diode is used as the light source, and a scanning optical system unit including a polygon mirror, a lens, and a mirror can be used.

  The development process is mainly divided into a one-component contact development method that does not require a carrier and a two-component development method that includes a toner and a carrier, and any of them can be used. In the present invention, a two-component development method is preferably used from the viewpoint of suppressing and removing deposits on the surface of the photoreceptor.

  As a two-component development method, a magnetic brush of a two-component developer having a nonmagnetic toner and a magnetic carrier is formed on a developer carrier (development sleeve) containing a magnet, and the magnetic brush is formed with a developer layer thickness. After coating with a regulating member to a predetermined layer thickness, the magnetic brush is transported to a developing area facing the photoreceptor, and the magnetic brush is applied while applying a predetermined developing bias between the photoreceptor and the developing sleeve in the developing area. Is a method in which the electrostatic latent image is visualized as a toner image by bringing the toner close to or in contact with the surface of the photoreceptor.

  As described above, by bringing the magnetic brush close to or in contact with the surface of the photoconductor, the deposits on the surface of the photoconductor can be reduced, and the surface of the photoconductor can be reduced by the inorganic fine particles contained in the toner. This is preferably used because it can effectively remove the deposits.

  Examples of the magnetic carrier that can be used in such a two-component developer include an iron powder carrier, a ferrite carrier, and a magnetic fine particle dispersed resin carrier in which magnetic fine particles are dispersed in a binder resin. In the iron powder carrier, since the specific resistance of the carrier itself is low, the charge of the electrostatic latent image leaks through the carrier, and the electrostatic latent image may be disturbed, thereby causing an image defect. Also, in the ferrite carrier, although the specific resistance of the carrier itself is relatively high, the magnetic brush tends to be stiff due to the large saturation magnetization, and the magnetic brush has uneven spots on the toner image. There is. Therefore, a magnetic fine particle dispersed resin carrier in which magnetic fine particles are dispersed in a binder resin is preferably used. The magnetic fine particle-dispersed resin carrier has a relatively higher specific resistance than that of a ferrite carrier, has a lower saturation magnetization, and a lower true specific gravity, thereby preventing electrostatic latent image charge leakage and a rigid magnetic brush. Therefore, it is preferable in that a good toner image free from image defects and unevenness in stitches can be formed.

  In the transfer process, the toner image on the surface of the photoconductor is transferred to the transfer material without contact with the photoconductor, such as corona transfer means, or a roller or an endless belt-shaped transfer member is brought into contact with the photoconductor. There are methods for transferring a toner image on the body surface onto a transfer material, and any method can be used.

  In the present invention, as in the charging step, a large amount of ozone is not generated, and a contact type transfer roller, a resin belt, or an elastic belt-like transfer member is preferably used from the viewpoint of suppression of charged products and low power. It is done.

  In the image forming method of the present invention, as shown in FIG. 2, the transfer residual toner on the photosensitive member is leveled after the transfer and before the charging step, thereby improving the recovery rate of the transfer residual toner during development. Therefore, it is preferable to further include a leveling step 6 having a bias applying means for the purpose of uniformizing the charging polarity of the transfer residual toner.

  In the leveling step 6, when the toner is negatively charged, it is preferable to apply a bias for negatively charging the transfer residual toner to reduce adhesion of the transfer residual toner to the charging member in the charging step. This improves the recovery rate of the transfer residual toner during development. Further, as the leveling member, a brush-like member is preferably used. Furthermore, it is preferable to provide a plurality of such leveling members because the transfer residual toner adheres to the charging member and the recovery rate of the transfer residual toner during development increases.

  Next, the electrophotographic photoreceptor of the present invention will be described in detail.

  The electrophotographic photoreceptor used in the image forming method of the present invention is formed by polymerizing or crosslinking a compound having a polymerizable functional group in the surface layer and curing.

  Charge transport is achieved by polymerizing a compound having a polymerizable functional group, curing by crosslinking, or polymerizing a compound having a polymerizable functional group as a protective layer on a layer in which a charge transport material is dispersed in an appropriate binder resin for a photoreceptor. Alternatively, it is obtained by forming a cured layer by crosslinking.

  Examples of the polymerizable functional group include a hydroxyl group, a carboxyl group, an amino group, an isocyanate group, and an epoxy group that cause a curing reaction via an addition reaction or a condensation reaction; vinyl group, acryloyloxy group, styrene group, vinyl ether Unsaturated polymerizable functional groups such as groups; those that cause a curing reaction via a chain reaction, such as ionic polymerizable functional groups such as epoxy groups; An unsaturated polymerizable functional group is preferable from the viewpoint of design diversity.

  Examples of a method for imparting a charge transport capability to the surface layer include a method using a compound obtained by chemically bonding the polymerizable functional group directly to a charge transport material.

  Although it does not specifically limit as a charge transport material, For example, heterocyclic compounds, such as poly-N-vinyl carbazole and polystyryl anthracene, and high molecular compound which has condensed polycyclic aromatics; Heterocycles, such as pyrazoline, imidazole, oxazole, triazole, and carbazole Compounds, triarylalkane derivatives such as triphenylmethane, triarylamine derivatives such as triphenylamine, low molecular weight compounds such as phenylenediamine derivatives, N-phenylcarbazole derivatives, stilbene derivatives, and hydrazone derivatives;

  Examples of means for polymerizing or cross-linking a compound having a polymerizable functional group include heat, ultraviolet light, and electron beam. An electron beam is used from the viewpoint of efficiently reacting an unsaturated polymerizable functional group and equipment. It is preferable to use it.

  The photosensitive layer of the electrophotographic photosensitive member used in the image forming apparatus of the present invention is formed on a conductive support, and is an undercoat layer having a barrier function and an adhesive function between the conductive support and the photosensitive layer. (Also referred to as a “conductive layer”).

  In the charge generation layer, the charge generation material is well dispersed with a dispersing device such as a homogenizer, ultrasonic dispersion, ball mill, vibration ball mill, sand mill, attritor and roll mill together with 0.3 to 4 times the amount of binder resin and solvent. The obtained dispersion is applied to a conductive support or a layer formed thereon, and formed by solidifying the coating film by drying or the like, or a vapor deposition film of the charge generating material, etc. It is formed as a single composition film. The film thickness is preferably 5 μm or less, and particularly preferably in the range of 0.1 to 2 μm.

  The photoconductor binder resin is not particularly limited as long as it is a resin that dissolves in a solvent and solidifies by drying or heat. Examples of the binder resin for the photosensitive member include polymers and copolymers of vinyl compounds such as styrene, vinyl acetate, vinyl chloride, acrylic acid ester, methacrylic acid ester, vinylidene fluoride, and trifluoroethylene, polyvinyl alcohol, and polyvinyl alcohol. Examples include acetal, polycarbonate, polyester, polysulfone, polyphenylene oxide, polyurethane, cellulose resin, phenol resin, melamine resin, silicon resin, and epoxy resin.

  Note that several types of charge generating materials and photosensitive resin binders can be combined as appropriate.

  When the surface layer is a charge transport layer, the charge transport layer becomes a curable surface layer, and the charge transport material is dispersed or dissolved in an appropriate solvent together with a compound that can be polymerized by irradiation with an electron beam. After the coating, it is formed by irradiating it with an electron beam.

  As the compound that can be polymerized and cross-linked by irradiation with an electron beam, an acryloyloxy group, a methacryloyloxy group, a styrene group, and the like are particularly preferable. These are appropriately selected without being limited to any of monomers, oligomers, macromers, and polymers. They can be used in combination.

  In addition, when the above charge transporting compound having charge transporting ability, preferably hole transporting ability and capable of being polymerized and cross-linked by electron beam irradiation is used, a charge transporting layer can be formed by itself. A compound having a polymerizable functional group having no function can be mixed as appropriate. Examples of the charge transporting compound include a known hole transporting compound having an unsaturated polymerizable functional group and a known hole transporting Any compound having an unsaturated polymerizable functional group added to a part of the functional compound may be used.

  In the case of an electrophotographic photoreceptor having a single layer structure, a photosensitive layer is formed using a solution in which at least a charge generating substance, a charge transporting substance, and a compound that can be polymerized and cross-linked by electron beam irradiation are dispersed or dissolved. The use of transportable compounds is preferred.

  When the surface layer is a protective layer, the protective layer is a layer formed by electron beam irradiation, and is composed of a compound that is polymerized or crosslinked and cured by this step. The photosensitive layer can be composed of a function-separated type photoreceptor in which the charge generation layer and the charge transport layer are laminated in order, a function separation type photoreceptor in which the charge transport layer and the charge generation layer are laminated in order, or a single layer photoreceptor However, a photoconductor structure in which a charge generation layer and a charge transport layer are laminated in this order is preferable, and several kinds of charge transport materials and binder resins can be appropriately combined.

  Since the protective layer needs to have a charge transport ability after curing, if the compound does not have a charge transport ability, the charge transport ability is imparted by adding the above-described charge transport material or conductive material. It is preferable that the charge transport material and the conductive material have a functional group that can be polymerized and crosslinked by irradiation. Moreover, several types can be combined as appropriate.

  In the above-described layer formation, the method for applying the solution to the conductive support or the layer on the conductive support includes, for example, application methods such as dip coating, spray coating, curtain coating, and spin coating. The dip coating method is preferable from the viewpoint of efficiency / productivity.

  In addition, it is preferable to add a polymerization inhibitor or the like to the compound having a chain polymerizable functional group and a solution containing the same in order to suppress a change with time of the material.

  In the present invention, various additives can be added to various layers such as a photosensitive layer and a protective layer. Examples of such additives include anti-degradation agents such as antioxidants and ultraviolet absorbers, and lubricants such as fluororesin fine particles in order to improve releasability.

Further, the surface of the electrophotographic photosensitive member used in the present invention was subjected to a hardness test using a Vickers square pyramid diamond indenter in an environment of 25 ° C. and 50% humidity, and HU (universal hardness value) when pressed at a maximum load of 6 mN. ) Is 150 N / mm ² or more and 220 N / mm ² or less, and the elastic deformation rate We is preferably 45% or more and 65% or less.

The universal hardness value HU of the surface of the photoreceptor is a hardness value obtained from a surface film physical property test using a Fischer scope H100V manufactured by Fischer Instruments. In the measurement, the facing angle is defined as 136 °. Using a square pyramid diamond indenter, when the measured load is pushed into the film stepwise, the indentation depth under load is electrically detected and read, and the hardness value indicates the test load. The universal hardness value HU is represented by the hardness value at the maximum indentation depth of the indenter, as shown in the following equation.
Universal hardness value HU = K × F / h ² [N / mm ² ]
[However, K: constant (1 / 26.43), F: test load (N), h: maximum indentation depth of indenter (mm)]

  The hardness value is preferably used because it can be measured with a smaller load than other hardness measurements and the like, and a material having elasticity and plasticity can obtain hardness including elastic deformation and plastic deformation.

When the universal hardness value HU of the photoreceptor surface is less than 150 N / mm ² , the abrasion resistance of the photoreceptor surface is not sufficient, and in long-term durability, the surface is scratched or scraped. A streak image or a decrease in image density is likely to occur. On the other hand, when the universal hardness value HU exceeds 220 N / mm ² , the handling property in producing the curable surface layer as described above tends to deteriorate.

  If the elastic deformation rate We is also less than 45%, scratches and the like are likely to occur due to the physical action of the photosensitive member surface and each member in each step of the image forming process. Further, the elastic force on the surface of the photoconductor is insufficient, and the toner may be pressure-bonded to the surface of the photoconductor to cause fusion. On the other hand, when the elastic deformation rate We exceeds 65%, the surface of the photoreceptor is too brittle, and a fatal damage is likely to occur due to a crack or an instantaneous external impact.

  Next, the inorganic fine particles contained in the toner of the present invention will be described in detail.

  In the present invention, by performing the above-described image formation using a toner to which specific inorganic fine particles are added, the toner is fused and filmed on the surface of the photoreceptor in a high humidity environment, and the image by the charged product. This is preferable because the flow can be improved.

  First, the reason why toner filming and fusion to the surface of the photoreceptor can be prevented by forming an image using toner added with inorganic fine particles having an abrasive effect (hereinafter referred to as abrasive) will be described below. It seems like. The untransferred toner remaining on the photoconductor after the transfer process of the image forming process comes into contact with the member that contacts the photoconductor, and a part of the toner remains in the vicinity of the contact member. At this time, by adding an abrasive to the toner, the photosensitive member is rubbed with a pressure at which the contact member contacts the photosensitive member. What is attached to the surface of the photoconductor in a convex shape with a size of several hundreds of nanometers to several tens of micrometers, such as filming or fusion with toner, can be applied with a larger pressure when passing through the contact member. The abrasive will act. Thus, the polishing effect can be efficiently obtained by the filming and fusion part.

  However, an ionic substance such as nitrate ion, which is a charged product, adheres extremely thinly to the surface of the photoreceptor. In order to remove the ionic substance efficiently, for example, it is conceivable to increase the contact pressure of the contact member. However, in this case, the life of the photoconductor is shortened because the photoconductor is shaved. It is not preferable. Therefore, in order to remove the charged product adhering to the photoreceptor without increasing the contact pressure of the contact member, it is necessary to increase the polishing ability of the abrasive itself.

  The conventional strontium titanate powder was insufficient for the removal of the charged product, but the present inventors thought that this was due to the shape of the strontium titanate particles.

  Conventional strontium titanate powder is manufactured through a sintering process, and the shape of the particles is spherical or polyhedral. For this reason, the contact area between the strontium titanate and the surface of the photoreceptor is small, and it is not sufficient for removing the charged product because it easily slips through the contact member and does not stay in the vicinity of the contact member. It is speculated that there was.

  The present inventors can efficiently remove charged products adhering to the photoreceptor by using inorganic fine particles of perovskite crystals having a cubic and / or cuboid particle shape as an abrasive added to the toner. I found out. Since the particle shape of the abrasive is a cube and / or a rectangular parallelepiped, the contact area between the abrasive and the photoreceptor surface can be increased, and the ridge line of the abrasive cube and / or the rectangular parallelepiped is formed on the photoreceptor surface. By contacting, not only toner fusion and filming but also good scraping property of the charged product can be obtained.

  The inorganic fine particles used in the present invention have a perovskite crystal structure. Among the inorganic fine particles of perovskite crystals, strontium titanate fine powder is used, but barium titanate fine powder and calcium titanate fine powder are also preferably used.

  The inorganic fine particles of the perovskite crystal used in the present invention have an average primary particle size of 30 to 300 nm, preferably 40 to 300 nm, and more preferably 40 to 250 nm. If the average particle size is less than 30 nm, the polishing effect of the particles at the contact portion is insufficient. On the other hand, if the average particle size exceeds 300 nm, the polishing effect is too strong.

  Further, the inorganic fine powder of the perovskite crystal does not necessarily exist as primary particles on the toner particle surface, and may exist as an aggregate, but even in such a case, the inclusion of an aggregate having a particle size of 600 nm or more is included. A ratio of 1% by number or less is preferable because good results can be obtained. When the particles and aggregates of 600 nm or more are contained in excess of 1% by number, even if the primary particle size is less than 300 nm, scratches are generated on the electrostatic charge latent image carrier, which is not preferable.

