MXPA06008694A - Toner, and developing agent, container packed with toner, process cartridge, image forming apparatus and method of image forming - Google Patents

Abstract

A toner that realizes high toner fill in toner images, being capable of producing highly fine images through reduction of image layer thickness, and that exhibits stable cleanability over a prolonged period of time;a developing agent utilizing the toner and capable of realizing high image quality;and utilizing the toner, a container packed with toner, process cartridge, image forming apparatus and method of image forming. There is provided a toner of approximately spherical configuration having a rugged surface, comprising a toner material containing at least a binder resin and a colorant, wherein the toner has a shape factor (SF-1), representing the degree of spherical configuration thereof, of 105 to 180 and there is a correlation between shape factor (SF-2) representing the degree of ruggedness of the toner and volume-average particle diameter of the toner, and wherein an inorganic oxide particle-containing layer lies within 1&mgr;m from the surface of the toner.

Description

TONER, DEVELOPER, TONER CONTAINER, PROCESS CARTRIDGE, IMAGE FORMATION DEVICE AND METHOD OF TRAINING IM GENES Field of the Invention The present invention relates to a toner for developing an electrostatic latent image in electrophotography, electrostatic recording, electrostatic printing or the like, a developer using the toner, a toner container for containing the toner, a process cartridge which uses toner, an image forming device that uses toner, and an imaging method that uses toner.

BACKGROUND OF THE INVENTION Electrophotography uses a developer to reveal an electrostatic latent image formed in a member having the electrostatic latent image. This developer can be classified into two types: a developer of a component consisting of toner, and a two-component developer consisting of a carrier and toner. The two component developer can provide relatively stable excellent images by mixing the carrier and the toner together to allow the toner particles to be charged positively or negatively.

The toner production process can be broadly divided into two general categories: dry process and wet process. In the first process, a binder resin, a colorant, a release agent, etc. are melted and mixed together, by heat, and pressure, cooled and pulverized into toner particles. Since this spraying process comprises the destruction of toner particles in a plate by means of air pressure and collision of the toner particles, the finely pulverized toner particles are not spherical and have irregularities. In the latter process, a binder resin, a colorant, a release agent, etc., are added to a solvent for polymerization, followed by drying to produce toner particles which are therefore spherical and have smooth surfaces. Along with the widespread use of the color imaging apparatus of recent years, small diameter toners for high definition color images are under study. For the production of small diameter toners, a wet process is more advantageous than a dry process. However, the wet process tends to produce spherical, smooth toner particles as described above, resulting in poor removal capacity. In In particular, cleaning problems frequently occur in the case of cleaning the blades. Against this background, several proposals have been under study to control the shape of the toner in the wet process. For example, Patent Literature 1 describes a toner comprising toner particles and an external additive and has the following characteristics: average circularity = 0.920 to 0.995: average particle diameter by weight = 2.0 μ to 9.0 μm; the proportion of particles with an average circularity of less than 0.950 is 2% to 40% on a number basis; and the external additive is present in the toner particles in the form of primary particles to secondary particles. Patent Literature 2 describes a toner composed of toner particles, where a coefficient of variation for the shape coefficient is 16% or less and a coefficient of variation in number in the size distribution based on number is 27% or less . Patent Literature 3 discloses a toner comprising resin particles and a colorant and satisfying the following conditions at the same time: GSDv < 1.25, SF = 125 to 140, D50, = 3 μm to 7 μm, (the proportion of particles with SF-1 of 120 or less) < 20% on even number basis, (the proportion of particles with SF-1 of 150 or less) < 20% on a number basis, and (the proportion of particles with SF-1 of 120 or less or an equivalent circle diameter of 4/5 or less) < 10% on a number basis. Patent Literature 4 discloses an image forming method using a toner where a coefficient of variation for the shape coefficient is 16% or less, a coefficient of variation of number in the distribution of size based on number is 27% or less, and a ratio of flocculation of toners from 3% to 35%. However, it is difficult for the strategies described in Patent Literatures 1 to 4 to provide high definition images and achieve long term stable removal capacity. More specifically, toner particles with specific shape factors, specified by these conventional techniques can not be removed well with a blade cleaning approach. Additionally, there is a problem that cleaning problems arise, particularly in the case where smaller diameters of the toner particles are employed together with the recent demand for high quality images and where the toner particles have smooth surfaces without irregularities. In this way, toners that can provide long-term removal capability and high definition images with reduced thickness of the image layer and toner particles have not yet been provided. densely packed, and related technologies that use these toners. [Patent Literature 1] Patent Application Japanese Revealed (JP-A) No. 11-174731 [Patent Literature 2] Patent Application Japanese Revealed (JP-A) No. 2000-214629 [Patent Literature 3] Patent Application Japanese Revealed (JP-A) No. 2000-267331 [Patent Literature 4] Japanese Patent Application Revealed (JP-A) No. 2002-62685 Description of the Invention It is an object of the present invention to solve the above conventional problems and provide a toner that can provide long term removal capacity and high definition images with reduced thickness of the image layer and densely packed toner particles, a developer capable of forming high quality images by the use of toner, a toner cartridge to contain the toner, a process cartridge using the toner, an image forming apparatus using the toner, and an image forming method that uses toner. The following is the means to solve the above problems: 1. A toner that includes: a toner material that it comprises a binder resin and a colorant, wherein the toner has a substantially spherical shape with irregularities on its surface, and wherein a surface factor SF-1 represented by the following Equation (1) representing the sphericity of the toner particles 105 to 180, a surface factor SF-2 represented by the following Equation (2) which represents the degree of surface irregularities of the toner particles correlates with the average volume diameter of the toner particles, and the particles of Toner have a layer that contains inorganic oxide particles within 1 μm of their surfaces. SF-1 = [(MXLNG) VAREA] x (100 / 4p) ... Equation (1) where MXLNG represents the maximum length through a two-dimensional projection of a toner particle, and AREA represents the area of the projection. SF-2 = [(PERI) V REA] x (10? / 4p) ... Equation (2) where PERI represents the perimeter of a two-dimensional projection of a toner particle, and AREA represents the area of the projection. 2. The toner according to 1., where SF-1 is 115 to 160 and the SF-2 is 110 to 300. 3. The toner according to one of 1., to 2., where the difference between the SF -2 of the toner particles whose particle diameter is smaller than the diameter of the most abundant toner particle in a particle size distribution and the SF-2 of the toner particles whose particle diameter is equal to or greater than the most abundant toner particle diameter in the particle size distribution is 8 or greater . 4. The toner according to any one of 1., to 3., wherein the layer containing inorganic oxide particles comprises silica. 5. The toner according to any one of 1., to 4., wherein the average particle diameter in volume is 3 μm to 10 μm. 6. The toner according to any of 1., to 5., where the ratio of the average particle diameter in volume (Dv) to the average particle diameter in number (Dn), (Dv / Dn), is 1.00 a 1.35. 7. The toner according to any of 1., to 6., where the proportion of toner particles that have an equivalent circle diameter, the diameter of a circle that has the same area as the projection of the toner particles , 2 μm is 20% or less on a number basis. 8. The toner according to any one of 1., to 7., wherein the porosity of the toner particles under pressure of 10 kg / cm2 is 60% or less. . The toner according to any of 1., to 8., where the toner is produced by emulsifying or dispersing a toner material solution or a dispersion of toner material in an aqueous medium to form toner particles. 10. The toner according to 9., wherein the solution of toner material or dispersion of toner material comprises an organic solvent, and the organic solvent is removed on or after the production of the toner particles. 11. The toner according to any of 9., to 10., wherein the toner material comprises a compound containing a group of active hydrogen and a polymer capable of reacting with the active hydrogen group-containing compound, the toner particles are produced by the reaction of the compound which it contains the group of active hydrogen with the polymer to produce an adhesive base material comprising the toner particles. 12. The toner according to 11., wherein the toner material comprises an unmodified polyester resin and the mass ratio of the polymer capable of reacting with the compound containing the active hydrogen group to the unmodified polyester resin ( polymer / unmodified polyester resin) is 5/95 to 80/20. 13. A developer that includes a toner according to any of 1., to 12. 14. Developer according to 13., where the developer is either a one-component developer and a two-component developer. 15. A toner container including a toner according to any of 1., to 12. 16. A process cartridge including: a member that carries the electrostatic latent image; and a developing unit configured to reveal an electrostatic latent image formed in the member carrying the electrostatic latent image by the use of a toner according to any of 1., to 12., to form a visible image. 17. An image forming apparatus that includes: a member that carries an electrostatic latent image; a forming unit of the electrostatic latent image configured to form an electrostatic latent image in the carrier member of the electrostatic latent image; a developing unit configured to reveal the electrostatic latent image by the use of a toner according to any of 1., to 12., to form a visible image; a transfer unit configured to transfer the visible image to a recording medium; and a fixing unit configured to fix the visible image transferred to the recording medium. 18. An image forming method that includes: forming an electrostatic latent image on a member carrying the electrostatic latent image; reveal the electrostatic latent image by the use of a toner according to any of 1., to 12., to form a visible image; transfer the visible image to a recording medium; and fix the visible image transferred to the recording medium. The toner of the present invention is a toner having a substantially spherical shape with irregularities on its surface and comprising a toner material comprising a binder resin and a colorant, wherein a surface factor SF-1 represented by Equation (1) ) above representing the sphericity of the toner particles 105 to 180, a surface factor SF-2 represented by the above equation (2) representing the degree of surface irregularities of the toner particles correlates with the average diameter in volume of the toner particles, and the toner particles have a layer containing inorganic oxide particles within 1 μm of their surfaces. In this way, a toner that can provide long-term removal capability and high-definition images with reduced thickness of image layer and densely packed toner particles is possible. The developer of the present invention comprises the toner of the present invention. In this way, the formation of electrophotographic images using this developer can provide long-term removal capacity and images High definition with reduced thickness of the image layer and densely packed toner particles, achieving stable formation of high quality images with good reproduction capacity. The toner cartridge of the present invention contains therein the toner of the present invention. In this way, the formation of electrophotographic images using the toner contained in the toner container can provide long-term removal capacity and high quality images with excellent properties (e.g., charge and transfer properties). The process cartridge of the present invention comprises an electrostatic latent image carrier member and a developing unit configured to reveal an electrostatic latent image formed in the electrostatic latent image carrier member by the use of the toner of the present invention to form a visible image . The process cartridge can be removably attached to an image forming apparatus, with user-friendly features, and uses the toner of the present invention. In this way, it offers excellent cleaning ability and excellent toner properties (for example, loading and transfer properties), making it possible to provide high quality images. The image forming apparatus of the present invention comprises: a member carrying an electrostatic latent image; an electrostatic latent image forming unit configured to form an electrostatic latent image in the electrostatic latent image carrier member; a developing unit configured to reveal an electrostatic latent image by use of the toner of the present invention to form a visible image; a transfer unit configured to transfer the visible image to a recording medium; and a fixing unit configured to fix the visible image transferred to the recording medium. In the image forming apparatus, the electrostatic latent image forming unit forms an electrostatic latent image on the electrostatic latent image carrier member, the transfer unit transfers a revealed visible image to a recording medium, and the fixed attachment unit the visible image transferred to the recording medium. In this way, it is possible to form high quality electrophotographic images that offer excellent toner removal capacity and excellent toner properties (for example load and transfer properties). The method of imaging of the present invention comprises the steps of: forming an electrostatic latent image on the carrier member of the electrostatic latent image; reveal the electrostatic latent image by the use of a toner of the present invention to form a visible image; transfer the visible image to a recording medium; and fix the visible image transferred to the recording medium. In the electrostatic latent image formation step, an electrostatic latent image is formed in an electrostatic latent image carrier member. In the transfer step, a revealed visible image is transferred to a recording medium. In the fixing step, the visible image transferred is fixed to the recording medium. In this way, it is possible to form high quality electrophotographic images that offer excellent toner removal capacity and excellent toner properties (eg, charge and transfer properties).

Brief Description of the Figures Figure 1 is a schematic diagram of a toner particle to explain the SF-1 form factor. Figure 2 is a schematic diagram of a toner particle to explain the SF-2 form factor. Figure 3 is a schematic view showing an example of a device for measuring the porosity of toner particles. Figure 4 is a schematic view showing an example of the process cartridge of the present invention. Figure 5 is a schematic view showing an example of carrying out the imaging method of the present invention by means of the image forming apparatus of the present invention. Figure 6 is a schematic view showing another example of carrying out the imaging method of the present invention by means of the image forming apparatus of the present invention. Figure 7 is a schematic view showing an example of carrying out the imaging method of the present invention by means of the image forming apparatus of the present invention (tandem color imaging apparatus). Figure 8 is a partially enlarged schematic view of the image forming apparatus of Figure V. Figure 9A is a photograph of toner particles in Example 1 accumulated in an electrostatic latent image carrier member. Figure 9B is a photograph of toner particles in Comparative Example 2 accumulated in an electrostatic latent image carrier member.

BEST MODE FOR CARRYING OUT THE INVENTION Toner The toner of the present invention has a form substantially spherical with surface irregularities, comprising a toner material comprising a binder resin and a colorant, and further comprising additional ingredients as needed. The form factor SF-1, which represents the sphericity of the toner particles, of the toner is 105 to 180, and there is a correlation between the form factor SF-2 which represents the degree of surface irregularities of the toner particles and the average particle diameter in volume. The shape of the toner is substantially spherical, including an oval shape. This improves the fluidity and facilitates its mixing with the carrier. In addition, other than the irregular toner particles, the spherical toner particles are uniformly charged by friction with the carrier and thus show a narrow distribution of the charge density, leading to a reduced background fogging. The spherical toner particles can also achieve an increased transfer ratio because they are revealed and transferred in strict accordance with the electric field lines. Figure 1 is a schematic diagram of a toner particle to explain the SF-1 form factor. Form factor SF-1 represents the sphericity of the toner shape and is represented by the following Equation (1) The SF-1 is a value obtained by dividing the square of the maximum length (MXLNG) through a two-dimensional projection of a toner particle by the projection area (AREA) and multiplying by 100p / 4. SF-1 = [(MXLNG) VAREA] x (100 / 4p) ... Equation (1) where MXLNG represents the maximum length through a two-dimensional projection of a toner particle, and AREA represents the area of the projection. The shape factor SF-1 is 105 to 180, preferably 115 to 160, and more preferably 120 to 150. If the SF-1 form factor is 100, the toner shape is a perfect sphere, the higher the be the form factor SF-1, more irregular is the shape of the toner. If the SF-1 form factor is greater than 180, the removal capacity is improved but the charge density distribution becomes wide, resulting in increased background fogging and reduced image quality due to that the toner shape deviates greatly from the sphere. Furthermore, since the development and transfer of the image are not carried out in strict accordance with the lines of the magnetic field due to the entrainment of air in the transfer, the toner is revealed between thin lines to result in reduced uniformity of the image. and poor image quality. Meanwhile, even when SF-1 is 105 and in this way the particles are closer to a perfect sphere, the toners in which the volume average particle diameter correlates the SF-2 form factor can still be removed with a blade cleaning approach and can provide high quality images due to its high image uniformity. For a toner to be substantially spherical, in a case of a toner produced by a dry pulverization process, it becomes spherical thermally or mechanically after spraying. For a thermal process, for example, the toner particles can be made spherical by spraying them in an atomizer together with heat flow. By a mechanical process, the toner particles can be made spherical by placing them in a mixer (e.g., a ball mill) for co-spraying with a medium of low ific gravity such as glass. It is noted, however, that this thermal process leads to the aggregation of toner particles to form large particles and thus requires an additional step of classification to remove them, and that this mechanical process leads to the generation of dust and thus requires similarly, an additional classification step to remove dust. In addition, the toner particles produced in an aqueous medium can be controlled so that their shapes vary from spherical to oval, by vigorously shaking the medium in one step to remove a solvent. The toner has irregularities in its surface. This toner is less adhesive to a photoconductor compared to a toner with a smooth surface, thus increasing its removal capacity. Figure 2 is a schematic diagram of a toner particle to explain the SF-2 form factor. The degree of surface irregularities of the toner particles is represented by the form factor SF-2 represented by the following Equation (2). SF-2 is a value obtained by dividing the perimeter square (PERI) of a two-dimensional projection of a toner particle by the projection area (AREA) and multiplying by 100 / 4p. SF-2 = [(PERI) V REA] x (100 / 4p) ... Equation (2) where PERI represents the perimeter of a two-dimensional projection of a toner particle, and AREA represents the area of the projection. The shape factor SF-2 is 110 to 300, preferably 115 to 200 and more preferably 118 to 150. If SF-2 is 100, it indicates that irregularities are not present on the surface of the toner; the greater is SF-2, irregularities are more conspicuous or visible. Yes SF-2 is greater than 300, the removal capacity is improved but the degree of surface irregularities of the toner it becomes larger and the distribution of charge density becomes wider, resulting in a degraded quality of the image due to increased background fogging. If SF-2 is 110 and in this way the surface of the toner is smooth, the toners in which the average particle diameter in correlation with the form factor SF-2, can still be removed with a cleaning approach of blade and can provide high quality images due to its narrow charge density distributions. Form factors SF-1 and SF-2 can be determined for example by using a scanning electron microscope (S-800, manufactured by Hitachi Ltd.), to make toner particle images and analyze them by an image analyzer ( LUSEX3, manufactured by NIRECO Corp.), using Equations (1) and (2) above. In the previous toner, the form factor SF-2 correlates with the volume average particle diameter (Dv). Since both the uniformity of the electrophotographic image and the removal capacity are influenced by the toner shape and the particle diameter of toner, it is possible to control the uniformity and the ability to remove the image by correlating the particle diameter average in volume with the form factor SF-2.

