JP2009014882A - Toner, developer, image forming method, process cartridge and image forming apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner that can shift a generation temperature of hot offset in a fixing zone to be relatively high, maintains favorable toner fluidity, toner storage property and the like, and can stably give fluidity and charge quantity of a developer for a long period of time, and particularly, a color toner having transparency, and to provide a developing device, a process cartridge, an image forming apparatus and an image forming method by which high-quality images with less contamination on a base can be obtained even when a spheric toner having a small particle diameter is used. <P>SOLUTION: The toner contains at least a binder resin, a colorant, a release agent and an external additive, wherein the toner is composed of: first toner particles including first toner base particles containing a release agent having an average dispersion particle diameter DWA of 0.1 to 0.6 μm per one particle with addition of an external additive having a particle diameter of 30 to 300 nm; and second toner particles including second toner base particles containing a release agent having an average dispersion particle diameter DWB of 0.8 to 3.0 μm per one particle with addition of an external additive having a particle diameter of 5 to 25 nm. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an electrostatic latent image developing toner, a developer, a developing device, and a process cartridge used for image formation by an electrostatic copying process such as a copying machine, a facsimile machine, and a printer, and an image forming apparatus using the toner. About.

  In an image forming apparatus such as a copying machine, a printer, or a facsimile machine, an electrostatic latent image by an electrophotographic method is formed by an image forming method in which a toner of colored resin particles including a pigment is used to make a visible image. By this image forming method, an image having high-accuracy image quality can be formed at high speed, a full color image can be formed as well as a monochrome image, and durability and stability that can withstand long-term use are achieved.

  Even in such an image forming method, which has been set to a sufficient level in the past, the image quality required recently has been increased, and further improvement has been demanded. In particular, high reproducibility is demanded for image portions that are conspicuous even with slight deterioration such as fine lines and minute dots. On the other hand, the actual situation is to deal with this by using a fine toner having a small particle diameter or using a spherical toner.

However, when a fine toner having a small particle size is used, it is difficult to provide a sufficient charge amount. The reason for this is that, since the particles are small, the surface area of the particles increases, and at the same time, the van der Waals force also increases, the fluidity decreases, and the friction with the frictional charge imparting material is insufficient. For this reason, when toner having a small particle diameter is used, problems such as toner scattering and fogging often occur. Further, since the adhesion to the photosensitive member becomes strong, there is a problem that the cleaning property is deteriorated by a cleaning method using an elastomer blade having a simple structure at a low cost.
On the other hand, the use of spherical toner enables high-definition latent images to be developed with high reproducibility because they fly and move with high fidelity to the electric field. However, since it is easy to roll on the photoconductor, the cleaning method using the blade is insufficiently cleaned.

In addition to these problems, a releasable material (silicone oil) has been conventionally applied so as not to cause toner offset on the surface of the fixing member. However, in recent years, a releasable material (wax) has been applied to the toner particles. An oilless toner is used.
The oilless toner containing the wax does not require the application of silicone oil, and the structure of the fixing device is simple. On the other hand, the releasability with oilless toner is better with the releasable material, but the fluidity of the toner deteriorates and the resin and wax are not compatible. Problems such as deterioration of reproducibility occur. Further, when oilless toner is stored for a long period of time, there is a problem that the toners are bound to each other due to the seepage of wax on the toner surface (see Patent Documents 1 to 4).

  In the oilless toner, if the wax particle diameter is small and dispersed in the fixing unit for fixing the toner image, the wax does not sufficiently ooze out on the toner surface when the toner is heated, and hot offset occurs at a low temperature. Also, if the wax particle size is dispersed widely, the color toner is incompatible with the resin and the wax, so the transparency deteriorates, and more wax is exposed on the toner particle surface, resulting in poor toner fluidity. In addition, problems such as sticking of toners due to oozing of wax occur when the toner is stored.

  Further, in the case of the latent image carrier and the two-component developer, the wax is likely to come into contact with the carrier, so that the latent image carrier and the carrier surface are likely to be contaminated, and background contamination and chargeability are likely to occur. Since the wax dispersion particle size is large in the fixing portion for fixing the toner, a large amount of wax is exposed on the surface of the toner particle, and a large amount of wax is present on the toner surface when the toner is heated, and the temperature at which hot offset occurs is shifted to a high level.

  The set temperature in the fixing unit of this copying machine is generally about 145 to 185 ° C., and the temperature is controlled even during standby (when the image forming apparatus is not performing an image forming operation). However, the temperature distribution in the axial direction of the fixing member (roller, belt, etc.) may cause a temperature rise of about 10 to 20 ° C. at the end of the fixing member. In order to prevent the occurrence of hot offset, paper wrapping, etc., toner characteristics such that hot offset does not occur up to 195 ° C. (set temperature 185 + 10 ° C.) or higher, and in some cases to about 205 ° C. (set temperature 185 + 20 ° C.). Must be set in advance.