  About the average particle diameter of the inorganic fine powder of the perovskite type crystal | crystallization used for this invention, 100 particle diameters were measured from the photograph image | photographed with the magnification of 50,000 times with the electron microscope, and the average was calculated | required. The particle size was determined as (a + b) / 2, where a is the longest side of the primary particles and b is the shortest side. Further, the charged product can be more efficiently removed by increasing the content of particles having a cubic and / or rectangular parallelepiped shape in the perovskite crystal inorganic fine powder used in the present invention to 50% by number or more. Therefore, it is preferable.

  The inorganic fine powder of perovskite crystal used in the present invention is added in an amount of 0.1 to 5.0% by mass, preferably 0.1 to 3.0% by mass, based on the toner particles. If the addition amount is less than 0.1% by mass, the effect of removing the deposits on the photoreceptor is insufficient, and if it is more than 5% by mass, the effect on the chargeability of the toner increases, which is not preferable.

  The inorganic fine powder of perovskite crystal used in the present invention may be surface-treated with a known surface treating agent. In the present invention, the surface treatment with a fatty acid having 8 to 35 carbon atoms or a metal salt of a fatty acid having 8 to 35 carbon atoms can be preferably used because the adhesion of the toner to the electrophotographic member including the photoreceptor can be improved. It is done. The number of carbon atoms of the fatty acid or metal salt thereof for surface treatment of the inorganic fine powder of the perovskite crystal is more preferably 10 to 30.

  When the number of carbons exceeds 35, the adhesion between the surface of the inorganic fine powder of the perovskite crystal and the fatty acid or metal salt thereof is reduced, and the surface is peeled off from the surface of the inorganic fine powder due to long-term use. The peeled fatty acid or fatty acid metal salt is not preferable because it causes image defects. When the number of carbon atoms of the fatty acid or fatty acid metal salt is less than 8, the effect of preventing the toner from adhering to the electrophotographic member containing the photoreceptor is lowered.

  A preferable treatment amount of the fatty acid or the metal salt thereof with respect to the inorganic fine powder is 0.1 to 15.0 mass%, more preferably 0.5 to 12.0 mass% with respect to the inorganic fine powder matrix.

  Inorganic fine powders of perovskite crystals used in the present invention include, for example, a strontium hydroxide added to a titania sol dispersion obtained by adjusting the pH of a hydrous titanium oxide slurry obtained by hydrolyzing a titanyl sulfate aqueous solution. And it can synthesize | combine by heating to reaction temperature. By setting the pH of the hydrous titanium oxide slurry to 0.5 to 1.0, a titania sol having good crystallinity and particle size can be obtained.

  For the purpose of removing ions adsorbed on the titania sol particles, an alkaline substance such as sodium hydroxide is preferably added to the dispersion of the titania sol. At this time, it is preferable that the pH of the slurry is not 7 or higher so that sodium ions and the like are not adsorbed on the surface of the hydrous titanium oxide. The reaction temperature is preferably 60 ° C. to 100 ° C., and in order to obtain a desired particle size distribution, the temperature rising rate is preferably 30 ° C./hour or less, and the reaction time is preferably 3 to 7 hours.

As a method for subjecting the inorganic fine powder produced by the above method to a surface treatment with a fatty acid or a metal salt thereof, there are the following methods. For example, the inorganic fine powder slurry can be put in an aqueous solution of fatty acid sodium under Ar gas or N ₂ gas atmosphere to deposit the fatty acid on the perovskite crystal surface. Also, for example, in an Ar gas or N ₂ gas atmosphere, the inorganic fine powder slurry is placed in a fatty acid sodium aqueous solution, and the desired metal salt aqueous solution is dropped while stirring to precipitate a fatty acid metal salt on the perovskite crystal surface. Can be adsorbed. For example, if a sodium stearate aqueous solution and aluminum sulfate are used, aluminum stearate can be adsorbed.

  Next, the toner used in the present invention will be described in detail.

  First, the binder resin that can be used in the present invention will be described.

  As the binder resin used in the present invention, commercially available resins can be used, but (a) a polyester resin, (b) a hybrid resin having a polyester unit and a vinyl copolymer unit, (c) Mixture of hybrid resin and vinyl copolymer, (d) Mixture of polyester resin and vinyl copolymer, (e) Mixture of hybrid resin and polyester resin, and (f) Polyester resin, hybrid resin and vinyl It is a resin selected from a mixture with a copolymer.

  When a polyester resin is used as the binder resin, a polyhydric alcohol and a polyvalent carboxylic acid, a polyvalent carboxylic acid anhydride, a polyvalent carboxylic acid ester, or the like can be used as a raw material monomer.

  Specifically, for example, as the dihydric alcohol component, polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (3.3) -2,2-bis ( 4-hydroxyphenyl) propane, polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.0) -polyoxyethylene (2.0) -2,2 -Alkylene oxide adducts of bisphenol A such as bis (4-hydroxyphenyl) propane, polyoxypropylene (6) -2,2-bis (4-hydroxyphenyl) propane, ethylene glycol, diethylene glycol, triethylene glycol, 1, 2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, Opentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, bisphenol A And hydrogenated bisphenol A.

  Examples of the trivalent or higher alcohol component include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene, etc. Can be mentioned.

  Divalent acid components include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid or anhydrides; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or anhydrides; And succinic acid substituted with 6 to 12 alkyl groups or anhydrides thereof; unsaturated dicarboxylic acids such as fumaric acid, maleic acid and citraconic acid or anhydrides thereof;

  Examples of the trivalent or higher polyvalent carboxylic acid component for forming a polyester resin having a crosslinking site include 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2 , 4-Naphthalenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, and anhydrides and ester compounds thereof.

  Among them, in particular, a bisphenol derivative represented by the following general formula (I) is used as a diol component, and a carboxylic acid component (for example, fumaric acid) composed of a divalent or higher carboxylic acid or an acid anhydride thereof, or a lower alkyl ester thereof. A polyester resin obtained by polycondensation using acid, maleic acid, maleic anhydride, phthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, etc.) as an acid component is preferable because it has good charging characteristics as a color toner. .

  In the binder resin contained in the toner used in the present invention, the “hybrid resin” means a resin in which a vinyl polymer unit and a polyester unit are chemically bonded. Specifically, it is a resin formed by a transesterification reaction between a polyester unit and a vinyl polymer unit obtained by polymerizing a monomer having a carboxylic acid ester group such as (meth) acrylic acid ester, preferably a vinyl polymer. A graft copolymer (or block copolymer) having a trunk polymer and a polyester unit as a branch polymer. In the present invention, “polyester unit” refers to a portion derived from polyester, and “vinyl polymer unit” refers to a portion derived from a vinyl polymer. The polyester monomer constituting the polyester unit is a polyvalent carboxylic acid component and a polyhydric alcohol component, and the vinyl polymer unit is a monomer component having a vinyl group.

  Vinyl monomers for producing vinyl polymer units include styrene; o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2, 4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn -Styrene such as dodecylstyrene, p-methoxystyrene, p-chlorostyrene, 3,4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene, p-nitrostyrene and derivatives thereof; ethylene, propylene, butylene, isobutylene Styrene unsaturated monoolefins such as butadiene, isoprene, etc. Unsaturated polyenes; vinyl halides such as vinyl chloride, vinyl chloride, vinyl bromide and vinyl fluoride; vinyl esters such as vinyl acetate, vinyl propionate and vinyl benzoate; methyl methacrylate, ethyl methacrylate, methacryl Propyl acid, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate Α-methylene aliphatic monocarboxylic acid esters such as methyl acrylate, ethyl acrylate, propyl acrylate, acrylic acid-n-butyl, acrylic acid isobutyl, acrylic acid-n-octyl, acrylic acid dode Acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, acrylic esters such as phenyl acrylate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether; vinyl methyl ketone, Vinyl ketones such as vinyl hexyl ketone and methyl isopropenyl ketone; N-vinyl compounds such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole and N-vinyl pyrrolidone; Vinyl naphthalenes; Acrylonitrile, methacrylonitrile, acrylamide And acrylic acid or methacrylic acid derivatives.

  In addition, unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid; maleic anhydride, citraconic anhydride, itaconic anhydride, alkenyl succinic anhydride, etc. Unsaturated dibasic acid anhydride; maleic acid methyl half ester, maleic acid ethyl half ester, maleic acid butyl half ester, citraconic acid methyl half ester, citraconic acid ethyl half ester, citraconic acid butyl half ester, itaconic acid methyl half ester, Alkenyl succinic acid half ester, fumaric acid methyl half ester, mesaconic acid methyl half ester unsaturated dibasic acid half ester; dimethylmaleic acid, dimethyl fumaric acid unsaturated dibasic acid ester; acrylic acid, meta Α, β-unsaturated acids such as rillic acid, crotonic acid and cinnamic acid; α, β-unsaturated acid anhydrides such as crotonic acid anhydride and cinnamic anhydride, the α, β-unsaturated acid and lower fatty acids And monomers having a carboxyl group such as alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid, acid anhydrides and monoesters thereof.

  Further, acrylic acid or methacrylic acid esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate; 4- (1-hydroxy-1-methylbutyl) styrene, 4- (1-hydroxy-1) -Methylhexyl) Monomers having a hydroxy group such as styrene.

  In the toner used in the present invention, the vinyl polymer unit of the binder resin may have a crosslinked structure crosslinked with a crosslinking agent having two or more vinyl groups. Examples of the crosslinking agent used in this case include aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; examples of diacrylate compounds linked by an alkyl chain include ethylene glycol diacrylate and 1,3-butylene glycol. Examples include diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, and those obtained by replacing acrylates of the above compounds with methacrylate. The diacrylate compounds linked by an alkyl chain containing an ether bond include, for example, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, poly Examples include tylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate, and those obtained by replacing acrylates of the above compounds with methacrylates; diacrylates linked by a chain containing an aromatic group and an ether bond. Examples of the compounds include polyoxyethylene (2) -2,2-bis (4-hydroxyphenyl) propane diacrylate, polyoxyethylene (4) -2,2-bis (4-hydroxyphenyl) propane diacrylate and the like The thing which replaced the acrylate of the compound of this with the methacrylate is mentioned.

  Polyfunctional cross-linking agents include pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate, and acrylates of the above compounds replaced with methacrylate; triallylcia Examples include nurate and triallyl trimellitate.

  In this invention, it is preferable that the monomer component which can react with the component of both resin units is included in any one or both of a vinyl-type polymer unit and a polyester unit. Examples of monomers that can react with the components of the vinyl polymer unit among the monomers constituting the polyester resin unit include unsaturated dicarboxylic acids such as phthalic acid, maleic acid, citraconic acid, and itaconic acid, or anhydrides thereof. It is done. Among the monomers constituting the vinyl polymer unit, those capable of reacting with the components of the polyester unit include those having a carboxyl group or a hydroxy group, and acrylic acid or methacrylic acid esters.

  As a method of obtaining a reaction product of a vinyl polymer unit and a polyester unit, there is a polymer containing a monomer component capable of reacting with each of the vinyl polymer unit and the polyester unit listed above. A method obtained by carrying out the polymerization reaction of one or both resins is preferred.

  Examples of the polymerization initiator used when producing a vinyl polymer unit that can be used in the present invention include 2,2′-azobisisobutyronitrile and 2,2′-azobis (4-methoxy-2, 4-dimethylvaleronitrile), 2,2′-azobis (-2,4-dimethylvaleronitrile), 2,2′-azobis (-2methylbutyronitrile), dimethyl-2,2′-azobisisobuty 1,1′-azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) -isobutyronitrile, 2,2′-azobis (2,4,4-trimethylpentane), 2-phenylazo-2, 4-dimethyl-4-methoxyvaleronitrile, 2,2′-azobis (2-methyl-propane), methyl ethyl ketone peroxide, acetylacetone Ketones, ketone peroxides such as cyclohexanone peroxide, 2,2-bis (t-butylperoxy) butane, t-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl hydro Peroxide, di-t-butyl peroxide, t-butylcumyl peroxide, di-cumyl peroxide, α, α'-bis (t-butylperoxyisopropyl) benzene, isobutyl peroxide, octanoyl peroxide, deca Noyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, m-trioyl peroxide, di-isopropyl peroxydicarbonate, di-2-ethylhexyl peroxide Sidicarbonate, di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxycarbonate, di-methoxyisopropyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxycarbonate, acetylcyclohexylsulfonyl Peroxide, t-butyl peroxyacetate, t-butyl peroxyisobutyrate, t-butyl peroxyneodecanoate, t-butyl peroxy 2-ethylhexanoate, t-butyl peroxylaurate, t -Butyl peroxybenzoate, t-butyl peroxyisopropyl carbonate, di-t-butyl peroxyisophthalate, t-butyl peroxyallyl carbonate, t-amyl peroxy 2-ethylhexanoate, di-t-butyl Peroxy hexahydro terephthalate, di -t- butyl peroxy azelate and the like.

  As a manufacturing method which can prepare the hybrid resin used for the toner which can be used for this invention, the manufacturing method shown to the following (1)-(6) can be mentioned, for example.

  (1) A method in which a vinyl polymer, a polyester resin, and a hybrid resin are blended after production, and the blended product is obtained by dissolving and swelling the resin component in an organic solvent (for example, xylene) and then distilling the organic solvent. Manufactured by. The hybrid resin is synthesized by separately producing a vinyl polymer and a polyester resin, then dissolving and swelling in a small amount of an organic solvent, adding an esterification catalyst and an alcohol, and performing a transesterification reaction by heating. The ester compound used can be used.

  (2) A method for producing a polyester unit and a hybrid resin component in the presence of a vinyl polymer after the production thereof. The hybrid resin component is added as necessary to the reaction of a vinyl polymer unit (a vinyl monomer can be added if necessary) and a polyester monomer (polyhydric alcohol, polycarboxylic acid), and the unit and monomer as necessary. Produced by reaction with polyester. Also in this case, an organic solvent can be appropriately used.

  (3) A method for producing a vinyl polymer unit and a hybrid resin component in the presence of a polyester resin after the production. The hybrid resin component is produced by a reaction between a polyester unit (a polyester monomer can be added if necessary) and a vinyl monomer, and a reaction between the unit and the monomer and a vinyl polymer unit added as necessary. . Also in this case, an organic solvent can be appropriately used.

  (4) After the vinyl polymer and the polyester resin are produced, either or both of a vinyl monomer and a polyester monomer (polyhydric alcohol, polycarboxylic acid) are added in the presence of these polymer units, and the added monomer. The hybrid resin component can be produced by carrying out a polymerization reaction under conditions according to the conditions. Also in this case, an organic solvent can be appropriately used.

  (5) After producing the hybrid resin, either one or both of a vinyl monomer and a polyester monomer (polyhydric alcohol, polyvalent carboxylic acid) are added to perform either or both of addition polymerization and condensation polymerization reaction. As a result, a vinyl polymer unit and a polyester unit are produced. In this case, as the hybrid resin component, those produced by the production methods (2) to (4) can be used, and those produced by known production methods can be used as necessary. it can. Furthermore, an organic solvent can be used as appropriate.

  (6) A vinyl polymer unit, a polyester unit and a hybrid resin component are obtained by mixing vinyl monomers and polyester monomers (polyhydric alcohol, polycarboxylic acid, etc.) and continuously performing addition polymerization and condensation polymerization reactions. Manufactured. Furthermore, an organic solvent can be used as appropriate.