As used herein "correlate" means that the SF-2 form factor varies depending on the volume average particle diameter, which means one of the following ratios: (1) SF-2 increases with increasing diameter volume average particle, and (2) SF-2 decreases with the increase in average particle diameter in volume. In view of the control of image uniformity and removal capacity, it is preferred that the volume average particle diameter correlates with the SF-2 form factor in such a way that SF-2 increases with increasing diameter average particle in volume. An example of the method for correlating the volume average particle diameter with the surface factor SF-2 for a toner having a substantially spherical shape with irregularities on the surface includes a method for changing the delivery rate of a solvent used in a step to cause the surface of the toner to contract when adjusting the temperature and / or the pressure, in a case where the toner is produced by suspension in solution, one of the wet processes. For example, if the volume average particle diameter is proposed to correlate with the SF-2 form factor to a greater degree, the temperature and the like can be adjusted to increase the supply speed of the solvent. If the volume average particle diameter correlates with the shape factor SF-2, or not, it can be determined for example by using a scanning electron microscope (S-800, manufactured by Hitachi Ltd.), to take images of toner particle and analyze them by an image analyzer (LUSEX3, manufactured by NIRECO Corp.). The volume average particle diameter (Dv) of the toner is preferably 3 μm to 10 μm, more preferably 3 μm to 7 μm and more preferably 3 μm to 6.5 μm. The use of toner with a volume average particle diameter of 10 μm or less can improve the reproduction capacity of fine lines. However, it is preferred that the volume average particle diameter is at least 3 μm because a too small volume average particle diameter reduces the developing property and the removal capacity. In addition, if the volume average particle diameter is less than 3 μm, the number of fine particles, small diameter of toner that are less likely to be revealed is increased on the surface of the carrier or on a developer roller, and from this way the friction and contact between the toner particles different from these fine particles and the developing roller or carrier may be insufficient so that the number of toner particles inversely charged increases to cause abnormalities such as background fogging, which makes it difficult to provide high quality images. The particle size distribution of the toner represented in terms of the average particle diameter ratio in volume (Dv) average particle diameter in number (Dn), (Dv / Dn), is preferably 1.00 to 1.35 and so more preferred, 1.00 to 1.15. It is possible to provide a uniform distribution of toner charge density by narrowing or sharpening the particle size distribution. If (Dv / Dn) is greater than 1.35, the charge density distribution of toner becomes too wide and the number of toner particles inversely charged increases. For these reasons, it is difficult to provide high quality images. The volume average particle diameter and the ratio (Dv / Dn) of the average particle diameter in volume to the average particle diameter in number can be determined by calculating the average particle diameters of 50,000 toner particles using a Counter of Coulter particles (Beckmann Coulter Inc.), even opening diameter of 50 μm corresponding to the sizes of the toner particles to be measured. In addition, the difference between the SF-2 of the toner particles whose particle diameter is more smaller than the most abundant toner particle diameter in the particle size distribution (hereinafter referred to as "SF-2 small diameter") and the SF-2 of the toner particles whose particle diameter is equal to or greater than the most abundant toner particle diameter in the particle size distribution (hereinafter referred to as "SF-2 large diameter"), ie, "SF-2 large diameter" "less than SF-2 of small diameter") is preferably 8 or greater, more preferably 12 or greater and more preferably 20 or greater; the upper limit is preferably monkeys of 50. The fact that this difference is less than 8 means that the toner particles whose particle diameter is smaller than the most abundant particle diameter in the particle size distribution and the particles of toner whose particle diameter is equal to or greater than the most abundant particle diameter in the particle size distribution have similar shapes. In this way, it may be difficult to obtain effects caused by creating a surface factor gradient. If the difference is greater than 50, the distribution of the charge density becomes additionally wide to cause problems such as reduced image uniformity, reduced transfer property, and generation of spills on the resulting images. Moreover, while the small diameter toner particles without irregularities on their surface are prone to slip through a cleaning blade, the large diameter toner particles with many irregularities, which can provide more excellent removal capacity, are They accumulate on the edge of the cleaning blade to form a "dump" which can thus remove the small diameter toner particles. It is noted that for "the most abundant particle diameter in the particle size distribution", the upper peak is used in the particle size distribution based on number. The toner transfer property is associated with the state of the aggregate toner particles revealed in a photoconductor. A regular, flat layer of toner can provide an excellent image without spills because a transfer pressure and an electric transfer layer are uniformly applied in the toner layer. An irregular toner layer causes spills and / or unevenness in the toner transfer. How uniformly the toner layer is revealed is affected by the uniformity of the toner charge density distribution and / or the uniformity of the toner fluidity. To obtain this uniformity, it is preferred that the toner particles be spherical and have smooth surfaces. Small diameter toners, in particular, have this tendency and the toner particles with smoother surfaces are packed uniformly in a photoconductor with a regular surface, providing excellent transferred images. In the meantime, once a densely packed toner layer is exposed to unusual conditions. - an increase in light in the transfer pressure as in the case of a transfer sheet with large irregularities (for example, a rough sheet) and / or micro-space download for transfer, results in a broad reduction in transfer efficiency in comparison with irregular toners. In addition, the inequalities in light transfer tend to become manifest due to the excellent average transfer ratio. Now, it is assumed that the toner particles fall into two categories: large diameter components and small diameter components. By increasing a surface factor gradient therebetween, the surfaces of the small diameter components are made smooth, that the small diameter components have a profound effect on improving the image quality such as reproducibility of fine lines and texture. of the grains, and provides large irregularities in the diameter components large, it is possible to prevent the creation of a toner layer packed excessively dense while increasing the proportion of irregular toner particles in the toner layer. Therefore, it is possible to provide excellent toner transfer ratio and a stable toner layer. The toner comprises a layer containing inorganic oxide particles within 1 μm of its surface. The layer containing inorganic oxide particles preferentially occupies 60% or more of the perimeter of the toner particle when viewed at the end and more preferably 75% or more. More preferably, it covers the entire surface of the toner particle; however, it can appear sporadically or it can form multiples each stacked one on top of the other. It is possible to maintain a controlled phase of toner by providing this layer containing inorganic oxide particles. If the layer containing inorganic acid particles within 1 μm of the toner surface is not provided, the controlled form of toner can not be maintained. In particular, when the toner is used over time as a mixed and agitated developer with carrier, the shape of the toner undergoes changes due to mechanical stress, resulting in reduced image uniformity and reduced removal capacity in some cases. If a layer containing inorganic oxide particles, or not, of the toner surface is formed within 1 μm, a transmission electron microscope (TEM) can be determined by looking at the cross section of the used toner particles. Examples of inorganic oxide particles include oxides of metals (eg, silicon, aluminum, titanium, zirconium, iron, magnesium), silica, alumina and titania. Among these, silica, alumina and titania are preferable and silica is more preferable. An example of a method for providing a layer containing inorganic oxide particles within 1 μm from the toner surface is as follows: for example, when a toner is produced by a process similar to solution suspension, one of the processes in wet, inorganic oxide particles are added in an above manner to an organic solvent before dissolving or dispersing a toner material in the organic solvent. Preferably, the inorganic oxide particles are added to the toner in an amount of 0.1 mass% to 2 mass%. If less than 0.1% by mass is used, the effect of inhibiting the flocculation of the toner particles can be damaged. If more than 2% by mass is used, it can result in several problems, splashing of toner between fine lines, contamination inside an image forming device, and tearing and tearing in a photoconductor. It is preferable to modify the surface of the toner using a hydrophobing agent. Examples of the hydrophobizing agent include dimethyldichlorosilane, trimethylchlorosilane, methyltrichlorosilane, alildimetildiclorosilano, alilfenilclorosilaño, dibencildimetilclorosilano, ometildimetilclorosilano bro, cloroetiltriclorosilano a-, p-cloroetiltriclorosilano, chloromethyldimethylchlorosilane, clorometiltriclorosilano, chlorosilane, hexafenildisilazano and hexatolildisilazano. The proportion of toner particles having an equivalent diameter in a circle (the diameter of a circle having the same area as the projection of the toner particle) of 2 μm is preferably 20% or less in a base in number and more preferably, 10% or less. By doing so it is possible to prevent the temporary reduction in image quality due to these fine toner particles. In fine toner particles with an equivalent circle diameter of 2 μm or less, the charge density per unit mass (μC / g) is higher due to its large surface area per unit mass, and therefore, it is less likely its development and transfer. In particular, after from a long time use, these fine toner particles remain in the developing device to reduce the volume average particle diameter of the toner and the surfaces of the charging members such as a magnetic carrier are firmly stuck. In this way, they undesirably inhibit the electrification of the large-diameter toner particles (e.g., the newly added toner particles), and the toner particles that are insufficiently charged expand the charge density distribution and form affected images with background fogging, thus reducing the quality of the image over time. The proportion (% by number) of toner particles with a given diameter in given circles can be determined using a flow particle image analyzer (FPIA-210, manufactured by Sysmex Corp.). More specifically, an aqueous solution of 1% NaCl is prepared using primary sodium chloride, and filtered through a 0.45 μm pore size filter. to 50-100 ml of this solution 0.1-5 ml of a surfactant (preferably, alkylbenzene sulfonate) is added as a dispersing agent, followed by the addition of 1-10 mg of sample. The sample is then treated with ultrasound for 1 minute using an ultrasound treatment apparatus to prepare a dispersion with a final particle concentration of 5000-15000 / μL for the measurement. The measurement is made based on the equivalent diameter in a circle, the diameter of a circle that has the same area as the 2D image and a particle of toner taken by a CCD camera. In view of the resolution of the CCD camera, measurement data are collected on the particles with an equivalent circle diameter of 0.6 μm or more. The porosity of the toner particles is preferably 60% or less under pressure of 10 kg / cm2 and more preferably 55% or less. The lower limit is preferably 45%. Doing so reveals a regular toner layer with a minimum volume in a photoconductor, producing an image with reduced thickness of the image layer and increased image uniformity. In this way, it is possible to provide high quality images. The porosity of the toner particles can be measured using, for example, a porosity measuring device shown in Figure 3. The porosity measuring device includes a torque meter 1, a conical rotor 2, a cell 3 of load, a weight 4, a piston 5, a sample container 6, an agitator 7, and a lifting stage 8. The porosity can be measured from the following way. The sample container 6 is first charged with a given amount of toner, and it is attached to the measuring device. The torque meter 1 is operated to rotate the conical rotor 2, and the rotating conical rotor 2 is placed in the toner powder. Before the actual measurements, toner powder is placed under pressure of 10 kg / cm2 for compression. The volume and weight of the compressed toner powder are measured to calculate its porosity while taking its specific weight taken into consideration. In this measurement, the smaller the porosity at a given pressure, the more toner particles are more likely to pack, and the packaged particles show a regular structure such as a packed, closed structure. The same holds true for a revealed toner. The production process and constituent material of the toner of the present invention are not limited in a particular way so long as the above requirements are met, and can be selected from those known in the art.; for example, small diameter toners that are substantially spherical and have irregularities in their surfaces that are preferable. Examples of the toner production process include the spraying and sorting method, and suspension polymerization, emulsion polymerization and polymer suspension to form toner base particles when emulsifying, suspending or flocculate an oil phase in an aqueous medium. The method of spraying one to produce base toner particles by melting and kneading toner material. It is noted that in this spraying method, impacts to the base particles, resulting from toner, can be applied to control their shapes so that the average circularity is in a range of 0.97 to 1.00. In this case, these mechanical impacts are applied to the toner base particles using, for example, a hybridizer or a mechanofusion machine. In the suspension polymerization method, a dye, a release agent, etc., is dispersed in a mixture of an oil-soluble polymerization initiator and polymerizable monomers, and the resulting monomer mixture is emulsified and dispersed by emulsification which is will describe later in an aqueous medium containing a surfactant, a solid dispersing agent, etc. After a polymerization reaction to produce toner particles, a wet process can be performed to bond the inorganic particles to their surfaces. At this point, the inorganic particles are preferably joined after removal of the excess surfactant or the like by washing. By using any of the following polymerizable monomers, it is possible to introduce functional groups to the surfaces of the resin particles. Examples of these polymerizable monomers include acids such as acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, and maleic acid anhydride; acrylamide, methacrylamide, diacetoneacrylamide and methylol derivatives thereof, acrylates and methacrylates having amino groups, such as vinylpyridine, vinylpyrrolidine, vinylimidazole, ethylenimine, and dimethylaminoethyl methacrylate. Alternatively, functional groups can be introduced by using a dispersing agent having an acid group and / or basic group that adsorbs to the surface of the resin particle. In the emulsion polymerization method, a water-soluble polymerization initiator and polymerizable monomers emulsify in water using a surfactant, followed by production of latex by general emulsion polymerization. Separately, a dye, a release agent, etc. is dispersed in an aqueous medium to prepare a dispersion, which is then mixed with the latex. The latex particles then set to the particle size of the toner, heat up and fuse together to produce toner particles. Subsequently, a wet process can be carried out described later for the union of inorganic particles. Functional groups can be introduced to the surface of the resin particles by using monomers similar to those that can be used for latex suspension polymerization. In the present invention, a toner produced by emulsifying or dispersing a solution of toner material or a dispersion of toner material in an aqueous medium is preferable, because the range of choice of the available resins is wide, a high property of fixing at low temperature, toner particles can be easily produced, and it is easy to control the particle diameter, the particle size distribution, and the shape. The toner material solution is prepared by dissolving the toner material in a solvent and the dispersion of toner material is prepared by dispersing the toner material in a solvent. The toner material comprises an adhesive base material obtained by reacting together a compound containing an active hydrogen group, a polymer capable of reacting with the compound containing an active hydrogen group, and a binder resin, a release agent, and a dye. The toner material comprises additional ingredients such as particles of resin and / or a charge control agent on a base as needed.