JP 2002-365847 A JP 2003-131430 A JP 2005-107744 A JP 2004-133440 A

  The present invention has been made to solve the above-described problems all at once, and includes toner particles containing wax having a small dispersion diameter in toner particles, and toner containing wax having a large dispersion diameter in toner particles. An object of the present invention is to provide a toner capable of adjusting both the amount of particles and the properties of both dispersion diameters at the same time.

  Further, the present invention provides a toner having a different particle size of the release agent contained therein, and those having a small particle size of the release agent are relatively uniformly dispersed in the toner particles. And the toner fluidity is good, and it is possible to prevent the wax from oozing out during the storage of the toner and to prevent the toner from solidifying as much as possible. When used as a component developer, an object of the present invention is to provide a toner which does not contaminate the latent image carrier or the carrier surface and hardly causes a background stain or a decrease in chargeability.

  Furthermore, the present invention provides stable chargeability, prevents the wax from detaching from the toner surface by agitating the developing part, and carrier chargeability by the wax adhering to the carrier particle surface in the two-component developer due to the wax existing on the toner surface. In the two-component developer, the amount of developer pumped onto the developing sleeve is reduced by the wax adhering to the carrier particle surface. Provided is a developing device, a process cartridge, and an image forming apparatus capable of obtaining a high-quality image over a long period of time by providing a toner that does not change and therefore does not vary in image density and can obtain good fluidity. The purpose is that.

The features of the present invention, which is a means for solving the above problems, are listed below.
(1) A toner comprising at least a binder resin, a colorant, a release agent, and a charge control agent, the first toner particles and the second toner particles,
The release agent in the first toner particles has an average dispersed particle size per particle in the range of 0.1 to 0.6 μm,
The release agent in the second toner particles has an average dispersed particle size per particle in the range of 0.8 to 3.0 μm.
Toner characterized by the above.
(2) In the toner according to (1), the average dispersed particle diameter of the release agent per particle in the first toner particles is DWA (μm), and the release particle per particle in the second toner particles. When the average dispersed particle size of the mold is DWB (μm), the ratio (XB) (wt%) of the second toner particles in the toner has a relationship represented by the following formula (1). Features toner.
−30.8 (DWA × DWB) + 68.3 ≧ XB ≧ −23.5 (DWA × DWB) +43.4 (1)
(3) The toner according to (1) or (2), wherein the charge control agent is at least one selected from an azo metal complex compound, a quaternary ammonium salt, and a salicylic acid metal complex compound. .
(4) In the toner according to any one of (1) to (3), the first and second toner particles have a weight average particle diameter in the range of 4.0 to 9.5 μm, and the weight average particle A toner having a ratio (D4 / Dn) of a diameter (D4) to a number average particle diameter (Dn) in a range of 1.00 to 1.40.
(5) In the toner according to any one of (1) to (4), the first and second toner particles have a shape factor SF-1 in the range of 100 to 180, and a shape factor SF-2. In the range of 100-180.
(6) The toner according to any one of (1) to (5), wherein the binder resin of the first and second toner particles is obtained by a polymerization method.
(7) In the toner according to any one of (1) to (6), the first and second toner particles have a substantially spherical shape, and the shapes thereof are a major axis r1, a minor axis r2, and a thickness r3. (Where r1 ≧ r2 ≧ r3), the ratio of the minor axis r2 to the major axis r1 (r2 / r1) is in the range of 0.5 to 1.0, and the thickness r3 A toner having a ratio (r3 / r2) to the minor axis r2 in the range of 0.7 to 1.0.
(8) A developer for developing an electrostatic latent image on an image carrier, wherein the developer comprises the toner according to any one of (1) to (7) and a carrier made of a magnetic material. A developer characterized by containing.
(9) The developer according to (8), wherein the magnetic material is a magnetic carrier coated with a resin.
(10) In the developing device arranged to face the image bearing member carrying the electrostatic latent image, the developing device uses the developer described in (8) or (9). apparatus.
(11) In a process cartridge that integrally supports an image carrier that carries an electrostatic latent image and at least a developing device that is disposed to face the image carrier, and is detachable from an image forming apparatus main body, A process cartridge comprising the developing device according to (10).
(12) In the image forming apparatus including at least an image carrier that carries an electrostatic latent image, and a developing device that is disposed to face the image carrier, the image forming device is described in (10). An image forming apparatus using the developing device.

  According to the present invention, the temperature at which hot offset occurs at the fixing portion is increased, and fluidity, particularly transparency and toner storage stability in color toners are maintained well, and stable fluidity and charge amount are maintained over a long period. A stable toner and developer can be provided. In addition, a high-quality image with less background stains can be obtained by the developing device, process cartridge, and image forming apparatus of the present invention using such excellent toner.