  In the production methods (1) to (6), a plurality of types of polymer units having different molecular weights and different degrees of crosslinking can be used for the vinyl polymer unit and the polyester unit. The vinyl polymer or vinyl polymer unit in the present invention means a vinyl homopolymer or vinyl copolymer, a vinyl monopolymer unit or a vinyl copolymer unit.

  Furthermore, the molecular weight distribution measured by gel permeation chromatography (GPC) of a resin having a polyester unit that can be used in the present invention has a main peak in the region of molecular weight 3,500 to 15,000, Preferably, it has a molecular weight of 4,000 to 13,000, and Mw / Mn is preferably 3.0 or more, more preferably 5.0 or more. When the main peak is in a region having a molecular weight of less than 3,500, the high temperature offset resistance of the toner decreases. On the other hand, when the main peak is in a region having a molecular weight of more than 15000, sufficient low-temperature fixability of the toner and OHP permeability are deteriorated. Moreover, when Mw / Mn is less than 3.0, good offset resistance is reduced.

  Further, the toner used in the present invention preferably contains a wax as a release agent because the fixability can be remarkably improved.

  Examples of the wax that can be used in the present invention include the following. Oxides of aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, alkylene copolymers, microcrystalline wax, paraffin wax, Fischer-Tropsch wax, and aliphatic hydrocarbon waxes such as oxidized polyethylene wax, or the like Block copolymers of these: waxes mainly composed of fatty acid esters such as carnauba wax, behenyl behenate, and montanic acid ester wax, and those obtained by partially or fully deoxidizing fatty acid esters such as deoxidized carnauba wax Is mentioned. In addition, saturated linear fatty acids such as palmitic acid, stearic acid, and montanic acid; unsaturated fatty acids such as brandic acid, eleostearic acid, and valinalic acid; stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauvir alcohol, and seryl alcohol Saturated alcohols such as melyl alcohol; polyhydric alcohols such as sorbitol; fatty acids such as palmitic acid, stearic acid, behenic acid, and montanic acid; and stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauvir alcohol, seryl alcohol, Esters of alcohols such as merisyl alcohol; fatty acid amides such as linoleic acid amide, oleic acid amide, lauric acid amide; methylene bis stearic acid amide, ethylene biscapric acid Saturated fatty acid bisamides such as amide, ethylene bislauric acid amide, hexamethylene bis stearic acid amide; ethylene bis oleic acid amide, hexamethylene bis oleic acid amide, N, N ′ dioleyl adipic acid amide, N, N ′ dioleyl Unsaturated fatty acid amides such as sebacic acid amides; Aromatic bisamides such as m-xylene bisstearic acid amide and N, N ′ distearyl isophthalic acid amides; calcium stearate, calcium laurate, zinc stearate, magnesium stearate, etc. Aliphatic metal salts (generally referred to as metal soaps); waxes grafted with aliphatic hydrocarbon waxes using vinyl monomers such as styrene and acrylic acid; fatty acids such as behenic acid monoglycerides and many others Price Lumpur partial ester; methyl ester compounds having hydroxyl groups obtained by and hydrogenated vegetable oils and the like.

  Examples of the wax that can be particularly preferably used in the present invention include aliphatic hydrocarbon waxes and esterified products that are esters of fatty acids and alcohols. For example, low molecular weight alkylene polymer obtained by radical polymerization of alkylene under high pressure with Ziegler catalyst or metallocene catalyst under low pressure; alkylene polymer obtained by thermally decomposing high molecular weight alkylene polymer; synthesis containing carbon monoxide and hydrogen A synthetic hydrocarbon wax obtained from the distillation residue of hydrocarbons obtained from the gas by the age method or by hydrogenating them is preferred. Furthermore, what carried out the fractionation of the hydrocarbon wax by the use of the press perspiration method, the solvent method, the vacuum distillation or the fractional crystallization method is more preferably used. The hydrocarbon as a base is synthesized by the reaction of carbon monoxide and hydrogen using a metal oxide catalyst (mostly two or more multi-component systems) [for example, the Jintol method, the Hydrocol method (the fluidized catalyst bed Hydrocarbon compounds synthesized by use); hydrocarbons with up to several hundred carbon atoms obtained by the age method (using the identified catalyst bed) from which a large amount of wax-like hydrocarbons can be obtained; alkylene such as ethylene by Ziegler catalyst Polymerized hydrocarbons are preferred because they are linear hydrocarbons with little branching, small and long saturation. In particular, a wax synthesized by a method that does not rely on polymerization of alkylene is also preferred from its molecular weight distribution. Paraffin wax is also preferably used.

  The wax that can be used in the present invention preferably has a peak temperature of the maximum endothermic peak in the range of 30 to 200 ° C. in the endothermic curve in differential thermal analysis (DSC) measurement in the range of 60 to 130 ° C. . More preferably, it is in the range of 65 to 125 ° C, and particularly preferably in the range of 65 to 110 ° C.

  When the maximum endothermic peak temperature of the wax is in the range of 60 to 130 ° C., moderate fine dispersibility in the toner particles can be achieved, which is preferable in order to exhibit the effects of the present invention. On the other hand, when the maximum endothermic peak is less than 60 ° C., the blocking resistance of the toner deteriorates. Conversely, when the maximum endothermic peak exceeds 130 ° C., the fixability tends to deteriorate.

  As the colorant used in the toner used in the present invention, known dyes and / or pigments are used. A pigment alone may be used, but it is preferable to use a dye and a pigment together to improve the clarity when a full-color image forming apparatus is used.

  Examples of the color pigment for magenta toner include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perlin compounds. Specifically, C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48: 2, 48: 3, 48: 4, 49, 50, 51, 52, 53, 54, 55, 57: 1, 58, 60, 63, 64, 68, 81: 1, 83, 87, 88, 89, 90, 112, 114, 122, 123, 144, 146, 150, 163, 166, 169, 177, 184, 185, 202, 206, 207, 209, 220, 221, 254, C.I. I. Pigment violet 19, C.I. I. Bat red 1, 2, 10, 13, 15, 23, 29, 35, etc. are mentioned.

  Examples of the magenta toner dye include C.I. I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121, C.I. I. Disper thread 9, C.I. I. Solvent Violet 8, 13, 14, 21, 27, C.I. I. Oil-soluble dyes such as Disper Violet 1, C.I. I. Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40, C.I. I. Basic dyes such as basic violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, and 28 may be mentioned.

  Examples of the color pigment for cyan toner include C.I. I. Pigment Blue 1, 2, 3, 7, 15: 2, 15: 3, 15: 4, 16, 17, 60, 62, 66; I. Bat Blue 6, C.I. I. Examples include Acid Blue 45 or a copper phthalocyanine pigment in which 1 to 5 phthalimidomethyl groups are substituted on a phthalocyanine skeleton having a structure represented by the following formula (B).

〔式中、ｎは１〜５の整数を示す。〕

[In formula, n shows the integer of 1-5. ]

  Examples of the colored pigment for yellow include condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal compounds, methine compounds, and allylamide compounds. Specifically, C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 62, 65, 73, 74, 83, 93, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 155, 168, 174, 180, 181, 185, 191, C.I. I. Bat yellow 1, 3, 20 and the like. In addition, C.I. I. Direct Green 6, C.I. I. Basic Green 4, C.I. I. Dyes such as Basic Green 6 and Solvent Yellow 162 can also be used.

  As the black colorant that can be used in the present invention, carbon black, iron oxide particles, and those that are toned in black using the yellow / magenta / cyan colorant shown above can be used.

  In the toner used in the present invention, it is preferable to use a toner obtained by mixing a colorant in advance with the binder resin of the present invention to form a master batch. Then, the colorant can be favorably dispersed in the toner by melt-kneading the colorant master batch and other raw materials (binder resin, wax, etc.).

  When using a resin that can be used in the present invention to masterbatch the colorant, even when a large amount of colorant is used, the dispersibility of the colorant is not deteriorated, and the dispersibility in the toner particles is improved, Excellent color reproducibility such as color mixing and transparency. Further, a toner having a large covering power on the transfer material can be obtained. Further, by improving the dispersibility of the colorant, it is possible to obtain an image with excellent durability stability of toner chargeability and maintaining high image quality.

  The amount of the colorant used in the toner is preferably 0.1 to 15 parts by mass, more preferably 0.5 to 12 parts by mass, and most preferably 2 to 10 parts by mass with respect to 100 parts by mass of the binder resin. This is preferable in terms of color reproducibility and developability.

  In the toner used in the present invention, a known charge control agent can be used in order to stabilize the chargeability. The charge control agent varies depending on the type of charge control agent and the physical properties of other toner particle constituent materials, but generally 0.1 to 10 parts by mass per 100 parts by mass of the binder resin is preferably contained in the toner particles. More preferably, 0.1 to 5 parts by mass are contained. As such a charge control agent, there are known one that controls the toner to be negatively charged and one that controls the toner to be positively charged. One or two kinds of various kinds of charge control agents are used depending on the kind and use of the toner. The above can be used.

  Negatively chargeable charge control agents include salicylic acid metal compounds, naphthoic acid metal compounds, dicarboxylic acid metal compounds, polymer compounds having sulfonic acid or carboxylic acid in the side chain, boron compounds, urea compounds, silicon compounds, calixarene Etc. are available. As the positively chargeable charge control agent, a quaternary ammonium salt, a polymer compound having the quaternary ammonium salt in the side chain, a guanidine compound, an imidazole compound, or the like can be used. The charge control agent may be added internally or externally to the toner particles.

  In particular, the color toner that can be used in the present invention is preferably an aromatic carboxylic acid metal compound that is colorless, has a high toner charging speed, and can stably maintain a constant charge amount.

  The toner used in the present invention is preferably used after adjusting the fluidity of the toner by mixing the fluidizing agent with a mixer such as a Henschel mixer after pulverization / classification or surface modification.

  As the fluidizing agent that can be used in the present invention, known inorganic fine powders can be used. The number average particle size of the inorganic fine powder as the fluidizing agent is preferably 0.02 to 0.30 μm.

  Since the number average particle diameter of the inorganic fine particles as a fluidizing agent is in the range of 0.02 to 0.30 μm, the spacer effect between the toner and the toner of the inorganic fine particles is more exerted, thereby improving the fluidity of the toner. It becomes easy to do. When the number average particle diameter of the inorganic fine particles is smaller than 0.02, it is difficult to obtain the spacer effect, and a large amount of addition is required, which may cause deterioration in developability and fixability. On the other hand, when the number average particle diameter of the inorganic fine particles is larger than 0.30 μm, the adhesion to the toner particle surface is lowered, and the spacer effect is hardly obtained.

  Examples of the inorganic fine powder that can be used in the present invention include fluorine resin powders such as vinylidene fluoride fine powder and polytetrafluoroethylene fine powder, titanium oxide fine powder, alumina fine powder, wet process silica, and dry process silica. There are fine powdered silica, treated silica obtained by subjecting them to surface treatment with a silane compound, an organosilicon compound, a titanium coupling agent, silicone oil and the like. Among these, wet process silica, dry process silica, titanium oxide fine powder, alumina fine powder and the like are particularly preferably used.

  As a wet process silica, in particular, a sol-gel method in which a solvent is removed from a silica sol suspension obtained by hydrolysis and condensation reaction with a catalyst in an organic solvent in which water is present, and then dried to form particles. There are silica particles that are produced. The silica particles produced by the sol-gel method preferably have a sharp particle size distribution, and spherical particles can be obtained, and particles having a desired particle size distribution can be obtained by changing the reaction time.

The dry process silica is a fine powder produced by vapor phase oxidation of a silicon halogen compound, which is called so-called dry process silica or fumed silica, and is manufactured by a conventionally known technique. . For example, a thermal decomposition oxidation reaction of silicon tetrachloride gas in an oxyhydrogen flame is used, and the basic reaction formula is as follows.
SiCl ₄ + 2H ₂ + O ₂ → SiO ₂ + 4HCl

  In this production process, it is also possible to obtain a composite fine powder of silica and other metal oxides by using other metal halogen compounds such as aluminum chloride or titanium chloride together with silicon halogen compounds. .

  In the case of titanium oxide fine powder, fine particles of titanium oxide obtained by low-temperature oxidation (thermal decomposition, hydrolysis) of sulfuric acid method, chlorine method, volatile titanium compounds such as titanium alkoxide, titanium halide, titanium acetylacetonate are used. . As the crystal system, any of anatase type, rutile type, mixed crystal type thereof, and amorphous type can be used.

  And if it is alumina fine powder, buyer method, improved buyer method, ethylene chlorohydrin method, underwater spark discharge method, organoaluminum hydrolysis method, aluminum alum pyrolysis method, ammonium aluminum carbonate pyrolysis method, aluminum chloride flame Alumina fine powder obtained by a decomposition method is used. As the crystal system, α, β, γ, δ, ξ, η, θ, κ, χ, ρ type, mixed crystal type, amorphous type, α, δ, γ, θ, mixed crystal can be used. A mold or an amorphous material is preferably used.

  As a method for hydrophobizing the inorganic fine powder, it is applied by chemical or physical treatment with an organosilicon compound that reacts or physically adsorbs with the inorganic fine powder.

  As a preferred method, silica fine powder produced by vapor phase oxidation of a silicon halogen compound is treated with an organosilicon compound. Examples of such organosilicon compounds are hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane. , Bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilylacrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, dimethyl Dimethoxysilane, diphenyldiethoxysilane, hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane 1,3-diphenyltetramethyldisiloxane, and dimethylpolysiloxane containing 2 to 12 siloxane units per molecule and containing hydroxyl groups bonded to one Si at each terminal unit. These are used alone or in a mixture of two or more.

  As inorganic fine particles that can be used in the present invention, the above-described wet process silica or dry process silica treated with a coupling agent having an amino group or silicone oil is used as necessary to achieve the object of the present invention. It doesn't matter. The added amount is 0.01 to 8 parts by mass, preferably 0.1 to 4 parts by mass with respect to 100 parts by mass of the toner.

  Next, a procedure for manufacturing toner will be described.

  The toner used in the present invention is obtained by melt-kneading a binder resin, a colorant, wax, and an arbitrary material, cooling and pulverizing, and performing spheroidizing treatment and classification treatment of the pulverized product as necessary, It is particularly preferable to produce this by mixing the fluidizing agent as necessary.

  First, in the raw material mixing step, as a toner internal additive, at least a resin and a colorant are weighed and mixed in a predetermined amount and mixed. Examples of the mixing apparatus include a double-con mixer, a V-type mixer, a drum-type mixer, a super mixer, a Henschel mixer, and a Nauter mixer.

  Further, the toner raw materials blended and mixed as described above are melt-kneaded to melt the resins and disperse the colorant and the like therein. In the melt-kneading step, for example, a batch kneader such as a pressure kneader or a Banbury mixer, or a continuous kneader can be used. In recent years, single-screw or twin-screw extruders have become mainstream due to the advantage of being capable of continuous production. For example, KTK type twin screw extruder manufactured by Kobe Steel, TEM type twin screw extruder manufactured by Toshiba Machine Co., Ltd. In general, a twin-screw extruder manufactured by Kay Sea Kay, a co-kneader manufactured by Buss, or the like is used. Furthermore, the colored resin composition obtained by melt-kneading the toner raw material is rolled by a two-roll roll after melt-kneading, and then cooled through a cooling step of cooling by water cooling or the like.