Adhesive Base Material The adhesive base material exhibits adhesion to a recording medium such as paper, comprises an adhesive polymer produced by reaction of the compound containing a group of active hydrogen with the polymer capable of reacting therewith in the aqueous medium, and may comprise in addition a binder resin selected suitably from those known in the art. The weight average molecular weight of the adhesive base material is not particularly limited and can be determined appropriately depending on the proposed use. For example, the weight average molecular weight is preferably 1,000 or more, more preferably 2,000 to 10,000,000 and more preferably 3,000 to 1,000,000. If the weight average molecular weight is less than 1,000, the hot transfer property can be reduced. The storage module of the adhesive base material is not limited in a particular way and can be determined in an appropriate manner depending on the proposed purpose. For example, the temperature at which the module storage is equal to 10,000 dynes / cm2 at a measurement frequency of 20 Hz (ie, TG ') is generally 100 ° C or more and more preferably, 110 ° C to 200 ° C. If TG 'is less than 100 ° C, the anti-hot transfer property can be reduced. The viscosity of the adhesive base material is not particularly limited and can be determined appropriately depending on the purpose proposed. For example, the temperature at which the viscosity is equal to 1,000 poises at a measurement frequency of 20 Hz (ie T?) Is generally 180 ° C or less and more preferably 90 ° C or 160 ° C. . Yes T? is greater than 180 ° C, the fixing property can be reduced at low temperature. In order to ensure excellent heat transfer property and an excellent property of low temperature setting, the TG 'is preferably greater than T ?, ie the difference between TG' and T? (or TG 'minus T?) is preferably 0 ° C or higher, more preferably 10 ° C or higher and more preferably, 20 ° C or higher. It is pointed out that the greater the difference, the more preferable it is. Furthermore, in order to ensure an excellent heat transfer property and an excellent property of fixing at low temperature, (TG 'minus T?) Is preferably in a range of 0 ° C to 100 ° C, so preferably from 10 ° C to 90 ° C and more preferably 20 ° C to 80 ° C. The adhesive base material is not particularly limited and can be determined adequately depending on the intended use; Preferred examples include polyester resins. Polyester resins are not limited in a particular way and can be determined adequately depending on the proposed use; Preferred examples include polyester resins modified with urea. The urea-modified polyesters are obtained by reacting, in the aqueous medium, (B) amines as the active hydrogen-containing compounds with (A) polyester prepolymers containing isocyanate groups as polymers capable of reacting with the active hydrogen-containing compounds . In addition, the urea-modified polyesters can include a mne bond in addition to a urea linkage. The molar ratio of the urea link to the urne linkage (urea link / urne link) is not particularly limited and can be determined appropriately; however, it is preferably in a range of 100/0 to 10/90, more preferably 80/20 to 20/80 and more preferably 60/40 to 30/70. When the molar ratio of the urea bond is less than 10, it can give Reduced hot transfer property result. Preferred specific examples of the urea-modified polyesters are the following groups (D- (10): (1) A mixture of (i) a urea-modified polyester prepolymer, modified with isophorone-diamine, the prepolymer obtained by reacting a polycondensation product of 2 moles of lene oxide adduct of bisphenol A and isophthalic acid with isophorone diisocyanate, and (ii) a polycondensation product of 2 moles of lene oxide adduct of bisphenol A and isophthalic acid; (2) A mixture of (i) a urea-modified polyester prepolymer, modified with isophorone diamine, the prepolymer obtained by reacting a polycondensation product of 2 moles of ethylene oxide adduct of bisphenol A and isophthalic acid with diisocyanate of isophorone, and (ii) a polycondensation product of 2 moles of ethylene oxide adduct of bisphenol A and terephthalic acid; (3) A mixture of (i) a urea-modified polyester prepolymer, modified with isophorone diamine, the prepolymer obtained by reacting a polycondensation product of 2 moles of ethylene oxide adduct of bisphenol A / 2 moles of adduct of propylene oxide of bisphenol A and terephthalic acid with isophorone diisocyanate, and (ii) a polycondensation product of 2 moles of ethylene oxide adduct of bisphenol A / 2 moles of propylene oxide adduct of bisphenol A and terephthalic acid; (4) A mixture of (i) a urea-modified polyester prepolymer, modified with isophorone-diamine, the prepolymer obtained by reacting a polycondensation product of 2 moles of ethylene oxide adduct of bisphenol A / 2 moles of adduct of propylene oxide of bisphenol A and terephthalic acid with isophorone diisocyanate, and (ii) a polycondensation product of 2 moles of ethylene oxide adduct of bisphenol A and terephthalic acid; (5) A mixture of (i) a modified urea-modified polyester prepolymer with hexamethylenediamine, the prepolymer obtained by reacting a polycondensation product of 2 moles of ethylene oxide adduct of bisphenol A and terephthalic acid with isophorone diisocyanate , and (ii) a polycondensation product of 2 moles of ethylene oxide adduct of bisphenol A and terephthalic acid; (6) A mixture of (i) a modified urea-modified polyester prepolymer with hexamethylenediamine, the prepolymer obtained by reacting a polycondensation product of 2 moles of ethylene oxide adduct of bisphenol A and terephthalic acid with diisocyanate of isophorone, and (ii) a polycondensation product of 2 moles of ethylene oxide adduct of bisphenol A / 2 moles of propylene oxide adduct of bisphenol A and terephthalic acid; (7) A mixture of (i) a modified urea-modified polyester prepolymer with ethylenediamine, the prepolymer obtained by reacting a polycondensation product of 2 moles of ethylene oxide adduct of bisphenol A and terephthalic acid with isophorone diisocyanate , and (ii) a polycondensation product of 2 moles of ethylene oxide adduct of bisphenol A and terephthalic acid; (8) A mixture of (i) a modified urea-modified polyester prepolymer with hexamethylenediamine, the prepolymer obtained by reacting a polycondensation product of 2 moles of ethylene oxide adduct of bisphenol A and terephthalic acid with diphenylmethane diisocyanate , and (ii) a polycondensation product of 2 moles of ethylene oxide adduct of bisphenol A and isophthalic acid; (9) A mixture of (i) a modified urea-modified polyester prepolymer with hexamethylenediamine, the prepolymer obtained by reacting a polycondensation product of 2 moles of ethylene oxide adduct of bisphenol A / 2 moles of oxide adduct propylene bisphenol A and terephthalic acid / dodecenylsuccinic anhydride with diphenylmethane diisocyanate, and (ii) a polycondensation product of 2 moles of ethylene oxide adduct with bisphenol A / 2 moles of propylene oxide adduct of bisphenol A and terephthalic acid; and (10) A mixture of (i) a modified urea-modified polyester prepolymer with hexamethylenediamine, the prepolymer obtained by reacting a polycondensation product of 2 moles of ethylene oxide adduct of bisphenol A and isophthalic acid with diisocyanate of toluene; and (ii) a polycondensation product of 2 moles of ethylene oxide adduct of bisphenol A and isophthalic acid; Compounds Containing Active Hydrogen Group Compounds containing active hydrogen groups serve as an extension agent or crosslinking agent when a polymer capable of reacting with the compounds containing active hydrogen groups is subjected to an extension or reaction reaction. crosslinking in the aqueous medium. The compound containing active hydrogen groups is not particularly limited and can be appropriately determined depending on the purpose proposed so long as it has an active hydrogen group. For example, when the polymer capable of reacting with the compound containing active hydrogen groups is a prepolymer (A) of polyester containing isocyanate groups, amines (B) are preferably used because high molecular weight polymers can be produced by reaction with the polyester prepolymer (A) containing isocyanate groups, for example, through the extension reaction or crosslinking reaction. The active hydrogen group is not limited in a particular way and can be determined appropriately depending on the proposed use; examples include hydroxyl groups (alcoholic hydroxyl group or phenolic hydroxyl group), amino groups, carboxyl groups, and mercapto groups. These groups can be used individually or in combination. Among these, an alcoholic hydroxyl group is particularly preferable. The amines (B) are not limited in a particular way and can be determined in an appropriate manner depending on the proposed use; examples include diamines (Bl), polyamines containing three or more amine (B2) groups, aminoalcohols (B3), aminomercaptans (B4), amino acids (B5), and compounds (B6) obtained by blocking the amino groups of (Bl) a (B5). These amines can be used individually or in combination. Among these, diamines (Bl), and mixtures of diamines (Bl) and a small one are more preferable. amount of polyamines (B2). Examples of the diamines (Bl) include aromatic diamines, alicyclic diamines, and aliphatic diamines. Examples of aromatic diamines include phenylenediamine, diethyltoluenediamine, and 4,4'-diaminodiphenylmethane. Examples of the alicyclic diamines include 4,4'-diamino-3, 3'-dimethyl-dicyclohexylmethane, diaminecyclohexane and isophorone diamine. Examples of aliphatic diamines include ethylenediamine, tetramethylenediamine and hexamethylenediamine. Examples of the polyamines containing 3 or more amine groups (B2) include diethylenetriamine and triphenetetramine. Examples of the amino alcohols (B3) include ethanolamine, and hydroxyethylaniline. Examples of the amino-mercaptans (B4) include aminoethyl mercaptan and aminopropyl mercaptan. Examples of amino acids (B5) include aminopropionic acid, aminocaproic acid. Examples of the compounds (B6) obtained by blocking the amino groups from (Bl) to (B5) include quetimine compounds, obtained from the above amines (Bl) to (B5) and ketones (for example, ketone, methyl ethyl ketone, and methyl isobutyl ketone), and oxazolidinone compounds.

To terminate an elongation reaction, crosslinking reaction, etc., between the compound containing active hydrogen groups and the polymer capable of reacting it, a reaction terminator may be used. The use of this reaction terminator is preferable because the molecular weight of the adhesive base material can be controlled within a desirable range. Examples of the reaction terminator include monoamines such as diethylamine, dibutylamine, butylamine and laurylamine, and compounds obtained by blocking these monoamines, such as ketimine compounds. For the mixing ratio of the amine (B) the polyester pre-polymer (A) containing isocyanate groups, the equivalent ratio of the isocyanate group [NCO] in the prepolymer (A) containing isocyanate groups to the amino group [NHx] in the amine (B) preferably 1/3 to 3/1, more preferably 1/2 to 2/1 and more preferably 1 / 1.5 to 1.5 / 1. If the equivalent ratio ([NCO] / [NHx]) is less than 1/3, it can result in a poor property of low temperature fixation. If the equivalent ratio is greater than 3/1, the molecular weight of the urea-modified polyester resin may decrease to result in a poor heat transfer property.

Polymers Capable of Reacting with Compounds that Contain Active Hydrogen Groups Polymers capable of reacting with the compounds containing active hydrogen groups (hereinafter referred to as "prepolymers" in some cases) are not particularly limited and can be appropriately selected from known resins in the technique, as long as they have at least one site capable of reacting with the compounds containing active hydrogen. Examples of these resins include polyol resins, polyacrylic resins, polyester resins, epoxy resins and derivatives thereof. These can be used individually or in combination. Among these, polyester resins are particularly preferable in view of their high melt flow and transparency. In the prepolymers, the site capable of reacting with the compounds containing active hydrogen groups is not particularly limited and can be appropriately selected from known substituents; examples include isocyanate group, epoxy group, carboxylic group and acid chloride group. These substituents can be included individually or in combination. Among these, an isocyanate group is particularly preferable.

Among the prepolymers, polyester resins containing groups that produce urea binding, or RMPE, are preferred, because the molecular weight of the high molecular weight component can be easily controlled, the excellent property of low temperature fixation can be measured. no oil for dry toners, and in particular, the excellent release property and an excellent fixing property can be ensured even when an oil-free fixing device is used. Examples of the groups that can produce a urea linkage include an isocyanate group. When the group that can form a urea linkage in the polyester resin RMPE is an isocyanate group, a suitable example of the polyester resin (RMPE) is the polyester prepolymer (A) containing isocyanate groups. The polyester prepolymer (A) containing isocyanate groups is not particularly limited and can be determined appropriately depending on the purpose intended; examples include polycondensation products resulting from polyols (PO) and polycarboxylic acids (PC), and those obtained by reaction of the compounds containing active hydrogen groups with polyisocyanates (PIC). Polyols (PO) are not limited in a particular way and can be determined appropriately depending on the proposed purpose; examples include diols (DIO), polyols containing three or more hydroxyl groups (TO), and mixtures of diols (DIO) and a small amount of (TO). These polyols (PO) can be used individually or in combination. For example it is preferable to use the diols (DIO) alone, or to use mixtures of diols (DIO) and a small amount of (TO). Examples of the diols (DIO) include alkylene glycols, alkylene ether glycols, alicyclic diols, alkylene oxide adducts of alicyclic diols, bisphenols and alkylene oxide adducts of bisphenols. The alkylene glycols have preferably 2 to 12 carbon atoms, and examples thereof include ethylene glycol, 1,2-propylene glycol, 1/3-propylene glycol, 1,4-butanediol and 1,6-hexanediol. Examples of alkylene ether glycols include diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, and polytetramethylene ether glycol. Examples of the alicyclic diols include 1,4-cyclohexane-dimethanol and hydrogenated bisphenol A. Examples of the alkylene oxide adducts of the alicyclic diols include those obtained by adding alkylene oxide such as ethylene oxide, propylene oxide, or butylene oxide to the alicyclic diols. The examples of bisphenols, including bisphenol A, bisphenol F, and bisphenol S. Examples of the alkylene oxide adducts of bisphenols include those obtained by adding alkylene oxide such as ethylene oxide, propylene oxide, or butylene oxide to bisphenols. . Among these, the alkylene glycols of 2 to 12 carbon atoms, and alkylene oxide adducts of the bisphenols are preferred. The alkylene oxide adducts of the bisphenols, and mixtures of the alkylene oxide adducts of the bisphenols and alkylene glycols of 2 to 12 carbon atoms are more preferable. For polyalcohols containing three or more hydroxyl groups (TO), these contain three to eight hydroxyl groups or those containing eight or more hydroxyl groups are preferable; examples include polyaliphatic alcohols containing three or more hydroxyl groups, polyphenols containing three or more hydroxyl groups, and alkylene oxide adducts of the polyphenols. Examples of the polyaliphatic alcohols containing three or more hydroxyl groups include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol and sorbitol. Examples of the polyphenols containing three or more hydroxyl groups include trisphenol PA, phenol novolac, and cresol novolac. Examples of ethylene oxide adducts of polyphenols containing three or more Hydroxyl groups include those obtained by adding alkylene oxides such as ethylene oxide, propylene oxide, or butylene oxide to polyphenols containing three or more hydroxyl groups. In the mixture of the diol (DIO) and the polyol containing three or more hydroxyl groups (TO), the mass ratio (DIO: TO) of the diol (DIO) to the polyol (TO) is preferably 100: 0.01-10 and more preferably, 100: 0.01-1. The polycarboxylic acids (PC) are not particularly limited and can be determined in an appropriate manner depending on the proposed purpose; examples include dicarboxylic acids (DIC), polycarboxylic acids containing three or more carboxyl groups (TC), and mixtures of dicarboxylic acids (DIC), and polycarboxylic acids (TC). These polycarboxylic acids can be used individually or in combination. It is preferable to use dicarboxylic acids (DIC), alone, or to use mixtures of dicarboxylic acids (DIC), and a small amount of the polycarboxylic acids (TC). Examples of the dicarboxylic acids include alkylene dicarboxylic acids, alkenylenedicarboxylic acids, and aromatic dicarboxylic acids.