  Hereinafter, the present invention will be described by way of embodiments with reference to the drawings. Changes and modifications are also included in the scope of the claims. The following description illustrates the best mode of the present invention and is not intended to limit the scope of the claims.

The toner of the present invention contains at least a binder resin, a colorant, a release agent, and a charge control agent, and the average dispersion particle size (DWA: μm) of each release agent is expressed by the following formula (1-1). ) First toner particles in the range of
It contains at least a binder resin, a colorant, a release agent, and a charge control agent, and the average dispersion particle size (DWB: μm) per release agent is in the range of the following formula (1-2). 2 toner particles.
0.1 ≦ DWA ≦ 0.6 (1-1)
0.8 ≦ DWB ≦ 3.0 (1-2)

In the toner of the present invention, the average dispersed particle size of the release agent per particle in the first toner particles is DWA (μm), and the average dispersed particle of the release agent per particle in the second toner particles. When the diameter is DWB (μm), the ratio (XB) (% by weight) of the second toner particles in the toner is preferably in a relationship represented by the following formula (1).
−30.8 (DWA × DWB) + 68.3 ≧ XB ≧ −23.5 (DWA × DWB) +43.4 (1)

  The toner of the present invention is a toner for developing an electrostatic latent image, and includes at least a binder resin, a colorant, a release agent, and a charge control agent. The toner particles in the present invention are obtained by a production method such as a pulverization method or a polymerization method (suspension polymerization, emulsion polymerization, dispersion polymerization, emulsion aggregation, emulsion association, etc.). However, toner base particles obtained by a production method other than these production methods can also be used for the toner of the present invention, and are not limited to the production methods described above.

  As an example of toner production by the pulverization method, first, a binder resin, a pigment or dye as a colorant, a charge control agent, a release agent, other additives, etc. are sufficiently mixed by a mixer such as a Henschel mixer. The components are well kneaded using a thermal kneader such as a batch type two-roll, three-roll, Banbury mixer, continuous twin-screw extruder, or continuous single-screw kneader. The kneaded product is cut after rolling and cooling. After cutting, the toner kneaded product is crushed, coarsely pulverized using a hammer mill, etc., and further pulverized by a fine pulverizer or mechanical pulverizer using a jet stream, and a classifier using a swirling air stream or the Coanda effect is used. Classification to a predetermined particle size using a conventional classifier.

Further, as an example of producing a toner by a polymerization method, a toner composition containing at least a polymer having an active hydrogen group, polyester, a colorant, a release agent, and a charge control agent is resinized in an aqueous medium. In the presence of the fine particles, it is preferable to form at least one of a crosslinking reaction or an elongation reaction, or emulsion polymerization to form toner particles.
Further, as a method of changing the dispersed particle diameter of the wax as the release agent, the above-described pulverization method is performed by increasing the kneading time when kneading the toner material or kneading the toner material with a low melt viscosity during kneading. In the polymerization method, the wax dispersion particle size can be changed by adjusting the dispersion time in the step of dispersing the wax.

  The dispersion diameter of the wax was measured by setting the particle diameter in the maximum direction as the dispersion diameter. Specifically, the toner base particles are embedded in an epoxy resin, cut into thin sections of about 100 μm, stained with ruthenium tetroxide, and then photographed while observing the toner cross section at a magnification of 10,000 times with a transmission electron microscope. Take a picture. In this photograph, the particle size of 50 waxes is evaluated as the average dispersion diameter of the wax.

  The charge control agent contained in the toner of the present invention is an azo metal complex compound, a quaternary ammonium salt compound, a salicylic acid metal complex compound, or the like, and specifically includes an azo complex dye, a fluorine-containing quaternary ammonium salt, or salicylic acid. Examples thereof include metal zinc derivatives.

The toner of the present invention has a weight average particle diameter of 4.0 to 9.5 μm and a ratio (D4 / Dn) of the weight average particle diameter (D4) to the number average particle diameter (Dn) of 1.00 to 1.00. It is preferable to use a toner in the range of 1.40. More preferably, a toner having a weight average particle diameter (D4) of 3.0 to 7.0 μm and a D4 / Dn ratio in the range of 1.00 to 1.25 is used.
By using such a toner, it is possible to obtain a vivid color image having a wide intermediate color reproduction region and a narrow absorption region in a full color image. It is said that the smaller the toner particle diameter is, the more advantageous it is for obtaining a high-resolution and high-quality image, but it is disadvantageous for transferability and cleaning property. Further, when the weight average particle diameter (D4) is smaller than this range, in the case of a two-component developer, the toner is fused to the surface of the magnetic carrier during a long period of stirring in the developing device, and the charging ability of the magnetic carrier is reduced. When used as a one-component developer, toner filming on the developing roller and toner fusion to a member such as a blade for thinning the toner are likely to occur.