  The cooled product of the colored resin composition obtained above is then pulverized to a desired particle size in a pulverization step. In the pulverization step, first, coarse pulverization is performed by a crusher, a hammer mill, a feather mill or the like, and further, fine pulverization is performed by a known wind-type pulverizer or mechanical pulverizer. In the pulverization step, the toner is pulverized to a predetermined toner particle size step by step. Further, the obtained finely pulverized product is subjected to surface modification = spheronization treatment in a surface modification step to obtain surface modified particles. After that, if necessary, the surface modified particles are classified into classifiers such as an inertia class elbow jet (manufactured by Nippon Steel & Mining Co., Ltd.), a centrifugal classifier turboplex (manufactured by Hosokawa Micron Co., Ltd.), or a high-voltage winder (new) Classification is performed using a sieving machine such as Tokyo Machine Co., Ltd. to obtain a toner having a weight average particle diameter of 3 to 11 μm.

  The toner coarse powder generated in the classification step is returned to the pulverization step and pulverized. Further, it is preferable in terms of toner productivity that the fine powder generated in the surface modification process is returned to the toner raw material blending process and reused.

  Furthermore, in the method for producing a toner of the present invention, it is preferable that inorganic fine particles for imparting fluidity are externally added to the toner obtained as described above as an external additive. As a method of externally adding an external additive to the toner, a predetermined amount of classified toner and various known external additives are blended, and high-speed agitation is applied to give a shearing force to a powder such as a Henschel mixer, a super mixer, or a Q mixer. It is preferable to stir and mix using a machine as an external additive machine. At this time, since heat is generated inside the external addition machine and agglomerates are easily generated, it is preferable to adjust the temperature by means such as cooling the periphery of the container portion of the external addition machine with water.

  Next, a mechanical pulverizer is preferably used in the toner pulverization step of the present invention.

  FIG. 4 is an example of a toner particle pulverizer system incorporating a mechanical pulverizer used in the present invention.

  In the mechanical pulverizer 301 shown in FIG. 4, the casing 313, the jacket 316 in the casing 313 that can pass cooling water, and the rotating body in the casing 313 attached to the central rotating shaft 312 rotate at high speed. A rotor 314 provided with a large number of grooves on the surface, a stator 310 provided with a large number of grooves on the outer surface of the rotor 314 at a constant interval, and a raw material to be treated. A raw material inlet 311 for introduction and a raw material outlet 302 for discharging the processed powder are configured. A space between the rotor 314 and the stator 310 is a grinding zone.

  In the mechanical pulverizer configured as described above, when a predetermined amount of powder raw material is charged into the raw material charging port 311 of the mechanical pulverizer shown in FIG. The impact generated between the rotor 314 introduced into the processing chamber and rotating at high speed in the pulverization processing chamber and provided with a number of grooves on the surface and the stator 310 provided with a number of grooves on the surface; These are crushed instantaneously by a large number of ultra high-speed vortices generated behind them and high-frequency pressure vibrations generated thereby. Thereafter, the material passes through the material discharge port 302 and is discharged. The air carrying the toner particles passes through the pulverization chamber and is discharged out of the apparatus system through the raw material discharge port 302, the pipe 219, the collecting cyclone 229, the bag filter 222, and the suction blower 224. Is done. In the present invention, since the powder raw material is pulverized in this way, it is preferable because a desired pulverization process can be easily performed without increasing the fine powder and coarse powder. These mechanical pulverizers are used in the pulverization step, but may be used in the surface modification step.

  Examples of such mechanical pulverizer include Kawasaki Heavy Industries Co., Ltd. pulverizer Kryptron, Turbo Industry Co., Ltd. turbo mill, Hosokawa Micron Co., Ltd. Inomizer, Nisshin Engineering Co., Ltd. super rotor, etc. Can do.

  In the present invention, the surface modification apparatus shown in FIG. 5 that can perform classification and surface modification treatment at the same time is preferably used.

  The batch type surface reforming apparatus shown in FIG. 5 includes a cylindrical main body casing 30, a top plate 43 installed on the upper portion of the main body casing so as to be openable and closable; a fine powder discharge section 44 having a fine powder discharge casing and a fine powder discharge pipe; A cooling jacket 31 through which cooling water or antifreeze can be passed; a plurality of square disks 33 on the upper surface, which are attached to the central rotating shaft in the main body casing 30 as surface modification means, in a predetermined direction Dispersion rotor 32, which is a disk-like rotating body that rotates at high speed; liner 34 that is fixedly arranged around dispersion rotor 32 at a constant interval and that has a large number of grooves on the surface facing dispersion rotor 32 A classification rotor 35 for continuously removing fine powder and ultrafine powder having a predetermined particle size or less in the finely pulverized product; cold air inlet 4 for introducing cold air into the main body casing 30; A charging pipe having a raw material charging port 37 and a raw material supplying port 39 formed on the side surface of the main body casing 30 for introducing finely pulverized material (raw material); discharging toner particles after the surface modification treatment to the outside of the main body casing 30; A product discharge pipe having a product discharge port 40 and a product extraction port 42 for opening and closing; an openable and closable raw material installed between the raw material input port 37 and the raw material supply port 39 so that the surface modification time can be freely adjusted A supply valve 38; and a product discharge valve 41 installed between the product discharge port 40 and the product extraction port 42.

  It is preferable for the surface of the liner 34 to have a groove for efficient surface modification of the toner particles. The number of square disks 33 is preferably an even number in consideration of the rotational balance.

  It is preferable that the classification rotor 35 rotates in the same direction as the rotation direction of the dispersion rotor 32 in order to increase the efficiency of classification and the surface modification efficiency of the toner particles.

  The fine powder discharge pipe has a fine powder discharge port 45 for discharging fine powder and ultrafine powder removed by the classification rotor 35 to the outside of the apparatus.

  The surface modifying apparatus has a cylindrical guide ring 36 as a guide means having an axis perpendicular to the top plate 43 in the main body casing 30. The upper end of the guide ring 36 is provided at a predetermined distance from the top plate, and the guide ring is fixed to the main body casing 30 by a support so as to cover at least a part of the classification rotor 36. The lower end of the guide ring 36 is provided at a predetermined distance from the rectangular disk 33 of the dispersion rotor 32.

  In the surface modification apparatus, a space between the classification rotor 35 and the dispersion rotor 32 is guided into a first space 47 outside the guide ring 36 and a second space 48 inside the guide ring 36. Divided by 36. The first space 47 is a space for guiding the finely pulverized product and the surface-modified particles to the classification rotor 35, and the second space guides the finely pulverized product and the surface-modified particles to the dispersion rotor. It is a space for. A gap between the plurality of rectangular disks 33 installed on the dispersion rotor 32 and the liner 34 is a surface modification zone 49, and the classification rotor 35 and a peripheral portion of the classification rotor 35 are classification zones 50. .

  The finely pulverized product introduced into the raw material hopper 380 is supplied into the apparatus from the raw material supply port 39 through the raw material supply port 37 through the raw material supply port 37 via the fixed amount feeder 315. In the surface reforming apparatus, the cold air generated by the cold air generating means 319 is supplied into the main body casing from the cold air inlet 46, and further, the cold water from the cold water generating means 320 is supplied to the cold water jacket 31 to Adjust the temperature to a predetermined temperature. The supplied finely pulverized product swirls in the first space 47 outside the cylindrical guide ring 36 by the swirl flow formed by the suction air volume by the blower 364, the rotation of the dispersion rotor 32 and the rotation of the classification rotor 35. However, the classification process is performed by reaching the classification zone 50 in the vicinity of the classification rotor 35. The direction of the swirl flow formed in the main body casing 30 is the same as the rotation direction of the dispersion rotor 32 and the classification rotor 35.

  Fine powder and super fine powder to be removed by the classifying rotor 35 are sucked from the slit of the classifying rotor 35 by the suction force of the blower 364 and passed through the fine powder discharge port 45 and the cyclone inlet 359 of the fine powder discharge pipe to the cyclone 369 and the bug 362. It is collected. The finely pulverized product from which fine powder and ultrafine powder have been removed reaches the surface modification zone 49 in the vicinity of the dispersion rotor 32 via the second space 48, and the square disk 33 (hammer) provided in the dispersion rotor 32 and the main body. The surface modification treatment of the particles is performed by the liner 34 provided in the casing 30. The particles subjected to the surface modification reach the classification rotor 35 again while turning along the guide ring 36, and fine particles and ultrafine particles are removed from the surface-modified particles by the classification rotor 35 classification. . After performing the treatment for a predetermined time, the discharge valve 41 is opened, and the surface-modified toner particles from which fine powder having a predetermined particle diameter or less and ultrafine powder are removed are taken out from the surface reforming apparatus.

  The toner particles adjusted to a predetermined weight average diameter, adjusted to a predetermined particle size distribution, and further surface-modified to a predetermined circularity are transferred to the external additive adding step by the toner particle transport means 321. .

  The surface reforming apparatus used in the present invention includes a dispersion rotor 32, a finely pulverized product (raw material) input unit 39, a classification rotor 35, and a fine powder discharge unit from the lower side in the vertical direction. Therefore, normally, the drive portion (motor or the like) of the classification rotor 35 is provided further above the classification rotor 35, and the drive portion of the dispersion rotor 32 is provided further below the dispersion rotor 32. The surface reforming apparatus used in the present invention is a finely pulverized product (raw material) classified into a classification rotor, such as a TSP classifier (manufactured by Hosokawa Micron Corporation) having only a classification rotor 35 described in JP-A-2001-259451. It is difficult to supply from the vertically upward direction of 35.

  In the present invention, it is preferable that the tip peripheral speed of the classification rotor 35 having the largest diameter is 30 to 120 m / sec. The tip circumferential speed of the classification rotor is more preferably 50 to 115 m / sec, and further preferably 70 to 110 m / sec. If it is slower than 30 m / sec, the classification yield tends to decrease, and the amount of ultrafine powder tends to increase in the toner particles. If it is faster than 120 m / sec, the problem of increased vibration of the device is likely to occur.

  Furthermore, it is preferable that the tip peripheral speed of the portion with the largest diameter of the dispersion rotor 32 is 20 to 150 m / sec. The tip peripheral speed of the dispersion rotor 32 is more preferably 40 to 140 m / sec, and further preferably 50 to 130 m / sec. When it is slower than 20 m / sec, it is difficult to obtain surface-modified particles having sufficient circularity, which is not preferable. When the speed is higher than 150 m / sec, particles are likely to be fixed inside the apparatus due to the temperature rise inside the apparatus, and the classification yield of the toner particles is likely to be lowered. By setting the tip peripheral speeds of the classification rotor 35 and the dispersion rotor 32 in the above range, the classification yield of the toner particles can be improved and the surface modification of the particles can be performed efficiently.

  Next, the shape of the toner that can be used in the present invention will be described in detail.

  As the shape of the toner that can be used in the present invention, the average circularity measured by FPIA2100 (manufactured by Sysmex Corporation) is preferably 0.920 to 0.970.

  The average circularity of the toner is measured using a flow type particle image measuring device “FPIA-2100 type” (manufactured by Sysmex Corporation), and is calculated using the following equation.

  Here, the “particle projected area” is the area of the binarized toner particle image, and the “peripheral length of the particle projected image” is the length of the contour line obtained by connecting the edge points of the toner particle image. Define. The measurement uses the perimeter of the particle image when image processing is performed at an image processing resolution of 512 × 512 (pixels of 0.3 μm × 0.3 μm).

  In the present invention, the circularity is an index indicating the degree of unevenness of the toner particles, and is 1.000 when the toner particles are completely spherical. The more complicated the surface shape, the smaller the circularity.

  The average circularity C, which means the average value of the circularity frequency distribution, is calculated from the following equation, where ci is the circularity (center value) at the dividing point i of the particle size distribution and m is the number of measured particles.

  In addition, “FPIA-2100”, which is a measuring apparatus used in the present invention, calculates the circularity of each particle, and then calculates the average circularity. 1.0 is divided into classes equally divided every 0.01, and the average circularity is calculated using the center value of the division points and the number of measured particles.

  As a specific measuring method, 10 ml of ion-exchanged water from which impure solids have been removed in advance is prepared in a container, and a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersant therein, followed by further measurement. Add 0.02 g of sample and disperse uniformly. As a means for dispersion, an ultrasonic disperser “Tetora 150 type” (manufactured by Nikka Ki Bios Co., Ltd.) is used, and dispersion treatment is performed for 2 minutes to obtain a dispersion for measurement. In that case, it cools suitably so that the temperature of this dispersion may not be 40 degreeC or more. In order to suppress variation in circularity, the installation environment of the apparatus is controlled at 23 ° C. ± 0.5 ° C. so that the temperature inside the flow type particle image analyzer FPIA-2100 is 26 to 27 ° C. Preferably, autofocus is performed using 2 μm latex particles every 2 hours.

  To measure the circularity of the toner particles, the flow type particle image measuring device is used, and the concentration of the dispersion is readjusted so that the toner particle concentration at the time of measurement is 3000 to 10,000 particles / μl. Measure more than one. After the measurement, using this data, data having an equivalent circle diameter of less than 2 μm is cut to determine the average circularity of the toner particles.

  Furthermore, “FPIA-2100”, which is a measuring apparatus used in the present invention, has a thinner sheath flow (7 μm) than “FPIA-1000” that has been used to calculate the shape of the toner. (To 4 μm) and the processing particle image magnification, and the processing resolution of the captured image is improved (256 × 256 → 512 × 512), so that the accuracy of toner shape measurement is improved, thereby making sure the fine particles are more reliable. A device that has achieved supplementation. Therefore, when it is necessary to measure the shape more accurately as in the present invention, the FPIA 2100 that can obtain information on the shape more accurately is more useful.

  When the average circularity is less than 0.920, the transferability of the toner is deteriorated, and the transfer residual toner may be excessively accumulated on the charging member to cause a charging failure. In addition, since the ratio of the inorganic fine particles having an abrasive action to the concave and convex portions on the surface of the toner increases, the effect of removing the charged product cannot be sufficiently obtained.

  When the average circularity is larger than 0.970, the toner fluidity is likely to occur because the fluidity as the toner is too good. In addition, when the above-described manufacturing method is used, the toner wettability, which will be described later, tends to deteriorate due to thermal factors for the toner in the manufacturing process. It is not preferable in terms.

  Therefore, the shape of the toner is preferably within the above range, but in the present invention, this range can be achieved by adjusting the pulverization condition and surface treatment modification condition of the toner.

  Next, the wettability of the toner that can be used in the present invention to a 45% aqueous methanol solution will be described in detail.

  As the wettability of the toner that can be used in the present invention, it is preferable that the transmittance is 10 to 80% in the measurement of UV transmittance in a 45% by volume aqueous solution of methanol. By being in this range, toner fusion and filming on the surface of the photoreceptor can be prevented.

The toner wettability is measured as follows. First, an aqueous solution having a volume mixing ratio of methanol: water of 45:55 is prepared. 10 ml of this aqueous solution is placed in a 30 ml sample bottle (Nippon Denka Glass: SV-30), and 20 mg of toner is impregnated on the liquid surface to cover the bottle. Thereafter, the mixture is shaken for 10 seconds at 2.5 S ⁻¹ with a Yayoi type shaker (model: YS-LD). At this time, the angle of shaking is such that the shaking column moves 15 degrees forward and 20 degrees backward, assuming that the vertical (vertical) of the shaker is 0 degree. The sample bottle is fixed to a fixing holder (with the sample bottle lid fixed on the extension at the center of the column) attached to the tip of the column. After removing the sample bottle, the dispersion after 30 seconds is used as a dispersion for measurement.