Examples of the alkylene dicarboxylic acids include succinic acid, adipic acid and sebacic acid. For alkenylene dicarboxylic acids, those having 4 to 20 carbon atoms are preferred, and examples thereof include maleic acid, and fumaric acid. For aromatic dicarboxylic acids, those having from 8 to 20 carbon atoms are preferred, and examples thereof include phthalic acid, isophthalic acid, terephthalic acid, and naphthalene dicarboxylic acid. Among these, alkenylene dicarboxylic acids having from 4 to 20 carbon atoms and aromatic dicarboxylic acids having from 8 to 20 carbon atoms are preferred. For polycarboxylic acids containing three or more carboxyl groups (TO), those containing three to eight carboxyl groups and those containing eight or more carboxyl groups are preferable, and examples thereof include aromatic polycarboxylic acids. For aromatic polycarboxylic acids, those having from 9 to 20 carbon atoms are preferred, and examples thereof include trimellitic acid and pyromellitic acid. For polycarboxylic acids (PC), acid anhydrides obtained from dicarboxylic acids (DIC), polycarboxylic acids containing three or more carboxyl groups (TC) and mixtures of dicarboxylic acids (DIC) and polycarboxylic acids (TC), or lower alkyl esters can be used. Examples of the lower alkyl ethers include methyl esters, ethyl esters and isopropyl esters. In the mixture of dicarboxylic acid (DIC) and polycarboxylic acid containing three or more carboxyl groups (TC), the mass ratio (DIC: TC) of dicarboxylic acid (DIC) to polycarboxylic acid (TC) is not particularly limited and it can be determined in an appropriate manner depending on the proposed purpose. For example, the mass ratio (DIC: TC) in the mixture is preferably 100: 0.01-10 and more preferably 100: 0.01-1. The mixing ratio of the polyols (PO) to the polycarboxylic acids (PC) in their polycondensation reaction is not particularly limited and can be determined appropriately depending on the proposed purpose, for example, the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] in the polyol (PO) to the carboxyl group [COOH] in the polycarboxylic acid (PC) is preferably 2/1 to l / l, more preferably 1. 5/1 to 1/1 and more preferably 1.3 / 1 to 1.02 / 1. The content of the polyol (PO) in the prepolymer (A) Polyester containing isocyanate groups is not particularly limited and can be determined in an appropriate manner depending on the purpose proposed. For example, the content is preferably 0.5% by mass to 40% by mass, more preferably 1% by mass to 30% by mass and more preferably, 2% by mass to 20% by mass. The content of the polyol (PO) in the polyester prepolymer (A) containing isocyanate groups is less than 0.5% by mass, can result in a poor heat-displacement property and the resulting toner does not have excellent thermal stability and excellent Fixation property at low temperature. If the content is greater than 40% by mass, poor fixing property at low temperature can result. The polyisocyanates (PIC) are not particularly limited and can be appropriately determined depending on the proposed purpose; examples include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic diisocyanates, aromatic aliphatic diisocyanates, isocyanurates, phenol derivatives thereof, and polyisocyanates blocked with oximes or caprolactams. Examples of the aliphatic psiisocyanates include tetramethylene diisocyanate, hexamethylene diisocyanate and 2,6-diisocyanato-methyl-ca-roate, octamethylene diisocyanate, decamethylene diisocyanate, diisocyanate of dodecamethylene, tetradecamethylene diisocyanate, trimethylhexane diisocyanates, and tetramethylhexane diisocyanates. Examples of the alicyclic polyisocyanates include isophorone diisocyanate, and cyclohexylmethane diisocyanate. Examples of the aromatic diisocyanates include toluene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, diphenylene-4,4'-diisocyanate, 4,4'-diisocyanato-3,3'-dimethylphenyl, 3-methyldiphenyl. -methane-4, 4 '-diisocyanate, and diphenyl-4,4'-diisocyanate. Examples of the aromatic aliphatic diisocyanates include a, a, a ', a-tetramethylxylylene diisocyanate. Examples of the isocyanurates include tris-isocyanatoalkyl isocyanurate, and triisocyanatocycloalkyl isocyanurates. These polyisocyanates can be used individually or in combination. In the reaction between the polyisocyanate and the polyester resin containing active hydrogen groups (for example, polyester resin containing hydroxyl groups), the equivalent ratio [NHO] / [OH] of the isocyanate group [NCO] in the polyisocyanate (PIC) to the hydroxyl group [OH] in the polyester resin containing hydroxyl groups is preferably 5/1 to l / l, more preferably 4/1 to 1. 2/1 and more preferably 3/1 to 1.5 / 1. If the isocyanate group [NCO] ratio exceeds , can result in a poor fixing property at low temperature. If the isocyanate group [NCO] ratio is less than 1, it can result in poor anti-transfer property. The content of the polyisocyanate component (PIC) in the polyester prepolymer (A) containing isocyanate group is not particularly limited and can be determined appropriately depending on the proposed purpose, for example, it is preferably 0.5 mass% to 40 mass%, more preferably 1% by mass to 30% by mass and more preferably, from 2% to 20% by mass. If the content is less than 0.5% by mass, it can result in poor heat transfer property and it can be difficult for the resulting toner to have excellent thermal stability and an excellent property of low temperature setting. If the content is greater than 40% by mass, it can result in a poor fixing property at low temperature. The average number of isocyanate groups contained per molecule of the polyester prepolymer (A) containing isocyanate groups is preferably one or more, more preferably 1.2 to 5 and more preferably 1.5 to 4. If the average number of groups isocyanate by The molecule is less than 1, the molecular weight and a polyester resin modified by the group to produce a urea bond (RMPE), may decrease to result in poor heat-displacement property. The weight average molecular weight (Mw) of the polymer capable of reacting with the compound containing active hydrogen groups is preferably 1,000 to 30,000 and more preferably 1,500 to 15,000, as determined by gel permeation chromatography (GPC) ) based on the molecular weight distribution of the polymer dissolved in tetrahydrofuran (THF). If the weight average molecular weight (Mw) of the polymer is less than 1,000, it may result in poor thermal stability of the toner, and if the weight average molecular weight (Mw) of the polymer is greater than 30,000, it may result a poor fixing property at low temperature. The determination of the average molecular weight distribution by GPC can be carried out in the following procedure, by way of example. A column is first equilibrated in a thermal chamber of 40 ° C. At this temperature, tetrahydrofuran (THF), a column solvent, is passed through the column at a flow rate of 1 ml / min, and a sample solution containing a concentration of 0.05-0.6% in resin mass in tetrahydrofuran, and 50-200 μl of the sample solution is passed through the column. In determining the molecular weight of the sample, a molecular weight calibration curve constructed of several monodisperse polystyrene standards is used to obtain a molecular weight distribution of the sample solution based on the relationship between the logarithm values of the curve and the heats of the account. For the polystyrene forms for the calibration curve, those with a molecular weight of 6 x 102, 2.1 x 102, 4 x 102, 1.75 x are preferably used. 104, 1.1 x 10s, 3.9 x 105, 8.6 x 105, 2 x 106, and 4.43 x 10s (produced by Pressure Chemical Corp., or Toyo Soda Manufacturing Co., Ltd). Also, preferably at least 10 different polystyrene standards are used. For a detector, a refractive index detector (Rl) is used.

Binder Resin The binder resin is not particularly limited and can be determined appropriately depending on the purpose proposed; examples include polyesters. Of these, unmodified polyester resins (i.e., polyester resins that are not modified) are particularly preferable. The addition of this unmodified polyester queen in the toner leads to improved properties of fixing at low temperature and make the image bright. Examples of the unmodified polyester resins include resins identical to the above polyester resins that contain a group that produces a urea bond (RMPE), ie, polycondensation products of polyols (PO) and polycarboxylic acids (PC). In view of the low temperature setting properties and the hot transfer property, preferably a part of the unmodified polyester resin is compatible with the polyester resin containing a group that produces a urea bond (RMPE) , that is to say, unmodified polyester resins and polyester resins (RPME) are preferentially part of a similar structure that allows them to be compatible. The weight average molecular weight (Mw) of the unmodified polyester resin is preferably from 1,000 to 30,000 and more preferably from 1,500 to 15,000 as determined by gel permeation chromatography (GPC) based on the molecular weight distribution of the polymer dissolved in tetrahydrofuran (THF). If the weight average molecular weight (Mw) of the unmodified polyester resin is less than 1,000, poor thermal stability of the toner may result. Therefore, the content of an unmodified polyester resin with an average molecular weight in Weight of less than 1,000 is 8% by mass to 28% by mass. If the weight average molecular weight (Mw) of the unmodified polyester resin is greater than 30,000, it can result in a poor property of low temperature fixation. The glass transition temperature of the unmodified polyester resins is generally from 30 ° C to 70 ° C, preferably from 35 ° C to 70 ° C, more preferably from 35 ° C to 70 ° C and more preferably, from 35 ° C to 45 ° C. If the vitreous transition temperature is below 30 ° C, it may result in poor thermal stability of the toner. If the vitreous transition temperature is above 70 ° C, it can result in an insufficient fixing property at a lower temperature. The hydroxyl number of the unmodified polyesters is preferably 5 mg KOH / g or more, preferably 10 mg KOH / g to 120 mg KOH / g and more preferably 20 mg KOH / g to 80 mg KOH / g. If the hydroxyl number is less than 5 mg KOH / g, it may be difficult for the resulting toner to achieve excellent thermal stability and an excellent property of low temperature fixation. The acid value of the unmodified polyester resins is preferably 1.0 mg KOH / g to 50.0 mg KOH / g, preferably 1.0 mg KOH / g to 45.0 mg KOH / g and more preferably 15.0 mg KOH / g at 45.20 mg KOH / g. In general, toner having an acid value can be easily charged in a negative manner. When the unmodified polyester resin is contained in the toner material, in the mixture, the mass ratio of the polymer capable of reacting with the compounds containing active hydrogen groups (for example, a polyester resin containing a group that produces a urea linkage) to the unmodified polyester resin is preferably 5/95 to 80/20 and more preferably 10/90 to 25/75. If the mass ratio of the unmodified polyester resin (PE) exceeds 95 in the mixture, the heat transfer property can be reduced and it can be difficult for the resulting toner to achieve excellent thermal stability and excellent low temperature fixing property. . If the mass ratio of unmodified polyester is less than 20, it can reduce the brightness of the image. The content of the unmodified polyester resin in the binder resin is preferably 50% by mass to 100% by mass, more preferably 75% by mass to 95% by mass and most preferably 80% by mass to 90% by mass, by way of example. If the content is less than 50% by mass, it can result in a poor property of low temperature fixation and / or reduce the brightness of the image.

Dye The dye is not particularly limited and can be selected appropriately from known dyes and known pigments, accordingly. Examples include carbon black, nigrosine dyes, iron black, Naphthol Yellow S, Hansa Yellow (10G, 5G, 6), cadmium yellow, yellow iron oxide, yellow ocher, chrome yellow, Yellow Titan, Yellow Polyazo, Oil Yellow, Hansa Yellow (GR, A, RN, R), Pigment Yellow L, Benzidine Yellow (G, GR), Permanent Yellow (NCG), Shooting Vulcan Yellow (5G, R), Tartrazine Lacquer, Yellow Quinoline lacquer, yellow anthracene BGL, isoindoline yellow, colcotar, red lead oxide, lead red, cadmium red, cadmium mercury red, antimony red, Permanent Red 4R, Para-Red, Fire Red, red of Parachlorothonitroaniline, Scarlet G Fleeting of Litol, Scarlet Brillante Fugaz, Carmina Brillante BS, Red Permanent (F2R, F4R, FRL, FRLL, F4RH), Scarlet VD Shooting, Rubine Vulcan Shooting, Scarlet Brilliant G, Rubine Litol GX, Red Permanent F5R , Carmina Brillante 6B, Pigment Scarlet 3B, Bordeaux 5B, Dark Red Toluid ina, Bordeaux Permanent F2K, Bordeaux Helium BL, Bordeaux 10B, Dark Red Light BO ?, Medium Dark Red BO ?, Eosin Lacquer, Rhodamina B Lacquer, Rhodamina Lacquer Y, Alizarina Lacquer, Tioindigo Red B, Dark Indigo Thioindigo Red, Oil Red, Quinacridone Red, Pyrazolone Red, Poliazo Red, Chromium Vermilion, Benzidine Orange, Perinone Orange , Orange Oil, Cobalt Blue, Cerulean Blue, Alkaline Blue Lacquer, Blue Pavón Lacquer, Victoria Blue Lacquer, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Blue Fleeting Sky, Indanthrene Blue (RS, BC ), Indigo, Ultramarine, Prussian Blue, Anthraquinone Blue, Shooting Violet B, Methyl Violet Lacquer, Cobalt Violet, Manganese Violet, Dioxazine Violet, Anthraquinone Violet, Chromium Green, Zinc Green, Chrome Oxide , viridian, emerald green, Green Pigment B, Green B Naphthol, Greenish Gold, Acid Green Lacquer, Malachite Green Lacquer, Phthalocyanine Green, Anthraquinone Green, titanium oxide, zinc white and lithopone. These can be used individually or in combination. The content of the toner dye is not limited in a particular way and can be determined in an appropriate manner depending on the proposed purpose; however, from 1% by mass to 15% by mass and more preferably from 3% by mass to 10% by mass is preferred. If the dye content is less than 1% by mass, the dyeing power of the toner can be degraded. If he Dye content is greater than 15% by mass, occurs in the toner abnormal dispersion of the pigment, and can reduce the dyeing power and electrical characteristics of the toner. The dyes can be used as a main batch combined with resin. The resin is not particularly limited and can be appropriately selected from those known in the art, examples include polymers of styrene or substituted styrene, styrene copolymers, polymethyl-methacrylates, polybutyl-methacrylates, polyvinyl chlorides, acetates of polyvinyl, polyethylenes, polypropylenes, polyesters, epoxy resins, epoxy-polyol resins, polyurethanes, polyamides, polyvinyl-butyrals, polyacrylic resins, rosins, modified rosins, terpene resins, aliphatic hydrocarbon resins, alicyclic hydrocarbon resins, petroleum resins aromatics, chlorinated paraffins and paraffins. These resins can be used individually or in combination. Examples of the styrene or substituted styrene polymers include polyester resins, polystyrenes, poly-p-chlorostyrenes, and polyvinyl-toluenes. Examples of styrene copolymers include styrene-p-chlorostyrene copolymers, styrene-propylene copolymers, styrene-vinyltoluene copolymers, copolymers of styrene-vinylnaphthalene, styrene-methyl acrylate copolymers, styrene-ethyl acrylate copolymers, styrene-butyl acrylate copolymers, styrene-octyl acrylate copolymers, styrene-methyl methacrylate copolymers, styrene-ethyl methacrylate copolymers, copolymers of styrene-butyl methacrylate, copolymers of styrene-chloromethacrylate of α-methyl, styrene-acrylonitrile copolymers, styrene-vinylmethyl-ketone copolymers, styrene-butadiene copolymers, styrene-isoprene copolymers, styrene-acrylonitrile-indene copolymers , styrene-maleic acid copolymers, and styrene-maleate ester copolymers. The main batch can be produced by mixing or kneading the resin of the main batch with the dye while a high cutting force is applied. Here, for increased interaction between the dye and the resin, an organic solvent may be added thereto. Alternatively, a so-called process of an intermittent process is preferably used, because in the intermittent process a wet dye cake can be used as it is without drying. The intermittent process is a process in which an aqueous paste of dye is mixed and kneaded with resin together with an organic solvent to thereby transfer the dye to the side of the resin to be removable from moisture and organic solvent.

For mixing and kneading, a high-cut dispersing device (for example, a triple roller mill) is preferably used.

Additional Ingredients The additional ingredients are not limited in a particular way and can be determined in an appropriate manner depending on the proposed purpose; examples include a release agent, a charge control agent, inorganic particles, cleaning improver, magnetic material, and metallic soap. The release agent is not limited in a particular way and can be appropriately selected from those known in the art; Suitable examples include waxes. Examples of these waxes include long chain hydrocarbons, waxes containing carbonyl groups, and polyolefin waxes. These waxes can be used individually or in combination. Among these, waxes containing carbonyl groups are preferable. Examples of the waxes containing carbonyl groups include polyalkanoic acid esters, polyalkanol esters, polyalkanoic acid amides, polyalkylene amides, and dialkyl ketones. Examples of the polyalkanoic acid esters include carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate and 1,18-octadecanediol distearate. Examples of the polyalkanol esters include tri-ethyl tristearate, and distearyl maleate. Examples of the polyalkanoic acid amide include behenyl amides. Examples of the polyalkyl amide include triaryl acid tristearyl amide. Examples of dialkyl ketones include distearyl ketone. Of these waxes containing carbonyl groups, polyalkanoic esters are more preferable. Examples of the polyolefin waxes include polyethylene waxes, and polypropylene waxes. Examples of the long chain hydrocarbons include paraffin waxes and Sasol wax. The melting point of the release agent is not limited in a particular way and can be determined in an appropriate manner depending on the proposed purpose; it is preferably from 40 ° C to 160 ° C, more preferably from 50 ° C to 120 ° C and more preferably from 60 ° C to 90 ° C. If the melting point of the release agent is below 40 ° C, the wax can impart thermal stability of the toner. If the melting point of the release agent is below 160 ° C, cold hardening may occur in the low temperature setting.

The melt viscosity of the release agent is preferably 5 cps at 1,000 cps and more preferably, 10 cps at 100 cps when measured at a temperature higher than the melting point of the release agent at 20 ° C. If the melting viscosity of the release agent is less than 5 cps, it may result in a poor release property. If the melt viscosity of the release agent is greater than 1,000 cps, it can result in poor heat transfer property and a poor property of low temperature fixation. The content of the release agent in the toner is not particularly limited and can be determined in an appropriate manner depending on the proposed purpose; preferably 0% by mass to 40% by mass and more preferably, 3% by mass to 30% by mass. If the content of the release agent is greater than 40% by mass, the fluidity of the toner can be reduced. The charge control agent is not particularly limited and can be appropriately selected from those known in the art. However, when a colored material is used for the charge control agent, the toner may look for different color tones; therefore, colorless materials are preferably used or materials close to white. Examples include, triphenylmethane dyes, molybdic acid chelate segments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (including modified quaternary ammonium fluoride salts), alkylamides, phosphorus or compounds thereof, tungsten or compounds of the same, fluoride activators, metal salts of salicylic acid, and metal salts of salicylic acid derivatives. This can be used individually or in combination. For the cargo control agent, commercially available products can be used; examples include Bontron P-51, a quaternary ammonium salt, Bontron E-82, a metal complex of oxinaphthoic acid, Bontron E-84, a metal complex of salicylic acid, and Bontron E-89, a phenol condensate (produced by Orient Chemical Industries, Ltd.); TP-302 and TP-415, both are a molybdenum metal complex of quaternary ammonium salt (produced by Hodogaya Chemical Co.); PSY Copy Load VP2038, a quaternary ammonium salt, PR Copy Blue, a triphenylmethane derivative, and NEG VP2036 Copy Charge and NX VP434 Copy Charge, both being a quaternary ammonium salt (produced by Hoechst Ltd.); LRA-901 and LR-147, a boron metal complex (produced by Japan Carlit Co., Ltd.); quinacridones; azo pigments; and high molecular weight compounds that have a functional group (by example, sulfonic group and carboxylic group). The charge control agent can be melted and kneaded with the main batch before dissolution or dispersion. Alternatively, the charge control agent can be dissolved or dispersed in the organic solvent together with the above toner ingredients which can be attached to the resulting toner particles. The proper content of the toner control agent in the toner varies depending on the type of the binder resin, the presence of an additive, the dispersion method, etc. However, it is preferably present in the toner in an amount of 0.1 parts by mass to 10 parts by mass per 100 parts by mass of the binder resin and more preferably 0.2 parts by mass to 5 parts by mass. If less than 0.1 parts by mass is used, it can be difficult to control the amount of charge. If more than 10 parts by mass is used, the toner is loaded excessively so that the effects of the control agent are reduced, causing the toner to be firmly attracted to the developer roller by the electrostatic attractive force. For these reasons, the fluidity of the developer can be reduced and / or the density of the image can be reduced.