In addition, these phenomena are greatly related to the content of fine powder. Particularly when the particle size of the toner particles is 3 μm or less exceeds 10% by weight, the adhesion to the magnetic carrier and the charging stability at a high level are intended. It will be a hindrance. Conversely, when the weight average particle diameter (D4) of the toner is larger than the above range, it is difficult to obtain a high-resolution and high-quality image. Further, in a color image, the reproducibility of intermediate colors is lowered, the graininess is increased, and the quality of the color image is lowered.
On the other hand, if the D4 / Dn ratio exceeds 1.40, the charge amount distribution is widened and the resolution is lowered, which is not preferable.

The toner charge amount (Q / M) is measured as follows.
The measurement is performed by the blow-off method. The outline is that a two-component developer consisting of a toner and a carrier is put in a cage made of a metal cylinder with a metal mesh on both sides of the cylinder, and the metal cylinder cage is set horizontally in the Faraday cage. The compressed gas is blown from the other end or both ends of the metal cylindrical cage to separate the toner and the carrier. The opening of the metal mesh is selected so that the toner particles pass through and the carrier cannot pass through. The charged toner particles pass through the wire mesh and are blown out of the cage, but the carrier remains in the cage.
The carrier in the cage retains a charge Q of the opposite polarity in the same amount as that of the charged toner removed, and charges the capacitor of capacitance C connected to the cage. The voltage V across the capacitor is measured, and the specific charge amount (charge amount) of the toner is obtained from the following equation.
Charge (Q) = Capacitance (C) x Voltage (V)
Using the developer amount (M), the specific charge amount (charge amount) of the toner per unit mass is represented by Q / M.
Faraday cage configuration: A cage made of a metal cylinder containing a two-component developer is completely insulated by another metal cylinder grounded.
The measurement is performed using a TB-200 model manufactured by Toshiba Chemical Corporation.

The particle size distribution and average particle size of the toner were measured as follows.
Measuring machine: Coulter Multisizer II (Beckman Coulter, Inc.)
Aperture diameter: 100 μm
Electrolyte: Isoton II (Beckman Coulter, Inc.)
Dispersion: Emulgen 109P (manufactured by Kao Corporation, polyoxyethylene lauryl ether HLB 13.6) 5% electrolytic solution Dispersion condition: Add 5 mL of dispersion into a 100 mL (mL: milliliter) beaker, and add 10 mg of measurement sample into it To do. And it disperse | distributes for 1 minute with an ultrasonic disperser, Then, 25 mL of electrolyte solution is added, and it disperses for another 1 minute with an ultrasonic disperser.

Measurement conditions: 70 mL of electrolyte solution is put into a 100 mL beaker. Then, a liquid in which the sample is dispersed is added. As a concentration condition for adding the dispersion liquid, an amount of the dispersion liquid that can measure 30,000 particles in 20 seconds is added. The particle size is measured for 20 seconds to determine the particle size distribution. From the obtained distribution, the weight average particle diameter (D4) and the number average particle diameter of the toner particles can be obtained.
As channels, 2.00 to less than 2.52 μm; 2.52 to less than 3.17 μm; 3.17 to less than 4.00 μm; 4.00 to less than 5.04 μm; 5.04 to less than 6.35 μm; 6 Less than 35 to 8.00 μm; less than 8.00 to less than 10.08 μm; less than 10.08 to less than 12.70 μm; less than 12.70 to less than 16.00 μm; less than 16.00 to less than 20.20 μm; Uses 13 channels of less than 40 μm; 25.40 to less than 32.00 μm; 32.00 to less than 40.30 μm, and targets toner particles having a particle size of 2.00 μm to less than 40.30 μm.

  The toner of the present invention is preferably a toner using toner particles having an average circularity of 0.92 or more. Further, the average circularity of such toner particles is preferably 0.92 or more from the viewpoint of obtaining high image quality because of excellent dot reproducibility and good transferability. Further, since the average circularity is high, the toner is uniformly developed and transferred, and the toner is less likely to clump and adhere uniformly in the halftone portion and the solid portion, and is uniformly distributed.

  This makes it possible to reproduce a uniform intermediate color with little color unevenness when the toners are stacked and color overlapped, and the color reproduction range can be further expanded. When the average circularity is less than 0.92 and the toner has a shape separated from the spherical shape, it is difficult to obtain a high-quality image having sufficient transferability or dust. Such irregularly shaped particles have many points of contact with the smooth medium on the photoreceptor and the charge concentrates on the tip of the protrusion, so van der Waals force and mirror force are more than those with relatively spherical particles. Wearing power is high. For this reason, in the electrostatic transfer process, the spherical particles are selectively moved in the toner in which the amorphous particles and the spherical particles are mixed, and the character portion and the line portion image are lost. In addition, the remaining toner must be removed for the next development step, and there is a problem that a cleaning device is necessary and the toner yield (the ratio of toner used for image formation) is low.