The dispersion is put into a 1 cm square quartz cell, and the transmittance (%) at a wavelength of 600 nm of the dispersion after 10 minutes is measured using a spectrophotometer MPS2000 (manufactured by Shimadzu Corporation).
Transmittance (%) = I / I ₀ × 100 (I: incident light beam, I ₀ : transmitted light beam)

  When the transmittance is less than 10%, the toner fluidity is likely to be generated because the fluidity as the toner is too good. In addition, if the toner fluidity is too good, the inorganic fine particles having a polishing effect may be detached from the toner surface, and the desired polishing effect may not be obtained.

  When the transmittance is higher than 80%, the fluidity as a toner is deteriorated, and thus contamination of other members may be deteriorated. Further, since the fluidity as a toner is deteriorated, the polishing effect of the inorganic fine particles having a polishing action cannot be obtained so much, and the toner fusion and filming to the surface of the photoreceptor are promoted, and the inorganic fine particles The polishing effect may be offset.

  Next, the magnetic carrier that can be used in the present invention will be described in detail.

  The magnetic carrier that can be used in the present invention is preferably a magnetic carrier in which a coating layer is formed on the surface of a known ferrite particle or magnetic fine particle-dispersed resin core, particularly preferably a coating layer on the surface of the magnetic fine particle-dispersed resin core. Is a magnetic carrier.

The magnetic carrier that can be used in the present invention preferably has a true density of 2.5 to 5.0 g / cm ^{3, and} if the true density of the magnetic carrier is within this range, scattering of the developer is suppressed and It is preferable because toner spent is suppressed, and it is particularly preferable that the magnetic carrier is a magnetic carrier in which a coating layer is formed on the surface of the magnetic fine particle dispersed resin core because the true density can be easily controlled within this range.

In the magnetic carrier that can be used in the present invention, the magnetic fine particles used in the magnetic fine particle dispersed resin core are preferably magnetite fine particles, and are nonmagnetic inorganic compounds for adjusting the true density and magnetic properties of the magnetic carrier. It is preferable to use certain hematite (α-Fe ₂ O ₃ ) fine particles in combination.

  As the binder resin constituting the magnetic fine particle dispersed resin core particles that can be used in the present invention, a thermosetting resin is preferable.

  Thermosetting resins include phenolic resins, epoxy resins, polyamide resins, melamine resins, urea resins, unsaturated polyester resins, alkyd resins, xylene resins, acetoguanamine resins, furan resins, silicone resins, polyimide resins, urethane resins. Is mentioned. These resins may be used alone or in combination of two or more, but preferably contain at least a phenol resin.

  The ratio of the binder resin and the magnetic fine particles constituting the core particles in the present invention is preferably binder resin: magnetic fine particles = 1: 99 to 1:50 on a mass basis.

  In the present invention, the carrier coating material preferably contains at least a binder resin and fine particles.

  As the binder resin for forming the coating material used for the magnetic carrier that can be used in the present invention, any known resin can be used. Preferably, polyvinyl fluoride, polyvinylidene fluoride, polytrifluoroethylene, Perfluoropolymers such as polyfluorochloroethylene, polytetrafluoroethylene, polyperfluoropropylene, copolymers of vinylidene fluoride and acrylic monomers, copolymers of vinylidene fluoride and trifluorochloroethylene, tetrafluoro Examples thereof include a copolymer of ethylene and hexafluoropropylene, a copolymer of vinyl fluoride and vinylidene fluoride, and a copolymer of vinylidene fluoride and tetrafluoroethylene.

  The above-mentioned resins can be used alone or in combination. In addition, a curing agent or the like can be mixed with a thermoplastic resin and cured for use.

  When a thermoplastic resin is used as the binder resin for forming the coating material, this thermoplastic resin has a weight average molecular weight of 10,000 in a gel permeation chromatograph (GPC) which is a soluble component of tetrahydrofuran (THF). It is preferable that it is thru | or 300,000 at the point which improves the intensity | strength of a coating material and the peeling resistance of a coating material and a core surface.

  The binder resin forming the coating material preferably has a main peak in the region of molecular weight 2,000 to 100,000 in the GPC chromatogram of the THF soluble component, and further has a molecular weight of 2,000 to 100,000. It is preferable to have a subpeak or shoulder in the region of 000. Most preferably, the resin forming the coating material has a main peak in the molecular weight range of 20,000 to 100,000 in the GPC chromatogram of the THF soluble component, and a molecular weight range of 2,000 to 19,000. It is preferable to have sub-peaks or shoulders. By satisfying the above molecular weight distribution, development durability capable of developing a large number of sheets even with a small particle size toner, charging stability to the toner, and prevention of adhesion of external additives to the carrier particle surface are further improved. improves.

  In the present invention, a silicone resin can also be used as the coating material resin from the viewpoint of adhesion to the core and prevention of spent. The silicone resin can be used alone, but is preferably used in combination with a coupling agent in order to increase the strength of the coating layer and control the charge to a preferable level. Furthermore, the coupling agent described above is preferably used as a so-called primer agent in which a part of the coupling agent is treated on the surface of the carrier core before coating the resin, and the subsequent coating layer is accompanied by a covalent bond. , It can be formed in a more adhesive state.

  Aminosilane is preferably used as the coupling agent. As a result, an amino group having positive chargeability can be introduced on the surface of the carrier, and negative charge characteristics can be imparted to the toner satisfactorily. Furthermore, in the case of a magnetic substance-dispersed resin carrier, the presence of an amino group activates both the lipophilic treatment agent that is preferably treated with the metal compound and the silicone resin. By further enhancing the properties and at the same time promoting the curing of the resin, a stronger coating layer can be formed.

  During the coating treatment of the coating layer, it is preferable to coat in a reduced pressure state at a temperature of 30 to 80 ° C.

The reason is not clear, but is expected to be described below.
(I) A moderate reaction proceeds at the coating stage, and the coating material is uniformly and smoothly coated on the surface of the carrier core.
(Ii) In the baking step, low temperature treatment at at least 160 ° C. is possible, and excessive crosslinking of the resin can be prevented, and the durability of the coating layer can be enhanced.

  The coating amount of the resin core forming the coating material is preferably 0.3 to 4.0 parts by mass with respect to 100 parts by mass of the core. The amount is preferably 0.4 to 3.5 parts by mass, and more preferably 0.5 to 3.2 parts by mass.

  The coating resin preferably contains fine particles in order to make the shape of the carrier surface more uniform and / or sharpen the charge distribution of the toner.

  As the fine particles, both organic and inorganic fine particles can be used. However, it is necessary to maintain the shape of the particles when the carrier is coated, and preferably, crosslinked resin particles or inorganic fine particles are preferably used. Can do. Specifically, a crosslinked polymethyl methacrylate resin, a crosslinked polystyrene resin, a melamine resin, a phenol resin, a nylon resin, and inorganic fine particles can be used alone or in combination from silica, titanium oxide, alumina, and the like. Among these, a crosslinked polymethyl methacrylate resin, a crosslinked polystyrene resin, and a melamine resin are preferable from the viewpoint of charge stability.

  These fine particles are preferably used in an amount of 1 to 40 parts by mass with respect to 100 parts by mass of the coating resin. By using it in the above range, charging stability and toner separation can be improved, and image defects can be prevented. When the amount is less than 1 part by mass, the effect of addition of fine particles cannot be obtained, and when the amount exceeds 40 parts by mass, the coating layer lacks during durability, resulting in poor durability.

  The particle diameter of the fine particles preferably has a peak value of 0.08 to 0.50 μm on the basis of the number in order to improve the toner separation. When the thickness is less than 0.08 μm, it is difficult to disperse the fine particles in the coating material. When the thickness exceeds 0.50 μm, the coating layer lacks during durability, resulting in poor durability.

  The coating resin may contain conductive fine particles so as not to reduce the specific resistance of the carrier excessively and to remove residual charges on the surface of the carrier.

The conductive particles preferably have a specific resistance of 1 × 10 ⁸ Ω · cm or less, and more preferably have a specific resistance of 1 × 10 ⁶ Ω · cm or less. Specifically, particles containing at least one kind of particles selected from carbon black, magnetite, graphite, titanium oxide, alumina, zinc oxide, and tin oxide are preferable. In particular, as a conductive particle, carbon black is preferably used without being able to remove residual charges on the carrier surface with a small addition amount, and having a small particle size and not inhibiting irregularities caused by fine particles on the carrier surface. be able to. The particle size of the carbon black has a peak value of 10 nm to 60 nm (more preferably 15 to 50 nm) on the basis of the number, so that residual charges on the carrier surface can be removed well and desorption from the carrier can be prevented well. This is preferable.

  The DBP oil absorption amount of carbon black is preferably 20 to 500 ml, more preferably 25 to 300 ml, and particularly preferably 30 to 200 ml for 100 g of carbon black.

  When the DBP oil absorption is in the above range, the residual charge on the carrier surface is efficiently removed, which is preferable for controlling the charging of the carrier. When the amount is less than 20 ml / 100 g, the structure of carbon black is short, so that efficient charge removal is not performed and the effect of addition is hardly exhibited.

  These conductive fine particles are preferably used in an amount of 1 to 15 parts by mass with respect to 100 parts by mass of the coating resin in order to reduce the specific resistance of the carrier and to remove residual charges on the carrier surface. When the amount is less than 1 part by mass, the effect of removing the residual charge on the carrier surface is hardly exhibited. When the amount exceeds 15 parts by mass, the dispersion in the coating material becomes unstable, and an excessive charge removing effect is obtained. Therefore, the charge imparting ability of the carrier itself may be reduced.

  The magnetic carrier that can be used in the present invention preferably has a number-based average particle size of 10 to 80 μm. Particles having an average particle size of less than 10 μm are likely to adhere to the carrier, and particles having an average particle size of more than 80 μm may not be able to be imparted with good charge due to a small specific surface area relative to the toner. In particular, in order to improve image quality and prevent carrier adhesion, the thickness is 15 to 60 μm, preferably 20 to 45 μm.

  The average particle diameter of the magnetic carrier is extracted as 300 or more carrier particles having a particle diameter of 0.1 μm or more randomly with a scanning electron microscope (100 to 5000 times), and measured as a carrier particle diameter with a horizontal ferret diameter using a digitizer. The number average particle diameter of the carrier is calculated.

The magnetic carrier that can be used in the present invention has a magnetization strength (σ1000) of 15 to 75 Am ² / kg (emu / g) measured under a magnetic field of 1000 × (10 ³ / 4π) · A / m (1000 oersted). The residual magnetization (σr) is preferably 7.5 Am ² / kg or less. When the strength of magnetization (σ1000) exceeds 70 Am ² / kg, the stress on the toner in the developer magnetic brush increases, the toner deteriorates, and the spent on the carrier is likely to occur. . Further, when the magnetization intensity (σ1000) is less than 15 Am ² / kg, the magnetic binding force to the sleeve is lost, and the carrier adheres and adheres to the surface of the photoconductor to cause a defect in the image. Further, when the remanent magnetization (σr) exceeds 7.5 Am ² / kg, poor fluidity may occur due to magnetic aggregation.

  As a method for producing a magnetic fine particle-dispersed resin core, there is a method in which a binder resin monomer and magnetic fine particles are mixed and the monomer is polymerized to obtain magnetic fine particle-dispersed core particles. At this time, as monomers used for polymerization, vinyl monomers, bisphenols and epichlorohydrin for forming epoxy resins; phenols and aldehydes for forming phenol resins; urea and aldehydes for forming urea resins Melamine and aldehydes are used. For example, as a method of producing magnetic fine particle dispersed core particles using a curable phenolic resin, magnetic fine particles are placed in an aqueous medium, and phenols and aldehydes are polymerized in the presence of a basic catalyst in the aqueous medium. There is a method of obtaining fine particle dispersed core particles.

  Other methods for producing magnetic fine particle-dispersed resin core particles include thoroughly mixing a vinyl-based or non-vinyl-based thermoplastic resin, magnetic material, and other additives with a mixer before heating rolls, kneaders, and extruders. There is a method of obtaining magnetic fine particle-dispersed core particles by melting and kneading using a kneader such as the above, cooling the mixture, and then pulverizing and classifying. At this time, it is preferable that the obtained magnetic fine particle-dispersed core particles are spheroidized thermally or mechanically and used as the magnetic fine particle-dispersed core particles for the resin carrier. As the binder resin, a thermosetting resin such as a phenol resin, a melamine resin, or an epoxy resin is preferable in terms of excellent durability, impact resistance, and heat resistance. The binder resin is more preferably a phenol resin in order to more suitably express the characteristics of the present invention.

  As phenols for producing a phenol resin, in addition to phenol itself, alkylphenols such as m-cresol, p-tert-butylphenol, o-propylphenol, resorcinol, bisphenol A and a part of benzene nucleus or alkyl group or Examples thereof include compounds having a phenolic hydroxyl group such as halogenated phenols, all of which are substituted with chlorine atoms or bromine atoms. Of these, phenol (hydroxybenzene) is more preferable.

  Examples of aldehydes include formaldehyde and furfural in the form of either formalin or paraaldehyde. Of these, formaldehyde is particularly preferable.

  The molar ratio of aldehydes to phenols is preferably 1 to 4, particularly preferably 1.2 to 3. When the molar ratio of aldehydes to phenols is less than 1, particles are difficult to generate, and even if they are generated, the resin does not easily cure, so the strength of the generated particles tends to be weak. On the other hand, when the molar ratio of aldehydes to phenols is larger than 4, unreacted aldehydes remaining in the aqueous medium after the reaction tend to increase.

  Examples of the basic catalyst used in the condensation polymerization of phenols and aldehydes include those used in the production of ordinary resol type resins. Examples of such a basic catalyst include aqueous ammonia, hexamethylenetetramine and alkylamines such as dimethylamine, diethyltriamine, and polyethyleneimine. The molar ratio of these basic catalysts to phenols is preferably 0.02 to 0.3.

  Hereinafter, methods for analyzing and measuring other physical properties related to the present invention will be described.

<Molecular weight distribution of binder resin, toner, and coating resin by GPC measurement>
The molecular weight of the chromatogram by gel permeation chromatography (GPC) is measured under the following conditions. For the measurement, HLC-8120GPC (manufactured by Tosoh Corporation) was used.
The column was stabilized in a heat chamber at 40 ° C., and tetrahydrofuran (THF) as a solvent was passed through the column at this temperature at a flow rate of 1 ml / min, and the sample concentration was adjusted to 0.05 to 0.6% by mass. About 50 to 200 μl of THF sample solution is injected and measured. In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the number of counts (retention time). Examples of standard polystyrene samples for preparing a calibration curve include those manufactured by Tosoh Corporation or Pressure Chemical Co. The molecular weights manufactured are 6 × 10 ² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 10 ⁴ , 5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9 × 10 ⁵ , 8 ^{.6 × 10 5, 2 × 10} 6, used as a 4.48 × 10 ^6, it is appropriate to use at least about 10 standard polystyrene samples. An RI (refractive index) detector is used as the detector.

As a column, in order to accurately measure a molecular weight region of 10 ^{3 to} 2 × 10 ⁶ , it is preferable to combine a plurality of commercially available polystyrene gel columns. For example, shodex GPC KF-801, 802, 803 manufactured by Showa Denko KK , 804, 805, 806, and 807, and combinations of μ-styragel 500, 10 ³ , 10 ⁴ , and 10 ⁵ manufactured by Waters.