Resin particles Resin particles are not limited in a way In particular, and can be selected from appropriate mannings of resins known in the art as long as the resin particles are capable of forming an aqueous dispersion in an aqueous medium, they can be either thermoplastic resin or thermosetting resin, and the examples include resins of vinyl, urethane resins, epoxy resins, polyamide resin, polyimide resins, silicone resins, phenol resins, melamine resins, urea resins, aniline resins, ionomer resins, and polycarbonate resins. Among these, vinyl resins are preferable. These can be used individually or in combination. The resin particles are preferably formed from a resin selected from vinyl resins, polyurethane resins, epoxy resins, and polyester resins in view of the easy production of an aqueous dispersion containing fine and spherical particles of resin. Vinyl resins are homopolymers or copolymers of vinyl monomers. Examples include styrene-ester (meth) acrylic resins, styrene-butadiene copolymers, copolymers of (meth) acrylic acid-acrylic ester, styrene-acrylonitrile copolymers, styrene-maleic anhydride copolymers, and styrene-acid copolymers ( met) acrylic. In addition, copolymers can also be used which they contain monomers having at least two unsaturated groups for the formation of the resin particles. The monomer containing at least two unsaturated groups is not particularly limited and can be appropriately determined depending on the proposed purpose; examples include sodium salt of sulfuric acid ester of ethylene oxide adduct of methacrylic acid (Eleminol RS-30, produced by Sanyo Chemical Industries Co.), divinylbenzene, and 1,6-hexanediol acrylate. The resin particles are formed by polymerization of the above monomers according to an appropriately selected conventional method. The resin particles are preferably produced in an aqueous dispersion. Examples of the method for preparing this aqueous dispersion containing the resin particles are the following (1) to (8): (1) in a case of the above vinyl resin, the vinyl monomers as a starting material are polymerized by suspension polymerization, emulsion polymerization, seeding polymerization or dispersion polymerization to directly prepare an aqueous dispersion of resin particles, (2) in a resin case obtained by reaction of polyaddition or polycondensation (for example, the above polyester resin, polyurethane resin, or epoxy resin), a precursor (monomers, oligomers or the like) or a solution containing the precursor is dispersed in an aqueous medium in the presence of an appropriate dispersing agent, and is heated or added with a curing agent for curing to prepare a aqueous dispersion of the resin particles; (3) In a case of resin obtained by polyaddition reaction or polycondensation (for example, the above polyester resin, polyurethane resin, or epoxy resin), an appropriately selected emulsifier is dissolved in a precursor (monomer, oligomer, or the like) ) or in a solution containing the precursor (preferably, a liquid solution, can be liquefied by heat), followed by addition of water to induce phase inversion emulsification to prepare an aqueous dispersion of resin particles; (4) resin that has been previously prepared by polymerization (addition polymerization, ring-opening polymerization, polyaddition, addition condensation or condensation polymerization) is sprayed in a blade-type or jet-type spray, the resulting resin powder is classified to produce resin particles, and the resin particles are dispersed in an aqueous medium in the presence of an appropriately selected dispersing agent to prepare an aqueous dispersion of the resin particles; (5) resin that has been prepared previously by polymerization (addition polymerization, ring opening polymerization, polyaddition, addition condensation or condensation polymerization) is dissolved in a solvent to prepare a resin solution, the resin solution is sprayed in the form of mist to produce particles of resin, and the resulting resin particles are dispersed in an aqueous medium in the presence of an appropriately selected dispersing agent to prepare an aqueous dispersion of the resin particles; (6) resin that has been prepared above by polymerization (addition polymerization, ring opening polymerization, polyaddition, addition condensation or condensation polymerization) is dissolved in a solvent to prepare a resin solution, the resin particles are precipitated by the addition of a lean solvent or by cooling the resin solution, the solvent is removed to recover the resin particles, and the resin particles obtained in this way are dispersed in an aqueous medium in the presence of an appropriately selected dispersing agent. for preparing an aqueous dispersion of the resin particles; (7) resin that has been prepared above by polymerization (addition polymerization, ring opening polymerization, polyaddition, addition condensation or condensation polymerization) is dissolved in a solvent to prepare a solution of resin, the resin solution is dispersed in an aqueous medium in the presence of an appropriately selected dispersing agent, and the solvent is removed upon heating or by vacuum to prepare an aqueous dispersion of the resin particles; and (8) resin that has been prepared above by polymerization (addition polymerization, ring opening polymerization, polyaddition, addition condensation or condensation polymerization) is dissolved in a solvent to prepare a resin solution, an emulsifier is dissolved appropriately selected in the resin solution, and water is added to the resin solution to induce phase inversion emulsification to thereby prepare an aqueous dispersion of resin particles; Examples of the toner include those produced by polymerization of known suspension, emulsion aggregation, or emulsion dispersion. Toners prepared in the following procedure are also preferable. A toner material containing a compound containing active hydrogen groups and a polymer capable of reacting with the compound is dissolved in an organic solvent to prepare a toner solution, the toner solution is dispersed in an aqueous medium to prepare a dispersion, where the compound containing active hydrogen groups is allowed to react with the polymer to produce a particulate adhesive base material, and the organic solvent is removed to prepare toner particles.

Toner Solution The preparation of the toner solution is carried out by dissolving the toner material in the organic solvent.

Organic Solvent The organic solvent is not particularly limited and can be determined in an appropriate manner depending on the purpose proposed, as it is a solvent capable of dissolving and dispersing the toner material. The organic solvent is preferably selected from volatile organic solvents with a boiling point of less than 150 ° C because it can be easily removed; examples include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethene, 1,1,2-trichloroethane, trichlorethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, methyl ethyl -ketone, and methyl isobutyl ketone. Among these organic solvents, toluene, xylene, benzene, methylene chloride, 1,2-dichloroethane, chloroform, carbon tetrachloride and the like are preferable. similar, and ethyl acetate is more preferable. These organic solvents can be used individually or in combination. The added amount of the organic solvent is not limited in a particular way and can be determined in an appropriate manner depending on the proposed purpose. A quantity of 40 parts by mass is preferably added to 300 parts by mass per 100 parts by mass of the toner material, more preferably 60 parts by mass to 140 parts by mass and more preferably 80 parts by mass to 120 parts in mass.

Dispersion The preparation of the dispersion is carried out by dispersing the toner solution in an aqueous medium. When the toner solution is dispersed in the aqueous medium, the solid dispersions (oil droplets) derived from the toner solution are formed in the aqueous medium.

Aqueous Medium The aqueous medium is not particularly limited and can be appropriately selected from those known in the art; examples include water, water miscible solvents and mixtures thereof. Between these, water is more preferable. Water-miscible solvents are not limited in particular as long as they are miscible in water, and examples include alcohols, dimethylformamide, tetrahydrofurans, cellosolves, and lower ketones. Examples of the alcohols include methanol, isopropanol and ethylene glycol. Examples of lower ketones include acetone and methyl ethyl ketone. These organic solvents can be used individually or in combination. The toner solution is preferably dispersed in the aqueous medium with agitation. The dispersion method is not particularly limited and a known dispersion device can be used. Examples of this dispersion device include a low velocity shear dispersing device, a high speed shear dispersing device, a friction type dispersion device, a high pressure jet dispersion device, and a high velocity dispersion device. Ultrasound scattering. Among these, a high speed cutting dispersion device is preferred because it is possible to adjust the diameter of the solid dispersion (oil droplets) from 2 μm to 20 μm. When using a high speed cutting dispersion device, the rotation speed, time of dispersion, dispersion temperature, etc., are not particularly limited and can be adjusted appropriately according to the proposed purpose. For example, the rotation speed is preferably 1,000 rmp to 30,000 rmp and more preferably 5,000 rmp to 20,000 rmp. In a case of a batch-type dispersion device, the dispersion time is preferably 0.1 to 5 minutes, and the dispersion temperature is preferably 0 ° C to 150 ° C and more preferably 40 ° C. C at 98 ° C. It is indicated in general, that the higher the dispersion temperature, the easier it disperses. As an example of the toner production process, a toner production process will be described in which a particulate adhesive base material is produced to obtain the toner. In this process, a phase of aqueous medium, the toner solution and the dispersion are prepared, the aqueous medium is added and the other steps are carried out (for example, synthesis of a prepolymer capable of reacting with the compounds containing hydrogen groups). active, and the synthesis of these compounds containing active hydrogen groups). The preparation of the aqueous medium phase can be carried out by dispersing the resin particles in the aqueous medium. The content of the resin particles of The aqueous medium is not particularly limited and can be determined appropriately depending on the proposed purpose, for example, an amount of 0.5% by mass to 10% by mass is preferably present. The preparation of the toner solution can be carried out by dissolving or dispersing toner materials, the compound containing active hydrogen groups, polymer capable of reacting with the compound, dye, charge control agent, unmodified polyester resin, etc., in the organic solvent. In addition, inorganic oxide particles such as silica or titania can be added to the organic solvent so as to form a layer containing inorganic oxide particles within 1 μm of the surface of the toner. Among the toner materials, ingredients other than the prepolymer (or polymer capable of reacting with the compound containing active hydrogen groups) can be added to the organic solvent at the time when the resin particles are dispersed therein, or it can be added to the aqueous medium phase at the time when the toner solution is added to this. The preparation of the dispersion can be carried out by emulsifying or dispersing the toner solution in the aqueous medium phase. Making both the compound containing active hydrogen groups and the polymer capable reacting with these compounds are subjected to an extension or crosslinking reaction leading to the formation of adhesive base material. For example, the adhesive base material (e.g., urea-modified polyester) can be produced in any of the following ways (1) to (3): (1) the toner solution containing the polymer capable of reacting with the compound containing active hydrogen groups (for example, the polyester-containing prepolymer (A) containing isocyanate groups) is emulsified or dispersed in the aqueous medium phase together with the compound containing active hydrogen groups to form solid dispersions, allowing the compound containing active hydrogen groups and the polymer capable of reacting with the compound containing active hydrogen groups is subjected to an extension or crosslinking reaction in the aqueous medium phase; (2) the toner solution is emulsified or dispersed in the aqueous medium in which the compound containing active hydrogen groups has been previously added, forming the solid dispersions, and then the compound containing active hydrogen groups and the polymer capable reacting with this compound are allowed to undergo extension or cross-linking reaction in the aqueous medium phase; and (3) after adding the toner solution to the aqueous medium phase followed by mixing, the compound containing active hydrogen groups is added thereto to form solid dispersions, and then the compound having active hydrogen groups and the polymer capable of reacting with this compound are allowed to undergo extension or crosslinking reaction at particle interfaces in the aqueous phase. In the case of the process (3), it should be noted that the modified polyester resin is formed preferentially on the surface of the toner particles, allowing the generation of a concentration gradient in the toner particles. The reaction conditions under which the adhesive base material is produced by emulsification or dispersion are not particularly limited and can be adjusted appropriately according to the combination of the active hydrogen group containing compound with the polymer capable of reacting with East. The reaction time is preferably 10 minutes to 40 hours and more preferably, 2 hours to 24 hours. The reaction temperature is preferably from 0 ° C to 150 ° C and more preferably from 40 ° C to 98 ° C. A suitable example of the method for stably forming in the aqueous medium phase the solid dispersions containing the compound containing active hydrogen groups and a polymer capable of reacting with this compound (for example, prepolymer A) of polyester containing isocyanate groups) is as follows: the toner solution in which the toner materials such as a polymer capable of reacting with the compound that dissolves or disperses in an organic solvent are dissolved in an organic solvent. contains groups of active hydrogen (eg, prepolymer A) of polyester containing isocyanate groups), dye, charge control agent, unmodified polyester resin, etc., is added to the aqueous medium phase, and dispersed by application of cutting force. It is noted that the description of the dispersion method is similar to that given above. In the preparation of the dispersion, a dispersion agent is preferably used where it is necessary in order to stabilize the solid dispersions (oil droplets derived from the toner solution), to obtain a desired particle shape, and to harden the particle size distribution. The dispersing agent is not limited in a particular way and can be determined in an appropriate manner depending on the proposed purpose. Suitable examples include surfactants, water insoluble inorganic dispersing agents, and polymeric protective colloids. These dispersing agents can be used individually or in combination.

Examples of the surfactants include anionic surfactants, cationic surfactants, nonionic surfactants and ampholytic surfactants. Examples of the anionic surfactants include alkylbenzene sulphonic acid salts, α-olefin sulphonic acid salts, and phosphoric acid esters. Among these, those having a fluoroalkyl group are preferable. Examples of the anionic surfactants having a fluoroalkyl group include fluoroalkylcarboxylic acids of 2-10 carbon atoms or metal salts thereof, disodium per-fluorooctanesulfonylglutamate, sodium-3-sulfonates. { omega- (C6-Cll) fluoroalkyloxy} -l- (C3-C4) alkyl, sodium-3-. { omega- (C6- C8) fluoroalkanoyl-N-ethylamino) -1-propanosylphonates, acids (C11-C20) fluoroalkylcarboxylics or metal salts thereof, (C7-C11) perfluoroalkylcarboxylic acids or metal salts thereof, (C4-C12) perfluoroalkylsulfonic acids or metal salts thereof, diethanolamide of perfluorooctanesulfonic acid, N-propyl-N- (2-hydroxyethyl) perfluorooctanesulfone amide, (C6-C10) perfluoroalkylsulfonaamidepropyltrimethylammonium salts, (C6-C16) monoperfluoroalkylethyl phosphate salts. Examples of commercially available surfactants that have a fluoroalkyl group include Surflon S-III, S-112 and 5-113 (manufactured by Asahi Glass Co.); Frorard FC-93, FC-96, FC-98 and FC-129 (manufactured by Sumitomo 3M Ltd); Unidyne DS-101 and DS-102 (manufactured by Daikin Industries, Ltd.); Megafac F-110, F-120, F-113, F-191, F-812 and F-833 (manufactured by Dainippon Ink and Chemicals, Inc.); ECTOP EF-102, 103, 104, 105, 112, 123A, 123B, 306A 501, 201 and 204 (manufactured by Tohchem Products Co.); and Futargent F-100 and F150 (manufactured by Neos Co.). Examples of the cationic surfactants include amine salts, and quaternary amine salts. Examples of the amine salts include alkyl amine salts, fatty acid derivatives of aminoalcohols, polyamine fatty acid derivatives, and imidazolines. Examples of the quaternary ammonium salts include alkyltrimethylammonium salts, dialkyldimethyl ammonium salts, alkyldimethylbenzyl ammonium salts, pyridinium salts, alkyl isoquinolinium salts, and benzethonium chlorides. Among these, preferable examples are primary, secondary or tertiary aliphatic amine acids, having a fluoroalkyl group, aliphatic quaternary ammonium salts such as (C6-C10) perfluoroalkylsulfone amide propyltrimethylammonium salts, benzalkonium salts, benzethonium chlorides. , pyridinium salts, and imidazolinium salts. The specific examples of commercially available products thereof include Surflon S-121 (manufactured by Asahi Glass Co.); Frorard FC-135 (manufactured by Sumitomo 3M Ltd); Unidyne DS-202 (manufactured by Daikin Industries, Ltd.); Megafac F-150 and F-824 (manufactured by Dainippon Ink and Chemicals, Inc.); Ectop EF-132 (manufactured by Tohchem Products Co.); and Futargent F-300 (manufactured by Neos Co.). Examples of the nonionic surfactants include fatty acid amide derivatives and polyalcohol derivatives. Examples of the ampholytic surfactants include alanine, dodecyldi (aminoethyl) glycine, dioctylaminoethyl) glycine, and N-alkyl-N, N-dimethylammonium-betaine. Examples of the water insoluble inorganic dispersing agents include tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica and hydroxyl apatite. Examples of polymeric protective colloids include acids, (meth) acrylic monomers containing hydroxyl groups, vinyl alcohol or esters thereof, vinyl alcohol esters and carboxyl group containing compounds, amide compounds or methylol compounds thereof, chlorides , homopolymers or copolymers of monomers containing a nitrogen atom or ring heterocyclic containing a nitrogen atom, polyoxyethylenes and celluloses. Examples of the acids include acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itanonic acid, crotonic acid, fumaric acid, maleic acid and maleic anhydride. Examples of the (meth) acrylic monomers containing hydroxyl groups include β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate. , 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerin monoacrylate, glycerin monomethacrylate, N-methylol-acrylamide and N-methylol-methacrylamide. Examples of vinyl alcohol ethers include vinyl methyl ether, vinyl ethyl ether, and vinyl propyl ether. Examples of vinyl alcohol esters and compounds containing carboxyl groups include vinyl acetate, vinyl propionate and vinyl butyrate. Examples of the amide compounds or methylol compounds thereof include acrylamide, methacrylamide, diacetone-acrylamide acid, and methylol compounds thereof. Examples of the chlorides include acrylic chloride, and methacrylic chloride. Examples of homopolymers or copolymers that have a nitrogen atom or heterocyclic ring containing a nitrogen atom include vinyl pyridine, vinyl pyrrolidone, vinyl imidazole and ethylene imine. Examples of the polyoxyethylenes include polyoxyethylene, polyoxypropylene, polyoxyethylene alkylamines, polyoxypropylene alkylamines, polyoxyethylene alkylamides, polyoxypropylene alkylamides, polyoxyethylene nonyl phenyl ethers, polyoxyethylene lauryl phenyl ethers, polyoxyethyrylate phenyl ethers, and polyoxyethylene nonyl phenyl esters. Examples of the celluloses include methyl cellulose, hydroxyethyl cellulose and hydroxypropyl cellulose. In the preparation of the dispersion, a dispersion stabilizer may be used as needed. Examples of the dispersion stabilizer include calcium phosphate and the like, which are soluble in acids or alkalis. When calcium phosphate is used as a dispersion stabilizer, the dispersion stabilizer can be removed from particles by dissolving it in an acid such as hydrochloric acid, and by washing the particles with water or by decomposing the dispersion stabilizer with oxygen. In the preparation of the dispersion, it is possible to use a catalyst for the extension or crosslinking reaction. Examples of this catalyst include dibutyl tin laurate and dioctyl tin laurate. An organic solvent is removed from the dispersion resulting (emulsified thick suspension). Examples of the method for removing the organic solvent include (1) a method in which the reaction system is gradually heated to completely evaporate the organic solvent present in the oil droplets., and (2) a method in which the solid dispersions are sprayed in a dry atmosphere to completely remove the water soluble organic solvent in the oil droplets to produce toner particles, together with evaporation of an aqueous dispersing agent. After the removal of the organic solvent, toner particles are formed. The toner particles can be washed and dried further. Subsequently, the toner particles can be optionally classified. The classification can be carried out by removing fine particles in solution by cyclone, decanting, centrifugation, etc. Alternatively, sorting can be carried out after the dry toner particles are obtained as a powder. The toner particles obtained in this way are mixed with particles such as colorant, release agent, charge control agent, etc., and applied to them, mechanical impact, thus preventing the particles such as the agent of release fall from the surfaces of the toner particles.