  Further, it is preferable that the ratio of toner particles having toner particles having a circularity of less than 0.92 is 30% by weight or less. Toner base particles having a large variation in circularity such that the ratio exceeds 30% is not preferable because the charge speed and level are broadened and the charge amount distribution is broadened.

The circularity of the toner particles is a value obtained by optically detecting the particles and dividing by the circumference of an equivalent circle having the same projected area. Specifically, the measurement is performed using a flow type particle image analyzer (FPIA-2000; manufactured by Sysmex Corporation).
That is, 100 mL of water from which impure solids have been removed is put in a 200 mL container, 0.2 mL of a surfactant is added as a dispersant, and about 0.2 g of a measurement sample is added. The suspension in which the sample is dispersed is subjected to dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the concentration and dispersion of the dispersion are set to 3,000 to 10,000 / μL, and the shape and distribution of the toner are measured.

As shown in FIG. 1, the ratio (% by weight) of the toner particles (second toner particles) containing the average dispersed particle diameter (DWB) of the release agent (wax) is the same as that of the release agent (wax). The total amount of toner particles (first toner particles) and second toner particles containing the average dispersed particle diameter (DWA), that is, 5 to 75% by weight of the total toner is preferable, and 10 to 70% by weight is more preferable. preferable.
If it is less than 5% by weight, the temperature at which hot offset occurs is lowered. On the other hand, if it exceeds 75% by weight, the temperature at which hot offset occurs is increased, but the toner fluidity, the toner storage property, and the filming property to the latent image carrier tend to deteriorate.

The toner particles of the present invention are preferably toner particles having a shape factor SF-1 in the range of 100 to 180 and a shape factor SF-2 in the range of 100 to 180.
2A and 2B are diagrams schematically showing the shape of the toner, and are diagrams for explaining the shape factor SF-1 and the shape factor SF-2.
The substantially spherical shape of the toner particles of the present invention is represented by a shape factor SF-1, and the value of SF-1 is preferably in the range of 100 to 180. Here, the shape factor SF-1 indicates the ratio of the roundness of the toner particle shape, and is represented by the following formula (2). A value obtained by dividing the square of the maximum length MXLNG of a shape formed by projecting toner particles on a two-dimensional plane by the figure area AREA and multiplying by 100π / 4.
SF-1 = {(MXLNG) ² / AREA} × (100π / 4) Equation (2)

  When the value of SF-1 is 100, the shape of the toner particles is a true sphere, and becomes irregular as the value of SF-1 increases. When the value of SF-1 exceeds 180, the cleaning property is improved, but the spherical shape is greatly deviated, so that the charge amount distribution is widened, the ground cover is increased, and the image quality is lowered. Further, since the development and transfer by the electric field are not faithful to the lines of electric force due to the resistance of air in movement, the toner is developed between the fine lines, the image uniformity is lowered, and the image quality is lowered. In particular, when reproducing a color image, the color unevenness of the halftone part and the solid part increases, and the graininess also increases and the quality of the color image decreases. The value of SF-1 is preferably 110 to 150, and more preferably 115 to 145.

In the toner of the present invention, the unevenness of the toner particle surface is represented by a shape factor SF-2, and the value of SF-2 is preferably in the range of 100 to 180. Here, the shape factor SF-2 indicates the ratio of the unevenness of the shape of the toner particles, and is represented by the following formula (3). A value obtained by dividing the square of the perimeter PERI of the figure formed by projecting the toner particles on a two-dimensional plane by the figure area AREA and multiplying by 100 / 4π.
^{SF-2 = {(PERI)} 2 / AREA} × (100 / 4π) ...... (3)

  When the SF-2 value is 100, unevenness does not exist on the toner particle surface, and as the SF-2 value increases, the unevenness of the toner particle surface becomes more prominent. When the value of SF-2 exceeds 180, the cleaning property is improved, but the unevenness on the surface of the toner particles is increased, the charge amount distribution is widened, the ground cover is increased, and the image quality is lowered. Further, in color image reproduction, the color unevenness of the halftone part and the solid part increases, and the graininess increases and the quality of the color image decreases. Even if the value of SF-2 is 100 and the surface is smooth, the above-described toner can be cleaned even by the blade cleaning method, and a high-quality image can be obtained because the charge amount distribution is narrow. Further, the SF-2 value of the toner particles is preferably 110 to 150, and more preferably 115 to 145.