<Measurement of maximum endothermic peak in DSC of toner and wax>
The maximum endothermic peak of the toner and the wax can be measured according to ASTM D3418-82 using a differential thermal analyzer (DSC measuring device) and DSC2920 (TA Instruments Japan).

Temperature curve: Temperature increase I (30 ° C. to 200 ° C., temperature increase rate 10 ° C./min)
Temperature drop I (200 ° C-30 ° C, temperature drop rate 10 ° C / min)
Temperature increase II (30 ° C. to 200 ° C., temperature increase rate 10 ° C./min)

  As a measuring method, 5 to 20 mg, preferably 10 mg of a measurement sample is accurately weighed. This is put into an aluminum pan, and an empty aluminum pan is used as a reference, and measurement is performed at a temperature rise rate of 10 ° C./min and normal temperature and humidity in a measurement temperature range of 30 to 200 ° C. The maximum endothermic peak of the toner is determined in the process of temperature increase II, the one having the highest height from the baseline in the region above the endothermic peak of the resin Tg, or the endothermic peak of the resin Tg overlaps with another endothermic peak. If this is difficult, the maximum endothermic peak of the toner of the present invention is defined as the highest peak from the maximum peak of the overlapping peaks.

<Measurement of toner particle size distribution>
As a measuring device, Coulter Counter TA-II or Coulter Multisizer II (manufactured by Coulter Inc.) is used. As the electrolytic solution, an about 1% NaCl aqueous solution is used. As the electrolytic solution, an electrolytic solution prepared using primary sodium chloride or, for example, ISOTON (registered trademark) -II (manufactured by Coulter Scientific Japan) can be used.

  As a measurement method, 0.1 to 5 ml of a surfactant (preferably alkylbenzenesulfone hydrochloride) is added as a dispersant to 100 to 150 ml of the electrolytic aqueous solution, and 2 to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample is suspended is dispersed for about 1 to 3 minutes with an ultrasonic disperser, and the volume and number of the sample are measured for each channel by the measuring device using a 100 μm aperture as the aperture. The volume distribution and the number distribution are calculated. From these obtained distributions, the weight average particle diameter of the sample is determined. As channels, 2.00 to 2.52 μm; 2.52 to 3.17 μm; 3.17 to 4.00 μm; 4.00 to 5.04 μm; 5.04 to 6.35 μm; 6.35 to 8. 00 μm; 8.00 to 10.08 μm; 10.08 to 12.70 μm; 12.70 to 16.00 μm; 16.00 to 20.20 μm; 20.20 to 25.40 μm; 25.40 to 32.00 μm; 13 channels of 32-40.30 μm are used.

<Analysis of composition of resin for carrier coating>
About 50 mg of a sample is put in a φ5 mm sample tube, and as a solvent, CDCl ₃ is added and dissolved to obtain a measurement sample. The measurement conditions are shown below.
Measuring apparatus: FT NMR apparatus JNM-EX400 (manufactured by JEOL Ltd.)
Measurement frequency: 400 MHz
Pulse condition: 6.9 μs
Data points: 32768
Frequency range: 10500Hz
Integration count: 16 times Measurement temperature: 25 ° C

  Further, the carrier coating resin may be separated from the carrier particles as necessary. As a method for separating the coating material from the carrier particles, a solvent soluble in the coating material (for example, acetone, toluene, etc.) is used, ultrasonic separation is performed with an ultrasonic disperser, and then the core particles are separated using a magnet. I do. Thereafter, using a centrifugal separator, the fine particles added to the coating material are separated, and the supernatant liquid (resin solution component) is separated and evaporated to dryness to obtain a resin component for carrier coating.

<Measurement of resistivity of magnetic carrier>
The specific resistance value of the magnetic carrier is measured using the measuring apparatus shown in FIG. If necessary, the sample is prepared by separating the toner and the magnetic carrier.

The specific resistance is measured by filling the cell E with sample particles, placing the lower electrode 11 and the upper electrode 12 in contact with the filled sample particles, applying a voltage between these electrodes, and the current flowing at that time. A method for obtaining the specific resistance by measuring is used. The specific resistance measurement conditions in the present invention are as follows: the contact area S between the filled sample particles and the electrode is about 2.4 cm ² , the sample thickness d is about 0.2 cm, and the load of the upper electrode is 240 g. The voltage is applied in the order of application conditions I, II, and III, and the current at the applied voltage in application condition III is measured. Thereafter, the thickness d of the sample was accurately measured, the specific resistance (Ω · cm) at each electric field strength (V / cm) was obtained by calculation, and the specific resistance at the electric field strength of 3000 V / cm was taken as the specific resistance of the sample. .
Application condition I: (0V → 1000V: Increase in steps of 200V every 30 seconds)
II: (Hold for 30 seconds at 1000V)
III: (1000V → 0V: Decrease in steps of 200V every 30 seconds)
Sample resistivity (Ω · cm) = (applied voltage (V) / measured current (A)) × S (cm ² ) / d (cm)
Electric field strength (V / cm) = applied voltage (V) / d (cm)

<Measurement of particle size of fine particles in carrier coating resin>
The particle size of the fine particles is 500 or more random particles having a particle size of 5 nm or more by scanning electron microscope (50,000 times) obtained by dissolving a coating material from a carrier in a solvent such as toluene. Extract and measure the major and minor axes with a digitizer. The average is the particle size, with the mode diameter that becomes the peak of the particle size distribution of 500 or more particles (from the column histogram separated every 10 nm). The average particle size is calculated.

<Measurement of particle size of carbon black in carrier coating resin>
The particle size of the carbon black was determined by randomly scanning 500 particles having a particle size of 5 nm or more with a scanning electron microscope (50,000 times) by dissolving a coating material from a carrier in a solvent such as toluene. Extract the above, measure the major and minor axes with a digitizer, and use the average value as the particle size, and the mode diameter that becomes the peak of the particle size distribution of 500 or more particles (from the histogram of the column separated every 10 nm) To calculate the average particle size.

<Measurement of DBP oil absorption of carbon black in resin for carrier coating>
The DBP oil absorption of carbon black is calculated from the DBP oil absorption (dibutyl phthalate oil absorption) according to JIS-K 6221-1982 6.1.2 A method (mechanical kneading method).

<Measurement of magnetization of magnetic carrier>
The strength of magnetization of the magnetic carrier is determined from the magnetic properties of the magnetic carrier and the true specific gravity of the magnetic carrier. The magnetic characteristics of the magnetic carrier can be measured by using an oscillating magnetic field type magnetic characteristic automatic recording apparatus BHV-30 manufactured by Riken Denshi Co., Ltd. As a measuring method, a cylindrical plastic container is filled with a magnetic carrier so as to be sufficiently dense, while an external magnetic field of 79.6 kA / m (1 kilo-Oersted) is formed, and in this state, the magnetic material filled in the container is filled. Measure the magnetization moment of the carrier. Further, the actual mass of the magnetic carrier filled in the container is measured to determine the magnetization strength (Am ² / kg) of the magnetic carrier.

<Measurement of true density of magnetic carrier>
The true density of the magnetic carrier particles can be measured by, for example, a dry automatic densimeter 1330 (manufactured by Shimadzu Corporation). The apparent density of the carrier particles can be measured according to JIS Z2504.

  Hereinafter, the present invention will be described in more detail with reference to specific production examples and examples, but the present invention is not limited thereto. “Part” means “part by mass”.

<Example of photoconductor production>
60 parts of powder composed of barium sulfate particles having a tin oxide coating layer (trade name: Pastoran PC1, manufactured by Mitsui Mining & Smelting Co., Ltd.), titanium oxide (trade name: TITANIX JR, manufactured by Teika Co., Ltd.), 15 parts, Resole type phenolic resin (trade name: Phenolite J-325, manufactured by Dainippon Ink & Chemicals, Inc., solid content 70%) 43 parts, silicone oil (trade name: SH28PA, manufactured by Toray Silicone Co., Ltd.) 0.015 Part, a silicone resin (trade name: Tospearl 120, manufactured by Toshiba Silicone Co., Ltd.) 3.6 parts, and a solution consisting of 50 parts 2-methoxy-1-propanol / 50 parts methanol is dispersed in a ball mill for about 20 hours. A conductive layer coating was prepared. The conductive layer coating material thus prepared was applied on an aluminum cylinder by a dipping method, and was heated and cured at 150 ° C. for 50 minutes to form a conductive layer having a thickness of 16 μm.

  Next, 10 parts of copolymer nylon resin (trade name: Amilan CM8000, manufactured by Toray Industries, Inc.) and 30 parts of methoxymethylated 6 nylon resin (trade name: Toresin EF-30T, manufactured by Teikoku Chemical Co., Ltd.) are methanolized. A solution dissolved in a mixed solution of 400 parts / n-butanol in 200 parts is dip-coated on the conductive layer, heated at 100 ° C. for 20 minutes and dried to form an intermediate layer having a thickness of 0.44 μm. Formed.

  Next, 20 parts of hydroxygallium phthalocyanine having strong peaks at 7.4 ° and 28.2 ° of black angle 2θ ± 0.2 ° of CuKα characteristic X-ray diffraction, polyvinyl butyral (trade name: ESREC BX-1, Sekisui (Chemical) 10 parts and cyclohexanone 600 parts were dispersed in a sand mill apparatus using glass beads having a diameter of 1 mm for 4 hours, and then 700 parts of ethyl acetate was added to prepare a dispersion for charge generation layer. This was applied onto the intermediate layer by a dip coating method, heated at 80 ° C. for 20 minutes and dried to form a charge generation layer having a thickness of 0.2 μm.

  Next, 70 parts of the hole transport compound of the following structural formula (C) and 100 parts of polycarbonate resin (Iupilon Z400: manufactured by Mitsubishi Engineering Plastics Co., Ltd.) are dissolved in a mixed solvent of 600 parts of monochlorobenzene and 200 parts of methylal. Thus, a charge transport layer coating was prepared. The charge transport layer coating material was dip-coated on the charge generation layer, heated at 100 ° C. for 40 minutes, and dried to form a charge transport layer having a thickness of 20 μm.

  Next, 450 parts of the hole transporting compound of the above structural formula (c) and 50 parts of polytetrafluoroethylene particles (manufactured by Daikin Industries: Lubron L2) were mixed with 600 parts of n-propyl alcohol, followed by dispersion treatment to protect it. A layer coating was prepared. This protective layer coating was applied on the charge transport layer and then dried at 50 ° C. for 10 minutes in the air.

After that, electron beam irradiation was performed for 3 seconds while rotating the aluminum cylinder under the conditions of an acceleration voltage of 110 kV and a dose of 1.5 Mrad in nitrogen. Subsequently, the temperature was increased from 25 ° C. to 120 ° C. over about 100 seconds in the nitrogen and cured. Reaction was performed. The oxygen concentration during electron beam irradiation and heat curing reaction was 10 ppm. Thereafter, in the air, a post-heat treatment was performed at 100 ° C. for 30 minutes to form a protective layer having a thickness of 5 μm to obtain an electrophotographic photosensitive member. The obtained electrophotographic photosensitive member had a universal hardness value HU of 210 N / mm ² and an elastic deformation rate We of 54%.

<Production Example 1 of Perovskite Crystalline Inorganic Fine Particle>
The hydrous titanium oxide slurry obtained by hydrolyzing the aqueous titanyl sulfate solution was washed with an alkaline aqueous solution. Next, hydrochloric acid was added to the hydrous titanium oxide slurry to adjust the pH to 0.7 to obtain a titania sol dispersion. NaOH was added to the titania sol dispersion to adjust the pH of the dispersion to 5.0, and washing was repeated until the electrical conductivity of the supernatant reached 70 μS / cm.

0.98-fold molar amount of Sr (OH) ₂ .8H ₂ O was added to the hydrous titanium oxide, and the mixture was placed in a SUS reaction vessel and purged with nitrogen gas. Further, distilled water was added so as to be 0.5 mol / liter in terms of SrTiO ₃ . The slurry was heated to 80 ° C. at a rate of 7 ° C./hour in a nitrogen atmosphere, and reacted for 6 hours after reaching 80 ° C. After the reaction, the reaction solution was cooled to room temperature, and the supernatant was removed. Then, the washing was repeated with pure water, and then filtered with Nutsche. The obtained cake was dried to obtain strontium titanate fine particles not passing through the sintering step. The strontium titanate fine particles were designated as inorganic fine particles A-1. Table 1 shows the physical properties of the inorganic fine particles A-1.

<Production Example 2 of Perovskite Crystalline Inorganic Fine Powder>
The hydrous titanium oxide slurry obtained by hydrolyzing the aqueous titanyl sulfate solution was washed with an alkaline aqueous solution. Next, hydrochloric acid was added to the hydrous titanium oxide slurry to adjust the pH to 0.8 to obtain a titania sol dispersion. NaOH was added to the titania sol dispersion to adjust the pH of the dispersion to 5.0, and washing was repeated until the electrical conductivity of the supernatant reached 70 μS / cm.

A 0.95-fold molar amount of Sr (OH) ₂ .8H ₂ O was added to the hydrous titanium oxide, and the mixture was placed in a SUS reaction vessel and purged with nitrogen gas. Further, distilled water was added so as to be 0.7 mol / liter in terms of SrTiO ₃ . The slurry was heated to 65 ° C. at 8 ° C./hour in a nitrogen atmosphere, and reacted for 5 hours after reaching 65 ° C. After the reaction, the reaction solution was cooled to room temperature, and the supernatant was removed. Then, the washing was repeated with pure water, and then filtered with Nutsche. The obtained cake was dried to obtain strontium titanate fine particles not passing through the sintering step. The strontium titanate fine particles were designated as inorganic fine particles A-2. Table 1 shows the physical properties of the inorganic fine particles A-2.

<Production Example 3 of Perovskite Crystalline Inorganic Fine Powder>
The hydrous titanium oxide obtained by hydrolysis by adding ammonia water to the aqueous titanium tetrachloride solution was washed with pure water, and 0.3% sulfuric acid was added to the hydrous titanium oxide slurry as SO _{3 with} respect to the hydrous titanium oxide. Added. Next, hydrochloric acid was added to the hydrous titanium oxide slurry to adjust the pH to 0.6 to obtain a titania sol dispersion. NaOH was added to the titania sol dispersion to adjust the pH of the dispersion to 5.0, and washing was repeated until the electrical conductivity of the supernatant liquid reached 50 μS / cm.

0.97-fold molar amount of Sr (OH) ₂ .8H ₂ O was added to the hydrous titanium oxide, and the mixture was placed in a SUS reaction vessel and purged with nitrogen gas. Furthermore, distilled water was added so as to be 0.6 mol / liter in terms of SrTiO ₃ . The slurry was heated to 60 ° C. at a rate of 10 ° C./hour in a nitrogen atmosphere, and reacted for 7 hours after reaching 60 ° C. After the reaction, the reaction solution was cooled to room temperature, and the supernatant was removed. Then, the washing was repeated with pure water, and then filtered with Nutsche. The obtained cake was dried to obtain strontium titanate fine particles not passing through the sintering step. The strontium titanate fine particles were designated as inorganic fine particles A-3. Table 1 shows the physical properties of the inorganic fine particles A-3.