Examples of the method for applying mechanical impact include a method in which impact is applied to the mixture by means of a blade rotating at high speed, and a method in which impact is applied when introducing the mixture into a high velocity flow. to cause the particles to collide with each other or to cause the composite particles to collide against an impact table. Examples of a device employed for this method include an angmill mill (manufactured by Hosokawamicron Corp.), modified type I mill (manufactured by Nippon Pneumatic Mfg. Co., Ltd.) to lower the air pressure of crushing, hybridization system (manufactured by Nara Machinery Co., Ltd.), a krypton system (manufactured by Kawasaki Heavy Industries Ltd.), and automatic mortars. The color of the toner is not limited in a particular way and can be determined appropriately depending on the purpose proposed; at least one of a black toner, cyan toner, magenta toner, and yellow toner. Toners of different colors can be obtained by using different colorants accordingly; a color tone is preferable.

Developer The developer used in the present invention comprises the toner of the present invention and additional appropriately selected ingredients such as a carrier. The developer can be either a one-component or two-component developer, however, when applied to high-speed printers that support increasing information processing speeds of recent years, a two-component developer is preferred for the purpose of achieve an excellent shelf life. In the case of a developer of a component comprising the toner of the present invention, variations in the toner particle diameter even after the consumption or addition of the toner, and the formation of toner film to a roller are minimized. developer and the addition of toner to the members (e.g., blades) because reduced layer thickness is prevented. In this way, it is possible to provide excellent and stable developing properties and excellent and stable images even after prolonged use of the developing unit (i.e., after long-term agitation of the developer). Meanwhile, in the case of a two-component developer comprising the toner of the present invention, even after many cycles of toner consumption and addition, variations in the particle diameter of the toner are reduced to a minimum and even after a long-time agitation of the developer In the developing unit, excellent and stable development properties can be obtained. The carrier is not limited in a particular way and can be selected in an appropriate manner depending on the proposed purpose; However, the carrier is preferably selected from those having a core material and a resin layer that coats the core material. The materials for the core are not particularly limited and can be appropriately selected from conventional materials, for example materials based on manganese-strontium (Mn-Sr) from 50 emu / ga to 90 emu / g and manganese-based materials. magnesium (Mn-Mg) are preferable. From the viewpoint of securing the image density, high magnetization materials such as iron powder (100 emu / g or more) and magnetite (75 emu / g to 120 emu / g) are preferable. In addition, low-magnetization materials (such as copper-zinc (Cu-Zn) -based materials (30 emu / ga 80 emu / g) are preferable from the point of view of achieving higher-grade images by reducing the contact pressure against the photoconductor that has toner particles at rest.These materials can be used individually or in combination.The particle diameter of the core material, in terms of the volume average particle diameter (D5o) is preferably 10 μm to 120 μm, and more preferably 40 μm to 100 μm. If the average particle diameter (volume average particle diameter (D50)) is less than 10 μm, the fine particles make up a large proportion of the size distribution of the carrier, causing in some cases splashing of the carrier due to reduced magnetization by a particle; on the other hand, if it exceeds 150 μm, the specific surface area of the particles decreases, causing toner spatter and reducing the reproducibility of the images, particularly the reproducibility of solid fillings in full color images. The materials for the resin layer are not particularly limited and can be appropriately selected from conventional resins depending on the proposed purpose; examples include amino resins, polyvinyl resins, polystyrene resins, halogenated olefin resins, polyester resins, polycarbonate resins, polyethylene resins, polyvinyl fluoride resins, polyvinylidene fluoride resins, polytrifluoroethylene resins, resins of polyhexafluoropropylene, copolymers of vinylidene fluoride and acrylic monomers, copolymers of vinylidene fluoride and vinyl fluoride, fluoroterpolymers such as terpolymers of tetrafluoroethylene, vinylidene fluoride and non-fluoride monomers, and silicone resins. These resins can be used individually or in combination. Examples of the amino resins include urea-formaldehyde resins, melamine resins, benzoguanamine resins, urea resins, polyamide resins and epoxy resins. Examples of polyvinyl resins include acrylic resins, polymethyl methacrylate resins, polyacrylonitrile resins, polyvinyl acetate resins, polyvinyl alcohol resins, and polyvinyl butyral resins. Examples of the polystyrene resins include polystyrene resins, and styrene-acrylic copolymer resins. Examples of the halogenated olefin resins include polyvinyl chloride. Examples of the polyester resins include polyethylene terephthalate resins, and polybutylene terephthalate resins. The resin layer may contain material such as conductive powder depending on the application; for the conductive powder, metal powder, carbon black, titanium oxide, tin oxide, zinc oxide and the like are exemplified. These conductive powders preferably have an average particle diameter of 1 μm or less. If the average particle diameter is greater than 1 μm, it can be difficult to control the electrical resistance. The resin layer can be formed by dissolving the silicone resin or the like in a solvent to prepare a coating solution, uniformly coating the surface of the core material with the coating solution by a known coating process, and drying and baking the resin. core material. Examples of the coating process include immersion process, spraying process and brush painting process. The solvent is not limited in a particular way and can be determined in an appropriate manner depending on the purpose proposed. Examples include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cellosolve and butylacetate. The baking process can be an external heating process or an internal heating process, and can be selected from for example, a process using a fixed type electric oven, a fluid type electric oven, a rotary type electric oven or an oven of burner, and a process that uses microwaves. The content of the resin layer of the carrier is preferably 0.01% by mass to 5.0% by mass. If the content is less than 0.01% by mass, it can be difficult to form a uniform layer of resin on the surface of the core material, on the other hand, if the content exceeds . 0% by mass, the resin layer becomes too thick so that the carrier particles can coagulate together. In this way, it can result in failure to obtain uniform carrier particles. When the developer is a two-component developer, the content of the developer in the two-component developer is not particularly limited and can be determined appropriately depending on the proposed purpose; for example, it is preferably 90% by mass to 98% by mass, more preferably 93% by mass to 97% by mass. In the case of a two-component developer, the toner with carrier is generally mixed in an amount of 1 part by mass to 10 parts by mass per 100 parts by mass of the carrier. Since the developer of the present invention comprises the toner of the present invention, allowing the toner particles to pack densely in a toner image, can provide high definition images with reduced thickness of the image layer and can achieve capacity. of long-term stable removal. The developer can be suitably applied to a variety of known electrophotographic image forming processes including a process for developing a magnetic component, a process for developing a non-magnetic component, and a two-component development process, particularly to a toner container, process cartridge, imaging apparatus, and imaging method of the present invention, all which will be described later.

Toner Container The toner container of the present invention is a container supplied with the toner or developer of the present invention. The toner container is not particularly limited and can be appropriately selected from conventional containers; for example, a toner container having a container main body and a layer is a suitable example. The size, shape, structure, material and various other characteristics of the container main body are not limited in a particular way and can be determined appropriately depending on the proposed purpose. For example, the main body of the container preferably has a cylindrical shape, more preferably a cylindrical shape in which spiral grooves are formed on its inner surface which allow the toner in the container to move to the outlet together with rotation of the main body, and in which all or part of the spiral grooves have a bellows function. The materials for the main body of the container are not limited in particular and are preferably those capable of providing exact dimensions when manufactured; examples include resins. For example, suitable examples are polyester resins, polyethylene resins, polypropylene resins, polystyrene resins, polyvinyl fluoride resins, polyacrylic acid resins, polycarbonate resins, ABS resins and polyacetal resins. The toner container of the present invention can be easily stored and transferred, and easily handled. The toner container can be suitably used for the delivery of toner by releasably attaching it to a process cartridge, imaging apparatus, etc., of the present invention which will be described below.

Process Cartridge The process cartridge of the present invention comprises an electrostatic latent image carrier member configured to carry or have an electrostatic latent image, and a developing unit configured to reveal the electrostatic latent image formed in the carrier member of the electrostatic latent image using a developer to thereby form a visible image, and further comprises additional units selected in an appropriate manner. The developer unit comprises a developer container for storing the toner or developer of the present invention, and a developer carrier for transporting and transferring the toner or developer stored in the developer container, and may further contain a thickness control member of the developer. layer to control the thickness of the toner layer to be transported. The process cartridge of the present invention can be removably attached to various electrophotographic apparatuses, faxes and printers, particularly to the image forming apparatus of the present invention which will be described later. The process cartridge of the present invention comprises, for example, as shown in Figure 4, an integrated photoconductor 101, a loading unit 102, a developing unit 104 and a cleaning unit 107 and if necessary, further comprises additional units. For photoconductor 101, a photoconductor similar to that described above can be used. For an exposure unit 103, a light source capable of high definition exposure is used.

For the loading unit 102, an arbitrary loading member can be used. The image forming apparatus of the present invention comprises the electrostatic latent image carrier member, developer device, cleaning device, etc., which are integrated into a process cartridge.

This unit can be detachably attached to the device itself. Alternatively, at least one of a charging device, exposure device, developing device and transfer and separation device are supported together with the electrostatic latent image carrier member to form a process cartridge, thereby forming a unit individual that can be detachably attached to the apparatus by means of the guide means (eg, rails) provided in the apparatus.

Image Formation Method and Image Formation Apparatus The image forming apparatus of the present invention comprises an electrostatic latent image carrier member, an electrostatic latent image forming unit, a developer unit, a transfer unit and a unit fixing, and further comprises additional units such as a load removal unit, a cleaning unit, a recycling unit and a control unit, which are optionally selected as needed. The imaging method of the present invention comprises an electrostatic latent image forming step, a developer step, a transfer step and a fixing step, and further comprises additional steps such as a charge removal step, a cleaning step, a recycling step and / or a control step, which are optionally selected as needed. The imaging method of the present invention can be carried out suitably using the image forming apparatus of the present invention. The electrostatic latent image formation step is performed by the electrostatic latent image deformation unit, the developing step is performed by the developing unit, the transfer step is performed by the transfer unit, the fixing step is performed by the fixing unit, and additional steps can be performed by the additional units.

Electrostatic Latent Image Formation Step and Electrostatic Latent Image Formation Unit The electrostatic latent image formation step is a step to form a latent image electrostatic in a member carrying an electrostatic latent image. The material, shape, size, structure and various characteristics of the member carrying the electrostatic latent image (referred to as "photoconductor" or "electrophotographic photoconductor" in some cases) are not particularly limited. A member carrying an electrostatic latent image can be appropriately selected from those known in the art. However, an electrostatic latent image carrier member in the form of a drum is a suitable example. For the material constituting the electrostatic latent image carrier member, inorganic photoconductive materials such as amorphous silicon and selenium, and organic photoconductive materials such as polysilane and phthalopolymethine are preferable. Among these, amorphous silicon is preferred in view of its long life. The formation of the electrostatic latent image is achieved by exposing, for example, the electrostatic latent image carrier member as well as the image after equally loading its entire surface. This step is carried out by means of the electrostatic latent image forming unit. The electrostatic latent image forming unit comprises a charging device configured to load equally the surface of the electrostatic latent image carrier member, and an exposure device configured to expose in image form the surface of the electrostatic latent image carrier member. The charging step is achieved by applying, for example, a voltage to the surface of the electrostatic latent image carrying member by means of the charging unit. The loading device is not limited in a particular way and can be selected in an appropriate manner depending on the proposed purpose; examples include contact loading devices equipped with a conductor or semiconductor roller, dusting, film or rubber blade; and known non-contact charging devices using corona discharge such as corotron or scorotron. The exposure step is achieved by selectively exposing, for example, the surface of the photoconductor by means of the exposure device. The exposure device is not particularly limited in that it is capable of image-like exposure on the surface of the charged member carrying the electrostatic latent image by means of the charging device, and can be appropriately selected depending on the intended use; the examples they include various exposure devices, such as optical copy devices, rod devices, laser optical devices, and liquid crystal chip optical devices. It is pointed out in the present invention that a backlighting system can be used for exposure, where an image-type exposure is made from the back side of the electrostatic latent image carrying member.

Development and Disclosure Unit The development step is a step of developing the electrostatic latent image using the toner or developer of the present invention to form a visible image. The formation of the visible image can be achieved, for example, by revealing the electrostatic latent image using the toner or developer of the present invention. This is done by means of the revealing unit. The developing unit is not particularly limited as long as it is capable of developing by means of the toner or developer of the present invention, and can be appropriately selected from known developer units depending on the intended use; Suitable examples include those that have at least one developer device, which is capable of housing the toner or developer of the present invention therein and is capable of directly or indirectly applying the toner or developer to the electrostatic latent image. A developer device equipped with the toner container of the present invention is more preferable. The developing device can be of the dry developed type or wet developed type and can be designed either for monochrome or multiple colors; Suitable examples include those which have a stirring unit for stirring the toner or developer to provide electric charges for friction electrification, and rotatable magnet roller. In the developing device, the toner and the carrier are mixed together and the toner is charged by friction, allowing the rotating magnetic roller to carry the toner particles in such a way that they rest on their surface. In this way, a magnetic dusting is performed. Since the magnet roller is arranged in the vicinity of the electrostatic latent image carrying member (photoconductor) some toner particles in the magnetic roller constituting the magnetic dust migrate electrically to the surface of the electrostatic latent image carrying member (photoconductor).

As a result, an electrostatic latent image is revealed by means of toner, forming a visible image, or a toner image, the surface of the member carrying the electrostatic latent image (photoconductor).