The toner particles of the present invention have a substantially spherical shape, and the shape is defined by a major axis r1, a minor axis r2, and a thickness r3 (where r1 ≧ r2 ≧ r3), and the major axis r1 and the minor axis r2. The ratio (r2 / r1) is preferably in the range of 0.5 to 1.0, and the ratio of the thickness r3 to the minor axis r2 (r3 / r2) is preferably in the range of 0.7 to 1.0. .
FIG. 3A is a diagram schematically showing the shape of the toner particles of the present invention. In FIG. 3A, when the substantially spherical toner particles are defined by a major axis r1, a minor axis r2, and a thickness r3 (provided that r1 ≧ r2 ≧ r3), the toner of the present invention is long The ratio of axis to minor axis (r2 / r1) (see FIG. 3 (b)) is 0.5 to 1.0, and the ratio of thickness to minor axis (r3 / r2) (see FIG. 3 (c)). Is preferably in the range of 0.7 to 1.0. When the ratio of the major axis to the minor axis (r2 / r1) is less than 0.5, the dot reproducibility and transfer efficiency are inferior because of being away from the true spherical shape, and high quality image quality cannot be obtained. If the ratio of thickness to short axis (r3 / r2) is less than 0.7, the shape is close to a flat shape, and a high transfer rate like a spherical toner cannot be obtained. In particular, when the ratio of the thickness to the minor axis (r3 / r2) is 1.0, the rotating body has a major axis as a rotation axis, and the fluidity of the toner can be improved.
In addition, r1, r2, r3 can be measured by the following method, for example. That is, the toner is uniformly dispersed and adhered on a smooth measurement surface, and 100 particles of the toner are magnified 500 times by a color laser microscope “VK-8500” (manufactured by Keyence Corporation) to obtain the 100 toners. The long axis r1 (μm), the short axis r2 (μm), and the thickness r3 (μm) of the particles can be measured and obtained from their arithmetic average values.

The toner of the present invention can further have an external additive.
As the external additive, inorganic fine particles and organic fine particles can be used. As the inorganic fine particles, metal compounds such as oxides, nitrides, carbides and carbonates are used. Specifically, silicon oxide (silica), aluminum oxide (alumina), titanium oxide (titania), zinc oxide, zirconium oxide, cerium oxide, tungsten oxide, manganese oxide, barium titanate, strontium titanate, titanate Examples thereof include oxides such as magnesium, calcium carbonate, and potassium carbonate, silicon nitride, aluminum nitride, and the like, nitrides such as carbon nitride, and carbides such as nitrogen carbide. In particular, oxides of silicon, titanium, and aluminum are preferably used. Organic fine particles include polymer fine particles such as vinyl resins, polyurethane resins, epoxy resins, polyester resins, polyamide resins, polyimide resins, silicon resins, phenol resins obtained by soap-free emulsion polymerization, suspension polymerization, and dispersion polymerization. , Polymer particles of melamine resin, urea resin, aniline resin, ionomer resin, polycarbonate resin. Such an inorganic or organic external additive is preferably subjected to a surface treatment to increase the hydrophobicity because it can prevent deterioration of flow characteristics and charging characteristics even under high humidity. Such surface treatment can be performed using a surface treatment agent. For example, silane coupling agents, silylating agents, silane coupling agents having an alkyl fluoride group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils and the like are preferable surface treatment agents. It is done. In such an external additive, the number average particle diameter of the primary particles before forming the aggregate is preferably 5 nm to 500 nm. The use ratio of the external additive composed of at least one kind of inorganic fine particles and organic fine particles is preferably 0.01 to 5% by weight, particularly 0.01 to 4.0% by weight of the toner. Is preferred.

  In order to remove the residual toner after transfer remaining on the photosensitive member or the primary transfer medium, a cleaning property improver in the blade cleaning method is contained in the toner particles or added to the toner as, for example, an external additive. Or can be contained in or added to the developer. Examples of such a cleaning property improver include fatty acid metal salts such as zinc stearate and calcium stearate, polymer fine particles produced by soap-free emulsion polymerization such as polymethyl methacrylate fine particles and polystyrene fine particles, and the like. . The polymer fine particles preferably have a relatively narrow particle size distribution and a number average particle size of 1 nm to 100 nm.

  For mixing external additives, a general powder mixer is used. For example, examples of the mixing apparatus that can be used include a Redige mixer, a Nauter mixer, and a Henschel mixer (FM20B, manufactured by Mitsui Miike Kogyo Co., Ltd.).

  The particle diameter of the external additive (inorganic fine particles) is measured by a particle size distribution measuring apparatus using dynamic light scattering, for example, DLS-700 manufactured by Otsuka Electronics Co., Ltd. However, since it is difficult to dissociate secondary agglomeration of toner particles whose surface has been treated, for example, with silicone oil, the particle size is directly determined from a photograph obtained by a scanning electron microscope or a transmission electron microscope. In this case, at least 100 or more inorganic fine particles are observed, and the average value of the major axis is obtained.