<Production Example 4 of Perovskite Crystalline Inorganic Fine Powder>
The hydrous titanium oxide slurry obtained by hydrolyzing the aqueous titanyl sulfate solution was washed with an alkaline aqueous solution. Next, hydrochloric acid was added to the hydrous titanium oxide slurry to adjust the pH to 0.65 to obtain a titania sol dispersion. NaOH was added to the titania sol dispersion, the pH of the dispersion was adjusted to 4.5, and washing was repeated until the electrical conductivity of the supernatant reached 70 μS / cm.

0.97-fold molar amount of Sr (OH) ₂ .8H ₂ O was added to the hydrous titanium oxide, and the mixture was placed in a SUS reaction vessel and purged with nitrogen gas. Further, distilled water was added so as to be 0.5 mol / liter in terms of SrTiO ₃ .

  The slurry was heated to 83 ° C. at 6.5 ° C./hour in a nitrogen atmosphere, and reacted for 6 hours after reaching 83 ° C. After the reaction, the mixture was cooled to room temperature, the supernatant was removed, and washing was repeated with pure water.

  Further, in a nitrogen atmosphere, the slurry was placed in an aqueous solution in which 6.5% by mass of sodium stearic acid (18 carbon atoms) was dissolved with respect to the solid content of the slurry. Zinc stearate was deposited on the mold crystal surface.

  The slurry was washed repeatedly with pure water and then filtered with Nutsche, and the resulting cake was dried to obtain strontium titanate fine particles whose surface was treated with zinc stearate. The surface-treated strontium titanate fine particles that have not passed through the sintering step are referred to as inorganic fine particles A-4. Table 1 shows the physical properties of the inorganic fine particles A-4.

<Production Example 5 of Perovskite Crystalline Inorganic Fine Powder>
The hydrous titanium oxide slurry obtained by hydrolyzing the aqueous titanyl sulfate solution was washed with an alkaline aqueous solution. Next, hydrochloric acid was added to the hydrous titanium oxide slurry to adjust the pH to 1.0 to obtain a titania sol dispersion. NaOH was added to the titania sol dispersion, the pH of the dispersion was adjusted to 5.0, and washing was repeated until the electrical conductivity of the supernatant reached 100 μS / cm.

1.02 times the molar amount of Sr (OH) ₂ .8H ₂ O was added to the hydrous titanium oxide, and the mixture was placed in a SUS reaction vessel and purged with nitrogen gas. Further, distilled water was added so as to be 0.3 mol / liter in terms of SrTiO ₃ . The slurry was heated to 90 ° C. at 70 ° C./hour in a nitrogen atmosphere, and reacted for 5 hours after reaching 90 ° C. After the reaction, the reaction solution was cooled to room temperature, and the supernatant was removed. Then, the washing was repeated with pure water, and then filtered with Nutsche. The obtained cake was dried to obtain strontium titanate fine particles having an average primary particle size of 320 nm. The strontium titanate fine particles were designated as inorganic fine particles a-1. Table 1 shows the physical properties of the inorganic fine particles a-1.

<Production Example 6 of Perovskite Crystalline Inorganic Fine Powder>
The hydrous titanium oxide slurry obtained by hydrolyzing the aqueous titanyl sulfate solution was washed with an alkaline aqueous solution. Next, hydrochloric acid was added to the hydrous titanium oxide slurry to adjust the pH to 4.0 to obtain a titania sol dispersion. NaOH was added to the titania sol dispersion, the pH of the dispersion was adjusted to 8.0, and washing was repeated until the electrical conductivity of the supernatant reached 100 μS / cm.

1.02 times the molar amount of Sr (OH) ₂ .8H ₂ O was added to the hydrous titanium oxide, and the mixture was placed in a SUS reaction vessel and purged with nitrogen gas. Further, distilled water was added so as to be 0.3 mol / liter in terms of SrTiO ₃ . The slurry was heated to 90 ° C. at 30 ° C./hour in a nitrogen atmosphere, and reacted for 5 hours after reaching 90 ° C. After the reaction, the reaction solution was cooled to room temperature, and the supernatant was removed. Then, the washing was repeated with pure water, and then filtered with Nutsche. The obtained cake was dried to obtain strontium titanate fine particles having an average primary particle diameter of 20 nm. The strontium titanate fine particles were designated as inorganic fine particles a-2. Table 1 shows the physical properties of the inorganic fine particles a-2.

<Production Example 6 of Perovskite Crystalline Inorganic Fine Powder>
The inorganic fine powder A-2 was sintered at 1000 ° C. and then crushed to obtain strontium titanate fine particles via a sintering process. Strontium titanate fine particles having an average primary particle size of 120 nm and an irregular particle shape were designated as inorganic fine powder a-3. Table 1 shows the physical properties of the inorganic fine powder a-3.

<Production example of hybrid resin for toner>
As a vinyl copolymer material, dicumyl peroxide was placed in a dropping funnel in 10 parts of styrene, 5 parts of 2-ethylhexyl acrylate, 2 parts of fumaric acid, and 5 parts of a dimer of α-methylstyrene. Also, 25 parts of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 15 parts of polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, Put 9 parts of terephthalic acid, 5 parts of trimellitic anhydride, 24 parts of fumaric acid and dibutyltin oxide in a 4-liter 4-neck flask made of glass, and put a thermometer, stirring rod, condenser and nitrogen inlet tube into the 4-neck flask. The four-necked flask was installed in a mantle heater. Next, after the inside of the four-necked flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and while stirring at a temperature of 130 ° C., the monomer of the vinyl copolymer and the cross-linking from the previous dropping funnel The agent and the polymerization initiator were added dropwise over about 4 hours. Next, the temperature was raised to 200 ° C. and reacted for about 4 hours to obtain a hybrid resin.

The molecular weight measurement result of the obtained hybrid resin by GPC was Mw 1.2 × 10 ⁵ and Mn 3.8 × 10 ³ .

<Production example of polyester resin for toner>
30 parts of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 10 parts of polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, terephthalic acid 20 parts, trimellitic anhydride 3 parts, fumaric acid 27 parts and dibutyltin oxide are put into a glass 4-liter four-necked flask, and a thermometer, a stirring rod, a condenser and a nitrogen inlet tube are attached to the four-necked flask. This four-necked flask was placed in a mantle heater. Under a nitrogen atmosphere, reaction was carried out at 210 ° C. for about 5.5 hours to obtain a polyester resin. The molecular weight measurement result of the obtained polyester resin by GPC was Mw of 8.7 × 10 ⁴ and Mn of 3.6 × 10 ³ .

<Toner Production Example 1>
Toner B-1 was prepared using the following materials and manufacturing method.
100 parts of the above hybrid resin C.I. I. Pigment Blue 15: 3 4.5 parts paraffin wax (W-1: maximum endothermic peak 73 ° C.) 5 parts After mixing the above materials with a Henschel mixer (FM-75 type, manufactured by Mitsui Miike Chemical Co., Ltd.), The mixture was melt kneaded with a twin screw extruder set at a temperature of 140 ° C. The obtained kneaded product was cooled and coarsely pulverized to 1 mm or less with a hammer mill to obtain a coarsely pulverized toner. The resulting coarsely pulverized toner was finely pulverized using a mechanical pulverizer as shown in FIG. As pulverization conditions, pulverization processing (processing α) was performed with the rotational speed of the rotor being 100 s ⁻¹ .

Next, the obtained finely pulverized product was removed using a surface modification treatment apparatus as shown in FIG. 5 while removing fine particles at a classification rotor rotation speed of 120 s ⁻¹ , while dispersing rotor rotation speed 100 s ⁻¹ (rotational peripheral speed) Was subjected to a surface treatment (treatment γ) for 45 seconds at 130 m / sec) to obtain a toner classified product.

Then, to 100 parts of the obtained toner classified product, 1.0% by mass of the inorganic fine particles (A-1) shown in Table 1 and 1.0% by mass of hydrophobic silica (S-1) having a BET specific surface area of 130 m ² / g. % Was added and mixed with a Henschel mixer (FM-75 type, manufactured by Mitsui Miike Chemical Co., Ltd.) at a rotation speed of 30 s ⁻¹ for 10 minutes to obtain a toner (B-1). The obtained toner (B-1) had a volume average particle size of 6.1 μm, an average circularity of 0.945, and a UV transmittance of 45% when stirred and mixed in a 45% methanol solution.

<Toner Production Examples 2 to 4>
In Toner Production Example 1 except that inorganic fine particles (A-2) to (A-4) were used in place of the inorganic fine particles (A-1), toner (B-1) to (B-2) was obtained. Table 2 shows the physical properties of the obtained toner.

<Toner Production Example 5>
A toner (B-5) was obtained in the same manner as in Toner Production Example 1 except that the same treatment as in Toner Production Example 1 was performed twice with the crushing treatment α. Table 2 shows the physical properties of the obtained toner.

<Toner Production Example 6>
In Toner Production Example 5, a toner (B-6) was obtained in the same manner as in Toner Production Example 5 except that the surface modification treatment γ was not performed. Table 2 shows the physical properties of the obtained toner.

<Toner Production Example 7>
Toner (B-7) was obtained in the same manner as in Toner Production Example 1, except that ester wax (maximum endothermic peak 66 ° C.) was used instead of paraffin wax (W-1) in Toner Production Example 1. Table 2 shows the physical properties of the obtained toner.

<Toner Production Example 8>
Toner (B-8) was prepared in the same manner as in Toner Production Example 1 except that paraffin wax (W-2: maximum endothermic peak 78 ° C.) was used instead of paraffin wax (W-1) in Toner Production Example 1. Got. Table 2 shows the physical properties of the obtained toner.

<Toner Production Example 9>
Toner (B-9) was obtained in the same manner as in Toner Production Example 1 except that the polyester resin was used in place of the hybrid resin in Toner Production Example 1. Table 2 shows the physical properties of the obtained toner.

<Toner Production Example 10>
-Preparation of resin particle dispersion 1 Styrene 370 g
30g of n-butyl acrylate
Acrylic acid 6g
24g dodecanethiol
Carbon tetrabromide 4g
While mixing and dissolving the above, 6 g of nonionic surfactant and 10 g of anionic surfactant dissolved in 550 g of ion-exchanged water are dispersed in a flask, emulsified, and slowly mixed for 10 minutes. Into this, 50 g of ion-exchanged water in which 4 g of ammonium persulfate was dissolved was added, and after nitrogen substitution, the contents in the flask were heated in an oil bath until the temperature reached 70 ° C. while stirring, and the emulsion polymerization was continued for 5 hours. Continued. Thus, a resin particle dispersion 1 was prepared by dispersing resin particles having an average particle diameter of 150 nm, Tg of 64 ° C., and a weight average molecular weight (Mw) of 12,500.

-Preparation of resin particle dispersion 2 280 g of styrene
120g of n-butyl acrylate
Acrylic acid 8g
While mixing and dissolving the above, 6 g of nonionic surfactant and 12 g of anionic surfactant dissolved in 550 g of ion-exchanged water are dispersed in a flask, emulsified, and slowly mixed for 10 minutes. Into this, 50 g of ion-exchanged water in which 3 g of ammonium persulfate was dissolved was added, and after nitrogen substitution, the contents in the flask were heated in an oil bath until the temperature reached 70 ° C. while stirring, and the emulsion polymerization was continued for 5 hours. The resin particle dispersion 2 was prepared by dispersing resin particles having an average particle size of 110 nm, a glass transition point of 56 ° C., and a weight average molecular weight (Mw) of 560,000.

Preparation of release agent particle dispersion 1 Polypropylene wax (melting point 85 ° C.) 50 g
Anionic surfactant 5g
200g of ion exchange water
The above was heated to 95 ° C. and dispersed using a homogenizer or the like, then dispersed with a pressure discharge type homogenizer, and a release agent particle dispersion 1 in which a release agent having an average particle size of 580 nm was dispersed was obtained. Prepared.

Preparation of Colorant Particle Dispersion 1 C.I. I. Pigment Blue 15: 3 20g
Anionic surfactant 2g
Ion exchange water 78g
The above was mixed and dispersed for 10 minutes at an oscillation frequency of 26 kHz using an ultrasonic cleaner to prepare a colorant particle dispersion (anionic) 1.

・ Preparation of liquid mixture Resin particle dispersion 1 180 g
Resin particle dispersion 2 80g
Colorant dispersion 1 30g
Release agent dispersion 1 50 g
The above was mixed in a round stainless steel flask using a homogenizer or the like and dispersed to prepare a mixed solution.

-Formation of Aggregated Particles 1.5 g of a cationic surfactant as an aggregating agent was added to the above mixed solution, and the mixture was heated to 50 ° C. while stirring the inside of the flask in a heating oil bath. After maintaining at 50 ° C. for 1 hour, it was confirmed by observation with an optical microscope that aggregated particles having a volume average particle diameter of about 6.2 μm were formed.

-Fusion Then, 3 g of an anionic surfactant was added thereto, and then the stainless steel flask was sealed, heated to 105 ° C while continuing to stir using a magnetic seal, and held for 3 hours. Then, after cooling, the reaction product was filtered, thoroughly washed with ion exchange water, and then dried to obtain a toner classified product.

Then, 1.0 part of the inorganic fine particles (A-1) shown in Table 1 and 1.0 part of hydrophobic silica (S-1) having a BET specific surface area of 130 m ² / g were added to 100 parts of the obtained toner classified product. The mixture was added and mixed with a Henschel mixer (FM-75 type, manufactured by Mitsui Miike Chemical Co., Ltd.) for 10 minutes at a rotation speed of 30 s ⁻¹ to obtain a toner (B-10). The toner (B-10) obtained had a volume average particle size of 6.3 μm, an average circularity of 0.960, and a UV transmittance of 10% when stirred and mixed in a 45% methanol solution.

<Toner Production Example 11>
In Toner Production Example 1, C.I. I. Pigment Blue 15: 3 instead of C.I. I. A toner (B-11) was obtained in the same manner as in Toner Production Example 1 except that 7.0 parts of Pigment Red 57: 1 was used. Table 2 shows the physical properties of the obtained toner.

<Toner Production Example 12>
In Toner Production Example 1, C.I. I. Pigment Blue 15: 3 instead of C.I. I. A toner (B-12) was obtained in the same manner as in Toner Production Example 1 except that 7.5 parts of Pigment Yellow 74 was used. Table 2 shows the physical properties of the obtained toner.

<Toner Production Example 13>
In Toner Production Example 1, C.I. I. Except for using 5.5 parts of carbon black instead of CI Pigment Blue 15: 3 and using hydrophobic silica (S-2) having a BET specific surface area of 200 m ² / g instead of hydrophobic silica (S-1), Toner (B-13) was obtained in the same manner as in Toner Production Example 1. Table 2 shows the physical properties of the obtained toner.

<Toner Production Example 14>
In Toner Production Example 1, C.I. I. Toner except that 90 parts of iron oxide particles were used instead of CI Pigment Blue 15: 3 and hydrophobic silica (S-2) having a BET specific surface area of 200 m ² / g was used instead of hydrophobic silica (S-1). In the same manner as in Production Example 1, a toner (B-14) was obtained. Table 2 shows the physical properties of the obtained toner.

<Toner Production Example 15>
A toner (b-1) was produced using the following materials and production method.
100 parts of the above polyester resin C.I. I. Pigment Blue 15: 3 4.5 parts paraffin wax (W-1: maximum endothermic peak 73 ° C.) 5 parts After mixing the above materials with a Henschel mixer (FM-75 type, manufactured by Mitsui Miike Chemical Co., Ltd.), The mixture was melt kneaded with a twin screw extruder set at a temperature of 140 ° C. The obtained kneaded product was cooled and coarsely pulverized to 1 mm or less with a hammer mill to obtain a coarsely pulverized toner. The resulting coarsely pulverized toner was finely pulverized using a mechanical pulverizer as shown in FIG. As pulverization conditions, pulverization processing (processing α) was performed with the rotational speed of the rotor being 100 s ⁻¹ .