Transfer and Transfer Unit The transfer step is a step of transferring the visible image to a recording medium. A preferred embodiment of the transfer comprises two steps: primary transfer in which the visible image is transferred to an intermediate transfer medium; and secondary transfer in which the visible image transferred to the intermediate transfer medium is transferred to the recording medium. A more preferable embodiment of the transfer comprises two steps: primary transfer in which a visible image is transferred to an intermediate transfer medium to form a complex image thereon by means of toners of two or more different colors, preferably toners full color, and secondary transfer in which the complex image is transferred to the recording medium. The transfer step is achieved, for example, by charging the electrostatic latent image carrier member (photoconductor) by means of a transfer load unit. This transfer step is carried out by means of the transfer unit. A preferable embodiment of the transfer unit has two units: a transfer unit configured to transfer a visible image to an intermediate transfer medium to form a complex image; and a secondary transfer unit configured to transfer the complex image to a recording medium. The intermediate transfer means is not limited in a particular way and can be selected from conventional transfer means depending on the proposed purpose; suitable examples include transfer bands. The transfer unit (i.e., the primary and secondary transfer units) preferably comprises a transfer device configured to charge and separate the visible image of the electrostatic latent image carrying member (photoconductor) and transfer it to the recording medium. The number of the transfer device to be provided may be either one or more. Examples of the transfer device include corona transfer devices utilizing corona discharge, transfer belts, transfer rollers, pressure transfer roller, and adhesion transfer devices. The recording medium in general is plain paper and can be determined appropriately depending on the purpose proposed as long as it is able to receive the revealed image in it, without fixing it. You can also use PET bases for OHP. The fixing step is a step of fixing a visible image transferred to a recording medium by means of the fixing unit. The fixing can be performed each time after each different toner is transferred to the recording medium or it can be performed in an individual step after all the different toners have been transferred to the recording medium. The fixing unit is not limited in a particular way and can be selected in an appropriate manner depending on the proposed purpose; examples include a heating pressurization unit. The heating pressurization unit is preferably a combination of a heating roller and the pressurizing roller, or a combination of a heating roller, a pressurizing roller, and an endless belt, by way of example. In general, the heating treatment by means of the pressurization unit by heating is preferably carried out at a temperature of 80 ° C to 200 ° C. It is pointed out in the present invention that a known optical fixation unit can be used in combination with or in place of the fixing step and the fixing unit, depending on the proposed purpose. The charge removal step is a step of applying a deviation to the electrophotographic photoconductor loaded to remove the charges. This is done properly by means of the load removal unit. The load removal unit is not particularly limited in so far as it is capable of applying a charge removal bias to the electrostatic latent image carrying member, and can be appropriately selected from conventional charge removal units depending on the purpose proposed. A suitable example thereof is a charge removal lamp and the like. The cleaning step is a step to remove the toner particles remaining in the electrostatic latent image carrying member. This is done properly by means of the cleaning unit. The cleaning unit is not particularly limited in so far as it is capable of removing the toner particles from the electrostatic latent image carrier member, and can be suitably selected from conventional cleaners depending on the intended use, examples include a cleaner of magnetic dusting, an electrostatic brush cleaner, a cleaner magnetic roller, a blade cleaner, a dust cleaner, and a wave cleaner. The recycling step is a step to recover the toner particles removed through the cleaning step to the developing unit. This is done properly by means of the recycling unit. The recycling unit is not limited in a particular way, and can be appropriately selected from conventional transportation systems. The control step is a step to control the previous steps. This is done properly by means of the control unit. The control unit is not limited in a particular way as long as the operation of each step can be controlled, and can be appropriately selected depending on the proposed use. Examples thereof include equipment such as sequencers and computers. One embodiment of the imaging method of the present invention by means of the image forming apparatus of the present invention will be described with reference to Figure 5. An image forming apparatus 100 shown in Figure 5 comprises a photoconductive drum 10 (FIG. hereinafter referred to as a photoconductor 10) as the electrostatic latent image carrier member, a charge roller 20 as the unit load, an exposure device 30 as the exposure unit, a developing device 40 as the developing unit, an intermediate transfer member 50, a cleaning device 60 having a cleaning blade as the cleaning unit, and a load removal lamp 70 as the load removal unit. The intermediate transfer member 50 is an endless belt, and is designed in a pattern that revolves around three rollers 51 positioned from the inside and rotates in the direction shown by the arrow by means of the rollers 51. One or more of the three rollers 51 also functions as a transfer bias roller capable of applying a certain transfer bias (primary bias) to intermediate transfer member 50. The cleaning device 90 having a cleaning blade is provided adjacent to the intermediate transfer member 50. A transfer roll 80 proximate to the intermediate transfer member 50 is provided as the transfer unit capable of applying a transfer bias to transfer a developed image (toner image) to a transfer sheet 95, a recording medium (secondary transfer). ). In addition, a corona charger 58 is provided around the intermediate transfer member 50 to apply loads to the toner image transferred in the medium 50 of intermediate transfer. The corona charger 58 is arranged between the contact region of the photoconductor 10 and the intermediate transfer medium 50 and the contact region of the intermediate transfer medium 50 and the transfer sheet 95. The developing device 40 comprises a developing web 41 (a developing carrier member), a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M and a cyan developing unit 45C, the developing units which are placed around the developing band 41. The black development unit 45K comprises a developer container 42K, a developer supply roller 43K, and a developing roller 44K. The yellow development unit 45Y comprises a developing container 42Y, a developer supply roller 43Y, and a developing roller 44Y. The magenta developing unit 45M comprises a developer vessel 42M, a developer supply roller 43M, and a developing roller 44M. The cyan developing unit 45C comprises a developer container 42C, a developer supply roller 43C, and a developing roller 44C. The developing web 41 is an endless band that revolves around a plurality of web rollers to be rotatable. A part of the developing web 41 is in contact with the electrostatic latent image carrier member 10.

In the imaging apparatus 100 shown in Figure 5, the photoconductive drum 10 is charged uniformly by, for example, the loading roller 20. The exposure device 30 then applies a beam of light to the photoconductive drum 10 to form an electrostatic latent image. The electrostatic latent image formed in the photoconductive drum 10 is provided with toner from the developing device 40 to form a visible image (toner image). The roller 51 applies a bias to the toner image to transfer the visible image (toner image) to the intermediate transfer medium 50 (primary transfer), and the toner image is then transferred to the transfer sheet 95 (secondary transfer). In this way, a transferred image is formed on the transfer sheet 95. Further in the present, the toner particles remaining in the photoconductive drum 10 are removed by means of the cleaning device 60, and the charges of the photoconductive drum 10 are removed by means of the lamp 70 for charge removal on a temporary basis. . Another embodiment of the imaging method of the present invention by means of the image forming apparatus of the present invention will be described with reference to Figure 6. The imaging apparatus 100 shown in Figure 6 has a configuration identical and working effects to those of the image forming apparatus 100 shown in Figure 5 except that this imaging apparatus 100 does not comprise the developing band 41 and that the black development unit 45K, the yellow development unit 45Y , the magenta development unit 45M and the cyan development unit 45C are placed around the periphery of the photoconductor 10. It is pointed out in figure 6 that members identical to those in Figure 5 are denoted by the same reference numerals. Yet another embodiment of the imaging method of the present invention by means of the image forming apparatus of the present invention will be described with reference to Figure 7. An image forming apparatus 100 shown in Figure 7 is an apparatus for imaging. formation of color images in tandem. The tandem imaging apparatus comprises a main copying machine body 150, a feeder table 200, a scanner 300, and an automatic document feeder (ADF) 400. The main body 150 of The copying machine has an intermediate belt transfer member 50 in the center. The intermediate transfer member 50 rotates around the support rollers 14, 15 and 16 and is configured to rotate in a clockwise direction in Figure 7. A device 17 of Cleaning for the intermediate transfer member is provided in the vicinity of the support roller 15. The cleaning device 17 removes toner particles remaining in the intermediate transfer member 50. In the intermediate transfer member 50 which rotates around the support rollers 14 and 15, four color image devices 18, yellow, cyan, magenta and black, which constitute a tandem developing unit 120, are arranged. An exposure unit 21 is arranged adjacent to the tandem development unit 120. A secondary transfer unit 22 is arranged through the intermediate transfer member 50 from the tandem development unit 120. The secondary transfer unit 22 comprises a secondary transfer belt 24, an endless belt, which revolves around a pair of rollers 23. A sheet of paper in the secondary transfer belt 24 is allowed to come into contact with the member 50. of intermediate transfer. An image fixing device 25 is arranged in the vicinity of the secondary transfer unit 22. The image fixing device 25 comprises a fixing band 26, an endless band, and a pressurizing roller 27 which is pressed by the fixing band 26. In the tandem image forming apparatus, an adjacent leaf inverter 28 is arranged to both the secondary transfer unit 22 as to the image fixing device 25. The leaf inverter 28 flips a transferred sheet to form images on both sides of the sheet. Next, the formation of full color images (color copy) will be described using the tandem development unit. At first, a source document is placed in a document tray 130 of the automatic document feeder 400. Alternatively, the automatic document feeder 400 is opened, the source document is placed on a contact glass 32 of a scanner 300, and the automatic document feeder 400 is closed. When a start switch is pressed (not shown), the source document placed in the feeder 400 automatic document is transferred to the contact glass 32, and the scanner is then operated to operate the first and second carriages 33 and 34. In a case where the source document is originally placed on the contact glass 32, the scanner 300 is It operates immediately after pressing the start switch. A light beam is applied from a light source to the document by means of the first carriage 33, and the light beam reflected from the document is further reflected by the mirror of the second carriage 34. The reflected light beam passes through a lens 35 imager, and is received by a reading sensor 36. In this way, the document is scanned in color (color image), producing 4 types of color information, black, yellow, magenta and cyan. Each piece of color information (black, yellow, magenta and cyan) is transmitted to the image forming unit 18 (black image forming unit, yellow image forming unit, magenta image forming unit, or color unit). cyan image formation) of the tandem development unit 120, and toner images of each color are formed in the imaging units 18. As shown in Figure 8, each of the image forming units 18 (black image forming unit, yellow image forming unit, magenta image forming unit and cyan imaging unit) of the unit 120 of tandem development comprise: an electrostatic latent image carrier member (electrostatic latent image carrier member for 10K black, electrostatic latent image carrier member for 10Y yellow, electrostatic latent image carrier member for 10M magenta, or carrier member). electrostatic latent image for cyan 10C); a charging device 60 for uniformly charging the electrostatic latent image carrying member, an exposure unit for forming an electrostatic latent image that corresponds to the color image in the electrostatic latent image carrier member when exposed to light (denoted by "L" in Figure 8) based on the corresponding color image information; a developing device 61 for developing the electrostatic latent image using the corresponding color toner (black toner, yellow toner, magenta toner or cyan toner) to form a toner image; a transfer magazine 62 for transferring the toner image to the intermediate transfer member 50, a cleaning device 63; and a load removal device 64. In this way, images of different colors (a black image, a yellow image, a magenta image and a cyan image) can be formed based on the information of the color image. The image of black toner formed in the photoconductor for black 10K, the image of yellow toner formed in the photoconductor for yellow 10Y, the image of magenta toner formed in the photoconductor for 10M magenta, and the cyan toner image formed in the photoconductor for 10C are transferred sequentially to the intermediate transfer member 50 which rotates by means of the support rollers 14, 15 and 16 (primary transfer). These toner images are superimposed on the intermediate transfer member 50 to form a composite color image (color transferred image).

Meanwhile, one of the feed rolls 142 of the feed table 200 is selected and rotated, whereby sheets (recording sheet) are ejected from one of the multiple feed cassettes 144 into the paper bank 143 and they are separated one by one by a separation roller 145. Subsequently, the sheets are fed to a feed path 146, transferred by a transfer roller 147 to a feed path 148 within the main machine body 150, and are damped against a sturdy roll 49 for stopping. Alternatively, one of the feed rollers 142 is rotated to eject sheets (recording sheets) placed in a manual feed tray. The sheets are then separated one by one by means of a separation roller 52, they are fed to a manual feeding path 53, and similarly, they are damped against the resistance roller 49 for stopping. It is noted that the resistance roller 49 is connected to ground in general, but can be biased to remove paper dust in the sheets. The resistance roller 49 is rotated synchronously with the movement of the composite color image in the intermediate transfer member 50 to transfer the sheet (recording sheet) between the intermediate transfer member 50 and the transfer unit 22. secondary, and the composite color image is transferred to the sheet by means of the secondary transfer unit 22 (secondary transfer). In this way, the color image is formed on the sheet. It is noted that after the image transfer, the toner particles remaining in the intermediate transfer member 50 are removed by means of the cleaning device 17. The sheet (recording sheet) having the transferred color image is transported by the secondary transfer unit 22 to the image fixing device 25, where the composite color image (image transferred to color) is fixed to the sheet (sheet of recording) by heat and pressure. Subsequently, the blade changes its direction by the action of a change hook 55, is ejected by an ejection roller 56 and is stacked in an exit tray 57. Alternatively, the blade changes its direction by the action of the shift hook 55, is flipped by means of the blade inverter 28, and transferred back to the image transfer section for the recording of another image on the other side . The sheet having images on both sides is then ejected by means of the eject roll 56, and is stacked in the output tray 57. Since the image forming method and the image forming apparatus of the present invention use the toner of the present invention, toner allows the Toner particles are densely packed in a toner image, high definition images can be provided with reduced thickness of the image layer and a stable long-term removal capacity can be achieved, it is possible to form well-defined images and high quality. Hereinafter, examples of the present invention will be described, which however should not be construed as limiting the invention to them. It is noted that "part" means "parts by mass" unless otherwise indicated.

Example 1 Synthesis of Organic Particle Emulsion A reaction vessel equipped with a stirrer and a thermometer was charged with 683 parts of water, 11 parts of a sodium salt of sulfuric acid ester of ethylene oxide adduct of methacrylic acid (Eleminol RS-30, produced by Sanyo Chemical Industries Co.), 83 parts of styrene, 83 parts of methacrylic acid, 110 parts of butyl acrylate and 1 part of ammonium persulfate, followed by stirring for 15 minutes at 400 rpm to produce a white liquid emulsion. The interior of the reaction vessel was heated to 75 ° C for 5 hours for reaction. 30 parts of a 1% strength aqueous solution of persulfate were added to the reaction vessel. ammonium, and the reaction vessel was allowed to stand for 5 hours at 75 ° C to produce an aqueous dispersion of vinyl resin (a copolymer consisting of styrene, methacrylic acid, butyl acrylate, and sodium salt of sulfuric acid ester of adduct of ethylene oxide of methacrylic acid). - Dispersion 1 of particles. The volume average particle diameter of the Particle Dispersion 1 measured using a laser diffraction particle size analyzer (LA-920, SHIMADZU Corp.) was 105 nm. In addition, an aliquot of Particle Dispersion 1 was dried to isolate a resin component. The glass transition temperature (Tg) of the resin component was determined to be 59 ° C, and its weight average molecular weight (Mw) was determined to be 150,000.

Aqueous Phase Preparation For the preparation of an aqueous phase, 990 parts of water, 99 parts of Particle Dispersion 1, 35 parts of a 48.5% aqueous solution of sodium dodecyldiphenylether disulfonate (Eleminol MON-7, produced by Sanyo Chemical Industries Ltd.), and 60 parts of ethyl acetate were mixed to produce a creamy white liquid. This was used as Phase 1 Aqueous.

Synthesis of Low Molecular Weight Polyester A reaction kit equipped with a condenser tube, a stirrer and a nitrogen gas inlet tube was charged with 229 parts of 2 mole of ethylene oxide adduct of bisphenol A, 529 parts of 3 mol of propylene oxide adduct of bisphenol A, 208 parts of terephthalic acid, 46 parts of adipic acid, and 2 parts of dibutyl tin oxide, allowing the reaction to take place for 8 hours at 230 ° C under normal pressure. The reaction was continued for an additional 5 hours under reduced pressure (10-15 mm Hg). Subsequently, 44 parts of trimellitic acid anhydride were added to the reaction vessel to allow the reaction to take place for 1.8 hours at 180 ° C under normal pressure. In this way, Low Molecular Weight Polyester 1 was synthesized. The Low Molecular Weight Polyester 1 obtained in this way has a number average molecular weight (Mn) of 2,500, weight average molecular weight (Mw) of 6,700, peak molecular weight of 5,000, glass transition temperature (Tg) of 43 ° C, and an acid value of 25.

Synthesis of Intermediate Polyester A reaction vessel equipped with a condenser tube, a stirrer and a nitrogen gas inlet tube was charged with 682 parts of 2 mol of adduct of ethylene oxide of bisphenol A, 81 parts of 2 mole of propylene oxide adduct of bisphenol A, 283 parts of terephthalic acid, 22 parts of trimellitic acid anhydride, and 2 parts of dibutyltin oxide, allowing the reaction to take place for 8 hours at 230 ° C under normal pressure. The reaction was continued for an additional 5 hours under reduced pressure (10-15 mm Hg) to yield Intermediate Polyester 1. The Intermediate Polyester 1 obtained in this way has a number average molecular weight (Mn) of 2,100, weight average molecular weight (Mw) of 95.00, vitreous transition temperature (Tg) of 55 ° C, acid value of 5. , and hydroxyl value of 51. Subsequently, a reaction vessel equipped with a condenser tube, a stirrer and a nitrogen inlet tube was charged with 410 parts of Intermediate Polyester 1, 89 parts of isophorone diisocyanate, and 500 parts of ethyl acetate, allowing the reaction to take place for 5 hours at 100 ° C to produce the prepolymer 1. The content of the free isocyanates in Polyester 1 was 1.53% by mass.