Here, the production method of the toner particles by the polymerization method will be described in detail as follows. For example, in the suspension polymerization method, a dispersion stabilizer, a colorant, a charge control agent, a release agent and, if necessary, a crosslinking agent are uniformly dispersed with a ball mill or the like to the monomer, and then polymerization is started. Add the agent, obtain the monomer phase, put the aqueous dispersion medium phase prepared by stirring with the monomer phase in a stirring tank, stir with a homogenizer, etc., and heat the resulting suspension after purging with nitrogen By completing the polymerization reaction, colored resin particles are obtained, which are washed and dried to obtain toner particles having a high degree of circularity.
Further, a toner particle material liquid in which at least a polyester prepolymer having a functional group containing a nitrogen atom, polyester, a colorant, a release agent, and a charge control agent is dispersed in an organic solvent is crosslinked and / or in an aqueous solvent. Obtained by extension reaction. Furthermore, in the emulsion polymerization method, it is possible to produce an appropriate particle size as toner particles by agglomerating while controlling sub-micron order particles.

  Crosslinking and / or forming particles in an aqueous medium by dissolving or dispersing at least a binder resin or a resin precursor of the binder resin, a release agent in an organic solvent or a polymerizable monomer. A constituent material using a toner obtained by an elongation reaction and a suitable manufacturing method will be described.

(polyester)
The polyester is obtained by a polycondensation reaction between a polyhydric alcohol compound and a polycarboxylic acid compound.
Examples of the polyhydric alcohol compound (PO) include dihydric alcohol (DIO) and trihydric or higher polyhydric alcohol (TO). (DIO) alone or a mixture of (DIO) and a small amount of (TO) preferable.

Examples of the dihydric alcohol (DIO) include alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.); alkylene ether glycol (diethylene glycol) , Triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); bisphenols (bisphenol A, bisphenol) F, bisphenol S, etc.); alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of the above alicyclic diol; Alkylene oxide bisphenol (ethylene oxide, propylene oxide, butylene oxide, etc.), etc. adducts.
Among them, preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols, and particularly preferred are alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. It is a combined use.

  The trihydric or higher polyhydric alcohol (TO) includes 3 to 8 or higher polyhydric aliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); trihydric or higher phenols (Trisphenol PA, phenol novolak, cresol novolak, etc.); and alkylene oxide adducts of the above trivalent or higher polyphenols.

  Examples of the polyvalent carboxylic acid (PC) include divalent carboxylic acid (DIC) and trivalent or higher polyvalent carboxylic acid (TC). (DIC) alone and (DIC) with a small amount of (TC) Mixtures are preferred. Divalent carboxylic acids (DIC) include alkylene dicarboxylic acids (succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acids (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acids (phthalic acid, isophthalic acid, terephthalic acid) And naphthalenedicarboxylic acid). Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms. Examples of the trivalent or higher polyvalent carboxylic acid (TC) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid). In addition, as polyhydric carboxylic acid (PC), you may make it react with polyhydric alcohol (PO) using the above-mentioned acid anhydride or lower alkyl ester (Methyl ester, ethyl ester, isopropyl ester, etc.).

  The ratio of the polyhydric alcohol (PO) to the polycarboxylic acid (PC) is usually 2/1 to 1/1, preferably as the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. Is 1.5 / 1 to 1/1, more preferably 1.3 / 1 to 1.02 / 1.

The polycondensation reaction between a polyhydric alcohol (PO) and a polycarboxylic acid (PC) is carried out in the presence of a known esterification catalyst such as tetrabutoxytitanate or dibutyltin oxide, and heated to 150 to 280 ° C. while reducing the pressure as necessary. The produced water is distilled off to obtain a polyester having a hydroxyl group. The hydroxyl value (mgKOH / g) of the polyester is preferably 5 or more, and the acid value (mgKOH / g) of the polyester is usually 1 to 30, preferably 5 to 20. By giving an acid value, it tends to be negatively charged, and furthermore, when fixing to a recording paper, the affinity between the recording paper and the toner is good and the low-temperature fixability is improved. However, when the acid value exceeds 30, there is a tendency to deteriorate with respect to the stability of charging, particularly environmental fluctuation.
The weight average molecular weight is 10,000 to 400,000, preferably 20,000 to 200,000. A weight average molecular weight of less than 10,000 is not preferable because offset resistance deteriorates. On the other hand, if it exceeds 400,000, the low-temperature fixability is deteriorated.

  In addition to the unmodified polyester obtained by the above polycondensation reaction, the polyester preferably contains a urea-modified polyester. The urea-modified polyester is obtained by reacting a terminal carboxyl group or hydroxyl group of the polyester obtained by the above polycondensation reaction with a polyvalent isocyanate compound (PIC) to obtain a polyester prepolymer (A) having an isocyanate group. Is obtained by at least one of cross-linking and elongation of the molecular chain by the reaction of the amine with amines.