  Next, the resulting finely pulverized product was classified by an elbow jet using an inertia classification method to obtain a toner classified product.

Then, to 100 parts of the obtained toner classified product, 1.0% by mass of the inorganic fine particles (a-1) shown in Table 1 and 1.0% by mass of hydrophobic silica (S-1) having a BET specific surface area of 130 mm ² / g. % Was added and mixed with a Henschel mixer (FM-75 type, manufactured by Mitsui Miike Chemical Co., Ltd.) for 10 minutes at a rotation speed of 30 s ⁻¹ to obtain a toner (b-1). The toner (b-1) obtained had a volume average particle size of 6.3 μm, an average circularity of 0.916, and a UV transmittance of 36% when stirred and mixed in a 45% methanol solution.

<Toner Production Example 16>
In the toner production example 15, a toner (b-2) was obtained in the same manner as in the toner production example 15 except that the inorganic fine particles (a-2) were used instead of the inorganic fine particles (a-1). Table 2 shows the physical properties of the obtained toner.

<Toner Production Example 17>
A toner (b-3) was obtained in the same manner as in the toner production example 15 except that the inorganic fine particles (a-3) were used in place of the inorganic fine particles (a-1) in the toner production example 15. Table 2 shows the physical properties of the obtained toner.

<Toner Production Example 18>
In Toner Production Example 15, the pulverization process was performed except that the rotation speed of the rotor was set to 80 s ⁻¹ and the pulverization process (process β) was performed. In the same manner as in Toner Production Example 15, a toner (b-4) was obtained. Table 2 shows the physical properties of the obtained toner.

<Toner Production Example 19>
In Toner Production Example 15, paraffin wax (W-3: maximum endothermic peak 63 ° C.) is used instead of paraffin wax (W-1), and inorganic fine particles (A-1) are used instead of inorganic fine particles (a-1). A toner (b-5) was obtained in the same manner as in Toner Production Example 15 except that it was used. Table 2 shows the physical properties of the obtained toner.

<Production Example 1 of Magnetic Fine Particle Dispersed Resin Core>
A magnetic fine particle-dispersed resin core (R-1) was prepared using the following materials.
・ Phenol 10 parts ・ Formaldehyde solution (37% by weight aqueous solution) 6 parts ・ Magnetite particles 76 parts ・ Hematite particles 8 parts The above materials, 5 parts by weight 28% ammonia water, and 10 parts water were placed in a flask while stirring and mixing. The temperature was raised and maintained at 85 ° C. for 30 minutes, followed by polymerization for 3 hours to cure. Then, after cooling to 30 degreeC and adding water, the supernatant liquid was removed, the precipitate was washed with water, and then air-dried. Subsequently, this was dried under reduced pressure (5 hPa or less) at a temperature of 60 ° C. to obtain a magnetic fine particle dispersed resin core (R-1) in which magnetic fine particles were dispersed.

<Manufacture example 1 of coating material for coating layers>
3 parts of a methyl methacrylate macromer having a weight average molecular weight of 5,000 having an ethylenically unsaturated group at one end, 46 parts of a monomer having the following compound (d) as a unit, 51 parts of methyl methacrylate, a reflux condenser, a thermometer, Add to a four-necked flask equipped with a nitrogen suction tube and a mixing type stirring device, add 100 parts of toluene, 100 parts of methyl ethyl ketone and 2.4 parts of azobisisovaleronitrile, and keep at 80 ° C. for 10 hours under a nitrogen stream. A graft copolymer solution (solid content: 35% by mass) was obtained. The weight average molecular weight according to gel permeation chromatogram (GPC) of the graft copolymer was 20,000.

  With respect to 30 parts of the obtained graft copolymer solution, 0.7 part of melamine resin (number average particle diameter 0.25 μm), 1.2 parts of carbon black (number average particle diameter 35 nm, DBP oil absorption 50 ml / 100 g) Then, 100 parts of toluene was stirred with a homogenizer to obtain a coating material (L-1).

<Manufacture example 2 of coating material for coating layers>
Take 20 parts of toluene, 20 parts of butanol, 10 parts of water, and 40 parts of ice in a four-necked flask, add 40 parts of a mixture of a 3: 2 molar ratio of CH ₃ SiCl ₃ and SiCl ₂ and a catalyst while stirring, and further, After stirring for 30 minutes, a condensation reaction was performed at 60 ° C. for 1 hour. Thereafter, the siloxane was thoroughly washed with water and dissolved in a toluene-methyl ethyl ketone-butanol mixed solvent to prepare a silicone varnish having a solid content of 10%.

  In this silicone varnish, with respect to 100 parts of siloxane solid content, 2.0 parts of ion-exchanged water and 2.0 parts of the following curing agent

と、２．０部の下記アミノシランカップリング剤
（ＣＨ₃）₂Ｎ−Ｃ₃Ｈ₆−Ｓｉ−（ＯＣＨ₃）₃ （へ）
を同時添加し、コート材（Ｌ−２）を得た。

And 2.0 parts of the following aminosilane coupling agent (CH ₃ ) ₂ N—C ₃ H ₆ —Si— (OCH ₃ ) ₃ (to)
Were simultaneously added to obtain a coating material (L-2).

<Magnetic carrier production example 1>
While stirring 100 parts of the magnetic fine particle dispersed resin core (R-1) while continuously applying shear stress, the coating material (L-1) is gradually added, and the solvent is volatilized at 70 ° C. to the core surface. The resin coating was performed. The resin-coated magnetic carrier particles were heat-treated with stirring at 100 ° C. for 2 hours, pulverized, and then classified with a sieve having an aperture of 76 μm. The average particle size was 35 μm, the specific resistance was 5.9 × 10 ⁹ Ω · A magnetic carrier (C-1) having cm, true specific gravity of 3.6 g / cm ³ , magnetization strength (σ1000) of 51.2 Am ² / kg, and residual magnetization of 4.9 Am ² / kg was obtained. Table 3 shows the physical properties of the obtained magnetic carrier.

<Magnetic carrier production example 2>
In Magnetic Carrier Production Example 1, a magnetic carrier (C-2) was obtained in the same manner as Magnetic Carrier Production Example 1 except that Mn—Mg ferrite was used instead of the magnetic fine particle dispersed resin core (R-1). . Table 3 shows the physical properties of the obtained magnetic carrier.

<Magnetic carrier production example 3>
In Magnetic Carrier Production Example 1, a magnetic carrier (C-3) was obtained in the same manner as Magnetic Carrier Production Example 1 except that the coating material (L-2) was used instead of the coating material (L-1). Table 3 shows the physical properties of the obtained magnetic carrier.

<Magnetic carrier production example 4>
In Magnetic Carrier Production Example 1, a magnetic carrier (C-4) was obtained in the same manner as Magnetic Carrier Production Example 1 except that Cu—Zn ferrite was used instead of the magnetic fine particle dispersed resin core (R-1). . Table 3 shows the physical properties of the obtained magnetic carrier.

<Example 1>
First, a developer was prepared. To 92 parts of the magnetic carrier (C-1), 8 parts of toner (B-1) was added and mixed with a tumbler mixer to obtain a developer.

Next, using a Canon full color copier IRC3220N remodeling machine (in which the photoconductor is changed to the photoconductor described in the photoconductor production example), N / N (23 ° C., 50% RH) at room temperature and normal humidity Images were evaluated and evaluated while supplying toner (B-1) under low humidity N / L (23 ° C., 5% RH) and high temperature high humidity (30 ° C., 80% RH). Durability was performed up to 10,000 sheets each while adjusting the development bias so that the image printing ratio was 10% and the toner loading on the transfer material (paper) was 0.55 mg / cm ² . The evaluation items and evaluation criteria are shown below. The obtained evaluation results are shown in Table 4.

[Evaluation item]
<Image density>
When the solid image was fixed at 180 ° C., the density of the fixed image was measured with a densitometer X-Rite500 type, and the average value of 6 points was taken as the image density.
A: Very good (1.50 or more)
B: Good (from 1.40 to less than 1.50)
C: Normal (1.30 or more and less than 1.40)
D: Slightly bad (1.20 or more, less than 1.30: lower limit of practical use level)
E: Bad (less than 1.20)

<Fog>
The residual toner on the surface of the photoreceptor when developing a solid white image is taped with a polyester tape, then peeled off, and the fog is evaluated based on the difference in density between the tape and the tape on the paper. did. For density measurement, a densitometer X-Rite 500 type was used, and the average value of 6 points was taken as the fog toner density.
A: Very good (1.5 or less)
B: Good (1.5 or more, less than 2.0)
C: Normal (2.0 or more, less than 2.5)
D: Slightly bad (2.5 or more, less than 3.0: practical use lower limit)
E: Bad (3.0 or more)

<Transfer efficiency>
After transferring the residual toner on the surface of the photoconductor with a polyester tape after transferring the solid image, the transferability is determined by the difference between the density of the tape that is peeled off and pasted on the paper, and the density of the tape that is pasted on the paper as it is. evaluated. For the density measurement, a densitometer X-Rite 500 type was used, and an average value of 6 points was taken as a residual toner density.
A: Very good (0.5 or less)
B: Good (0.5 or more, less than 1.0)
C: Normal (1.0 or more, less than 1.5)
D: Slightly bad (1.5 or more, less than 2.0: practical use lower limit)
E: Bad (2.0 or more)

<Fusion and filming>
Using the developer and the remodeling machine, a 30H image was formed after the end of 10,000 sheets, and the image and the surface of the photoreceptor were visually observed. evaluated. Note that the 30H image is a halftone image when 256 gradations are displayed in hexadecimal, 00H is solid white, and FFH is solid.
A: There are no streaks or unevenness on the image, and there is no fusion or filming on the surface of the photoreceptor.
B: There are no streaks or unevenness, but slight fusing and filming are observed on the surface of the photoreceptor.
C: Slight stripes and unevenness are observed, and fusion and filming are observed on the surface of the photosensitive member (lower limit for practical use).
D: There are many streaks and irregularities, and remarkable fusion and filming of the photoreceptor surface are observed (impractical level).

<Image flow>
After the endurance test of 10,000 sheets using the modified machine, with the intermediate transfer member released from the photoconductor, only the photoconductor was rotated for 30 minutes while applying the charging bias, and then stopped, and left as it was. Left for hours. Thereafter, the developing unit and the intermediate transfer member were returned to normal, and a character pattern with a printing ratio of 5% was drawn until the image flow disappeared. The following ranking was performed according to the number of images that could not be recognized.
A: Less than 5 sheets B: 5 sheets or more Less than 10 sheets C: 11 sheets or more Less than 20 sheets D: 21 sheets or more Less than 30 sheets E: 31 sheets or more

<Examples 2 to 16>
In Example 1, in place of the toner (B-1) and the carrier (C-1), a combination of toner and carrier as shown in Table 5 was used. And evaluated. The evaluation results are shown in Table 4. In Example 14, since the toner (B-14) is a magnetic one-component toner, the image was printed and evaluated without using a carrier.

<Comparative Examples 1-6>
In Example 1, in place of the toner (B-1) and the carrier (C-1), a combination of toner and carrier as shown in Table 6 was used. And evaluated. The evaluation results are shown in Table 5.

It is a schematic diagram showing an example of an image forming apparatus using the image forming method of the present invention. It is a schematic diagram showing an example of an image forming apparatus using the image forming method of the present invention. It is a schematic diagram showing an example of an image forming apparatus using the image forming method of the present invention. It is a schematic diagram which shows an example of the grinding | pulverization apparatus used for this invention. It is a schematic diagram which shows an example of the surface modification apparatus used for this invention. It is a schematic diagram of the apparatus used in order to measure the specific resistance of the magnetic carrier used for this invention.

Explanation of symbols

1 Photoconductor (electrostatic latent image carrier)
2 Charging device 3 Exposure device 4 Development device 5 Transfer device

Claims (6)

A charging step of charging the electrostatic latent image carrier, an electrostatic latent image forming step of forming an electrostatic latent image on the charged electrostatic latent image carrier, and developing the electrostatic latent image with a developer; The toner image is formed on the latent electrostatic image bearing member, and at the same time, the developing and collecting step for collecting the toner remaining on the latent electrostatic image bearing member after transfer, and the toner image on the latent electrostatic image bearing member are intermediate In an image forming method having at least a transfer step of transferring to a transfer body or transfer material,
The latent electrostatic image bearing member is an electrophotographic photosensitive member having an organic photosensitive layer, and has a curable surface layer.
The toner is a toner containing at least inorganic fine particles on the surface of toner particles containing at least a binder resin and a colorant, and the inorganic fine particles are strontium titanate, and the strontium titanate is a primary particle. Particles having an average particle diameter of 30 nm or more and 300 nm or less, a cubic particle shape and / or a rectangular parallelepiped particle shape, and a perovskite crystal, and an equivalent circle diameter (number basis) of the toner of 2 μm. An image forming method, wherein the average circularity of the particles is 0.920 to 0.970, and the UV transmittance of the toner with respect to a 45 volume% methanol aqueous solution is 10 to 80%.   The developer is a two-component developer having at least a toner and a magnetic carrier, and the magnetic carrier has a coating layer on the surface of a magnetic fine particle-dispersed resin core containing at least magnetic fine particles and a binder resin. The image forming method according to claim 1. The surface of the electrostatic latent image carrier is subjected to a hardness test using a Vickers square pyramid diamond indenter in an environment of 25 ° C. and 50% humidity, and the HU (Universal Hardness Value) when pressed at a maximum load of 6 mN is 150 N. / mm ² or more 220 N / mm ² or less, and an image forming method according to claim 1 or 2 elastic deformation rate We are equal to or less than 65% more than 45%.   The image forming method according to claim 1, wherein the charging step is a contact charging method.   5. The image forming method according to claim 1, further comprising a leveling step of leveling toner remaining on the electrostatic latent image carrier after transfer and before charging, and applying a bias. An image forming method according to claim 1. Charging means for charging the electrostatic latent image carrier, electrostatic latent image forming means for forming an electrostatic latent image on the charged electrostatic latent image carrier, and developing the electrostatic latent image with a developer; At the same time as the toner image is formed on the electrostatic latent image carrier, the developing and collecting means for collecting the toner remaining on the electrostatic latent image carrier after the transfer, and the toner image on the electrostatic latent image carrier are intermediate In an image forming apparatus having at least a transfer means for transferring to a transfer body or transfer material,
The latent electrostatic image bearing member is an electrophotographic photosensitive member having an organic photosensitive layer, and has a curable surface layer.
The toner is a toner containing at least inorganic fine particles on the surface of toner particles containing at least a binder resin and a colorant, and the inorganic fine particles are strontium titanate, and the strontium titanate is a primary particle. Particles having an average particle diameter of 30 nm or more and 300 nm or less, a cubic particle shape and / or a rectangular parallelepiped particle shape, and a perovskite crystal, and an equivalent circle diameter (number basis) of the toner of 2 μm. An image forming apparatus, wherein the average circularity of the particles is 0.920 to 0.970, and the UV transmittance of the toner with respect to a 45 volume% methanol aqueous solution is 10 to 80%.

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