Synthesis of ketimine compounds A reaction vessel equipped with a stirrer and a thermometer was charged with 170 parts of isoprona diamine and 75 parts of methyl ethyl ketone, allowing the reaction to take place for 5 hours at 50 ° C to produce Compound 1 of Cetimine. The amine value of Compound 1 of Cetimine obtained in this manner was 418.

Preparation of Main Lot Using a HENSCHEL MIXER (Mitsui Mining Company, Ltd.), 1200 parts of water, 540 parts of carbon black (Printex 35, produced by Deguessa Corp., DBP absorption = 42 ml / 100 mg, pH) were mixed. = 9.5), and 1200 parts of polyester resin, and additionally kneaded for 30 minutes at 150 ° C using a double roller. Subsequently, the resulting paste was spread by applying pressure, cooled and pulverized in a spray to produce Main Lot 1.

Oil Phase Preparation A reaction vessel equipped with a stirrer and thermometer was charged with 378 parts of Low Molecular Weight Polyester 1, 110 parts of carnauba wax, 32 parts of a charge control agent (E-84, zinc salicylate, produced by Orient Chemical Industries, Ltd.), and 947 parts of ethyl acetate, was heated at 80 ° C with stirring, it remained for 5 hours at 80 ° C, and was cooled to 30 ° C in 1 hour. Subsequently, 500 parts of Main Lot 1 and 500 parts of ethyl acetate were added to the reaction vessel, and stirred for 1 hour to produce Toner Constituent Solution 1. Then, 1324 parts of the Toner Constituent Solution 1 thus obtained to a reaction vessel, and dispersed using a bead mill (ULTRAVISCOMILL, manufactured by AIMEX Co., Ltd.), under the following conditions: Liquid feed rate = 1 kg / hr, Disk rotation speed = 6 m / sec, Counter diameter = 0.5 mm, Fill factor = 80 % in volume, and the number of dispersion operations = 3. In this way, they were dispersed in carbon black and wax. Subsequently, 1324 parts of a 65% ethyl acetate solution of the Low Molecular Weight Polyester 1 were added to the reaction vessel, followed by another dispersing operation using the bead mill under the above conditions. In this way, Pigment / Wax Dispersion 1 was obtained. The proportion of solids in Pigment / Wax Dispersion 1 was 50% by mass, when it was measured after heating at 130 ° C for 30 minutes.

Emulsification and Solvent Removal Step To a reaction vessel were added 749 parts of Pigment / Wax Dispersion 1, 115 parts of Prepolymer 1, and 2.9 parts of Compound 1 of Cetimine. Additionally, 2.0 parts of the solids of an organosilicon colloidal solution (MEK-ST-UP, produced by Nissan Chemical Industries, Ltd.) were added to the reaction vessel and, using a TK homomixer, mixed for 1 minute to 5,000 rmp. Subsequently, 1250 parts of the aqueous phase 1 were added and mixed using the TK homomixer for 30 minutes at 12,500 rpm, producing the Emulsion Thick Suspension 1. A reaction vessel equipped with a stirrer and a thermometer was charged with the Emulsion Thick Suspension 1, and heated at 40 ° C for 5 hours for the removal of a solvent. The slurry was then allowed to stand for 4 hours at 45 ° C to produce the Thickness Suspension 1 of Dispersion.

Washing and Drying One hundred parts of the Dispersion Thickness Suspension 1 was filtered under reduced pressure, the filter cake was added to 100 parts of deionized water and mixed using the TK homomixer for 10 minutes at 12,000 rpm followed by filtration.

Then, the resulting filter cake was added to 100 parts of a 10% aqueous solution (by mass) sodium hydroxide and mixed using the homomixer TK for 30 minutes at 12,000 rpm followed by filtration under reduced pressure. The resulting filter cake was added to 100 parts of a 10% aqueous solution (by mass) of hydrochloric acid and mixed using the TK homomixer for 10 minutes to 12 minutes., 000 rpm, followed by filtration. The resulting filter cake was added to 300 parts of deionized water and mixed using the TK homomixer for 10 minutes at 12,000 rpm followed by filtration (this procedure was performed twice). In this way, Filter Cake 1 was obtained. Filter Cake 1 was dried for 48 hours at 45 ° C in a circulation dryer and sieved through a 75 μm mesh to produce Toner 1.

Addition of External Additive To 100 parts of Toner 1 1.5 parts of hydrophobic silica were added and mixed using the HENSCHEL MIXER to produce the toner of Example 1.

Example 2 The toner of Example 2 was prepared in a manner similar to that described in Example 1 except that 2.5 parts of the solids of an organosilicon colloidal solution were used in the emulsification and solvent removal step.

Example 3 The toner of Example 3 was prepared in a manner similar to that described in Example 1 except that 3.5 parts of the solids of an organosilicon colloidal solution were used in the emulsification and solvent removal step.

Example 4 The toner of Example 4 was prepared in a manner similar to that described in Example 1 except that 4.5 parts of the solids of an organosilicon colloidal solution were used in the emulsification and solvent removal step.

Comparative Example 1 The toner of Comparative Example 1 was prepared in a manner similar to that described in Example 1 except that colloidal organosilicon solution was not added to the toner in the emulsification and solvent removal step.

Comparative Example 2 Through wet spraying, the toner of Comparative Example 2 was prepared in the following manner using polyester resin synthesized from bisphenol diol and a polycarboxylic acid. At the beginning, 86 parts of polyester resin (number average molecular weight (Mn) = 6,000, weight average molecular weight (Mw) = 50,000, and vitreous transition temperature (Tg) = 61 ° C), 10 parts are completely mixed. of rice wax (acid value = 0.5), and 4 parts of copper blue phthalocyanine pigment (produced by TOYO INK Corp.), using the HENSCHEL MIXER, were heated and melted using a roller mill for 40 hours at 80 ° C at 110 ° C, and cooled to room temperature. The resulting paste was pulverized and classified to produce toner particles. Using the HENSCHEL MIXER, 1.5 parts of hydrophobic silica were mixed with 100 parts of the toner particles to prepare the toner of Comparative Example 2. For the toners prepared in Examples 1 to 4 and Comparative Examples 1 and 2, the Surface factors SF-1 and SF-2, SF-2 small diameter, SF-2 large diameter, porosity, particle diameter of toner (Dv, Dv / Dn), the proportion of of 2 μm or less, and the presence of a layer of inorganic oxide particles. The results are shown in Table 1.

Surface Factors SF-1 and SF-2 Images of the toner particles are taken by a scanning electron microscope (S-800, manufactured by Hitachi Ltd.), and analyzed by an image analyzer (LUSEX3, manufactured by NIRECO Corp.), calculating the surface factors SF-1 and SF-2 using the following Equations (1) and (2). SF-1 = [(MXLNG) VAREA] x (100p / 4) ... Equation (1) where MXLNG represents the maximum length through a two-dimensional projection of a toner particle, and 'AREA represents the area of the projection . SF-2 = [(PERI) VAREA] x (100 / 4p) ... Equation (2) where PERI represents the perimeter of a • two-dimensional projection of a toner particle, and AREA represents the area of the projection. The proportion of toner particles with an equivalent circle diameter of 2 μm or less. The proportion (% by number) of the toner particles with an equivalent diameter of given circle can be determined using a flow particle image analyzer (FPIA-2100, manufactured by Sysmex Corp.). More flow (FPIA-2100, manufactured by Sysmex Corp.). More specifically, an aqueous solution of 1% NaCl was prepared using primary sodium chloride, and filtered through a filter with a pore size of 0.45 μm. The 50-100 ml of this solution added 0.1-5 ml of a surfactant (preferably, alkylbenzene sulfonate) as a dispersing agent, followed by the addition of 1-10 mg of sample. The mixture was then treated with ultrasound for 1 minute using an ultrasound apparatus to prepare a dispersion with a final particle concentration of 5,000-15,000 / μL for measurement. The measurement was made based on an equivalent circle diameter, the diameter of a circle having the same area as the 2D image of a toner particle taken by a CCD camera. In view of the resolution of the CCD camera, measurement data of the particles with an equivalent circle diameter of 0 were collected. 6 μm or more.

The porosity of the toner particles Using a porosity measuring device shown in Figure 3, the volume and mass of toner packed under pressure of 10 kg / cm2 were measured, calculating the porosity of the toner particles with their specific gravity previously measured taking into account.

Toner particle diameter The volume average particle diameter (Dv) and the number average particle diameter (Dn) of the toner particles were measured using a particle size analyzer (Multisizer II, Beckmann Coulter Inc.), at an aperture diameter of 100 μm, determining the particle size distribution (Dv / Dn) of the toner particles.

Presence of a layer of inorganic oxide particles Whether or not a layer of inorganic oxide particles within 1 μm is present from the toner surface of a toner particle was determined by looking at a cross section of the toner particle using a microscope electronic transmission (TEM).

Table 1 "SF-2 small diameter": toner particles with a particle diameter of less than 4 μm. "SF-2: large diameter": toner particles with a particle diameter of 4 μm or greater. It is noted that "most abundant particle diameter in the particle size distribution" is the peak value (4 μm) in the particle size distribution based on the number of the toner particles.

It can be learned from Table 1 that the surface factor SF-2 correlates with the average particle diameter in volume (Dv).

Developer Preparation 3 parts of each of the toners prepared in Examples 1 to 4 and Comparative Examples 1 and 2 were added to 97 parts of ferrite carrier 100-200 mesh coated with silicone resin, and mixed together using a ball mill. In this way, developers of two components were prepared. Each developer prepared in this way was evaluated for image uniformity, transfer ratio, uneven transfer occurrence, and removal capacity. For each developer, a half tone image is formed using an image forming apparatus (MS2800), manufactured by Ricoh Company, Ltd.), and the degree of surface roughness was visually evaluated based on the following criteria: A: Excellent (the surface of the half-tone image is very smooth) B: Good (although not as smooth as A, the surface of the half-tone image is almost free of roughness, not practical problems) C: Bad (the surface of the half-tone image is slightly rough, but still practically acceptable) D: Poor (the surface of the half-tone image is very rough, practically unacceptable).

Transfer Ratio (%) For each developer, a black filled image (size = 15 cm x 15 cm, average image density = 1.38 or more as measured by a Macbeth reflection densitometer) is formed using an image forming apparatus (MS2800), manufactured by Ricoh Company, Ltd.), and its transfer ratio was evaluated from the following Equation (3): Transfer ratio (%) = (the amount of toner particles transferred to a recording medium / the amount of toner particle revealed in an electrostatic latent image carrier member ) x 100 Equation (3) Transfer Inequality For each toner, a black filled image is formed using the image forming apparatus (MS2800), manufactured by Ricoh Company, Ltd.), and the occurrence of unequal transfer was determined visually and the inequality was evaluated on the basis of the following criteria: A: Excellent (not inequality) B: Good (little inequality, no practical problems) C: Bad (slight inequality, still practically acceptable) D: (very unequal, practically unacceptable).

Removal Capacity The presence of scratched marks on the photoconductor due to cleaning problem after image formation was determined visually and evaluated based on the following criteria: A: Excellent (no scratched photoconductor mark) B: Good (from one to two very thin scratched marks that were scarcely recognized by visual inspection, but no technical problem) C: Bad (a few scratched marks that can be recognized visually, but practically acceptable) D: Poor (several discrete scratched marks that are they can recognize visually - practically unacceptable).

Table 2 Figure 9A is an image representing laminated toner particles of Example 1 developed in a photoconductor, Figure 9B is an image representing laminated toner particles of Comparative Example 2 developed in a photoconductor. As shown in Figure 9A, the toner particles prepared in Example 1, spherical particles, did not scatter too much and the height of the toner laminate constituting the image is small. The toner particles of Comparative Example 2 shown in Figure 9B, in contrast, are scattered too much and the height of the rolled toner product constituting the image. The image densities of the two images in Example 1 and Comparative Example 2 are both 1.3. The results shown in Table 2 and Figures 9a and 9B disclose that the toners of Examples 1 to 4 have a more excellent image density and removal capacity than the toners of Comparative Examples 1 and 2 and are free of transfer inequality.

Industrial Applicability The toner of the present invention can provide long-term removal capability and high definition images with reduced thickness of the image layer and densely packed toner particles. In this way, the toner of the present invention can be used suitably for the formation of high quality images. The developer, the toner container, the process cartridge, the image forming apparatus, and the imaging method of the present invention, all of which use the toner of the present invention, can be used suitably for the formation of images of high quality.

Claims (18)

1. CLAIMS 1. A toner comprising: a toner material comprising a binder resin and a colorant, wherein the toner has a substantially spherical shape with irregularities on its surface, and wherein a surface factor SF-1 represented by the following Equation (1) representing the sphericity of the toner particles 105 to 180, a surface factor SF-2 represented by the following Equation (2) that represents the degree of surface irregularities of the toner particles correlates with the diameter volume average of the toner particles, and the toner particles have a layer containing inorganic oxide particles within 1 μm of their surfaces. SF-1 = [(MXLNG) VAREA] x (100 / 4p) ... Equation (1) where MXLNG represents the maximum length through a two-dimensional projection of a toner particle, and AREA represents the area of the projection. SF-2 = [(PERI) 2 / AREA] x (100 / 4p) ... Equation (2) where PERI represents the perimeter of a two-dimensional projection of a toner particle, and AREA represents the area of the projection. The toner according to claim 1, wherein SF-1 is 115 to 160 and SF-2 is 110 to 300. 3. Toner according to one of claims 1 to 2, where the difference between the SF-2 of the toner particles whose particle diameter is smaller than the toner particle diameter more abundant in a particle size distribution and the SF-2 of the toner particles whose diameter of particle is equal to or greater than the most abundant toner particle diameter in the particle size distribution is 8 or greater. 4. Toner according to any of claims 1 to 3, wherein the layer containing inorganic oxide particles comprises silica. 5. Toner according to any of claims 1 to 4, wherein the volume average particle diameter is 3 μm to 10 μm. 6. Toner according to any of claims 1 to 5, wherein the ratio of the volume average particle diameter (Dv) to the number average particle diameter (Dn), (Dv / Dn), is 1.00 to 1.35. 7. Toner according to any of claims 1 to 6, wherein the proportion of toner particles having an equivalent circle diameter, the diameter of a circle having the same area as the projection of the toner particles, of 2 μm is 20% or less on a number basis. The toner according to any of claims 1 to 7, wherein the porosity of the low toner particles Pressure of 10 kg / cm2 is 60% or less. The toner according to any of claims 1 to 8, wherein the toner is produced by emulsifying or dispersing a toner material solution or a dispersion of toner material in an aqueous medium to form toner particles. The toner according to claim 9, wherein the toner material solution or dispersion of toner material comprises an organic solvent, and the organic solvent is removed on or after the production of the toner particles. The toner according to one of claims 9 and 10, wherein the toner material comprises a compound containing an active hydrogen group and a polymer capable of reacting with the active hydrogen group-containing compound, the toner particles being produced by the reaction of the compound containing the active hydrogen group with the polymer to produce an adhesive base material comprising the toner particles. The toner according to claim 11, wherein the toner material comprises an unmodified polyester resin and the mass ratio of the polymer capable of reacting with the compound containing active hydrogen groups to the unmodified polyester resin (polymer / resin) of unmodified polyester) is 5/95 a 80/20. A developer comprising a toner according to any of claims 1 to 12. A developer according to claim 13, wherein the developer is any one of a one-component developer and two-component developer. 15. A toner container comprising a toner according to any of claims 1 to 12. 16. Process cartridge comprising: a member carrying an electrostatic latent image; and a developing unit configured to reveal an electrostatic latent image formed in the member carrying the electrostatic latent image by the use of a toner according to any of 1 to 12, to form a visible image. 17. An image forming apparatus comprising: a member carrying an electrostatic latent image; an electrostatic latent image forming unit configured to form an electrostatic latent image on the carrier member of the electrostatic latent image; a developing unit configured to reveal the electrostatic latent image by the use of a toner according to any of claims 1 to 12, to form a visible image; a transfer unit configured to transfer the visible image to a recording medium; and a fixing unit configured to fix the visible image transferred to the recording medium. 18. Method of imaging comprising: forming an electrostatic latent image on an electrostatic latent image carrier member; revealing the electrostatic latent image by the use of a toner according to any of claims 1 to 12, to form a visible image; transfer the visible image to a recording medium; and fix the visible image transferred to the recording medium.