  Examples of the polyvalent isocyanate compound (PIC) include aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, etc.); alicyclic polyisocyanates (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.) Aromatic diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, etc.); araliphatic diisocyanates (α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.); isocyanates; Those blocked with caprolactam or the like; and combinations of two or more of these.

The ratio of the polyvalent isocyanate compound (PIC) is usually 5/1 to 1/1, preferably as an equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] and the hydroxyl group [OH] of the polyester having a hydroxyl group. 4/1 to 1.2 / 1, more preferably 2.5 / 1 to 1.5 / 1. When [NCO] / [OH] exceeds 5, low-temperature fixability deteriorates. When the molar ratio of [NCO] is less than 1, when a urea-modified polyester is used, the urea content in the ester is lowered and hot offset resistance is deteriorated.
The content of the polyvalent isocyanate compound (PIC) component in the polyester prepolymer (A) having an isocyanate group is usually 0.5 to 40 wt%, preferably 1 to 30 wt%, more preferably 2 to 20 wt%. . If it is less than 0.5 wt%, the hot offset resistance deteriorates, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. On the other hand, if it exceeds 40 wt%, the low-temperature fixability deteriorates.
The number of isocyanate groups contained per molecule in the polyester prepolymer (A) having an isocyanate group is usually 1 or more, preferably 1.5 to 3 on average, more preferably 1.8 to 2 on average. Five. If it is less than 1 per molecule, the molecular weight of the urea-modified polyester will be low, and the hot offset resistance will deteriorate.

Next, as amines (B) to be reacted with the polyester prepolymer (A), a divalent amine compound (B1), a trivalent or higher polyvalent amine compound (B2), an amino alcohol (B3), an amino mercaptan (B4) ), Amino acid (B5), and amino acid block of B1 to B5 (B6).
Examples of the divalent amine compound (B1) include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′-diaminodiphenylmethane, etc.); alicyclic diamines (4,4′-diamino-3,3′-dimethyldicyclohexyl). Methane, diamine cyclohexane, isophorone diamine, etc.); and aliphatic diamines (ethylene diamine, tetramethylene diamine, hexamethylene diamine, etc.) and the like.
Examples of the trivalent or higher polyvalent amine compound (B2) include diethylenetriamine and triethylenetetramine.
Examples of amino alcohol (B3) include ethanolamine and hydroxyethylaniline.
Examples of amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan.
Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid.
Examples of the compound (B6) obtained by blocking the amino group of B1 to B5 include ketimine compounds and oxazolidine compounds obtained from the amines of B1 to B5 and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.).
Among these amines (B), preferred are B1 and a mixture of B1 and a small amount of B2.

  The ratio of amines (B) is equivalent to the equivalent ratio [NCO] / [NHx] of isocyanate groups [NCO] in the polyester prepolymer (A) having isocyanate groups and amino groups [NHx] in amines (B). Is usually 1/2 to 2/1, preferably 1.5 / 1 to 1 / 1.5, more preferably 1.2 / 1 to 1 / 1.2. When [NCO] / [NHx] exceeds 2 or less than 1/2, the molecular weight of the urea-modified polyester becomes low, and the hot offset resistance deteriorates.

  The urea-modified polyester may contain a urethane bond together with a urea bond. The molar ratio of the urea bond content to the urethane bond content is usually 100/0 to 10/90, 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%, the hot offset resistance is deteriorated.

  The urea-modified polyester is produced by a one-shot method or the like. Polyhydric alcohol (PO) and polyvalent carboxylic acid (PC) are heated to 150-280 ° C. in the presence of a known esterification catalyst such as tetrabutoxytitanate, dibutyltin oxide, etc., and water generated while reducing the pressure as necessary. Distill off to obtain a polyester having a hydroxyl group. Subsequently, at 40-140 degreeC, this is made to react with polyvalent isocyanate (PIC), and the polyester prepolymer (A) which has an isocyanate group is obtained. Further, this (A) is reacted with amines (B) at 0 to 140 ° C. to obtain a urea-modified polyester. When reacting (PIC) and when reacting (A) and (B), a solvent may be used if necessary. Solvents that can be used include aromatic solvents (toluene, xylene, etc.); ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.); esters (ethyl acetate, etc.); amides (dimethylformamide, dimethylacetamide, etc.) and ethers And those inert to isocyanates (PIC), such as tetrahydrofuran (such as tetrahydrofuran).

In addition, for at least one reaction of the crosslinking reaction or elongation reaction between the polyester prepolymer (A) and the amines (B), a reaction terminator can be used as necessary to adjust the molecular weight of the resulting urea-modified polyester. . Examples of the reaction terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), and those obtained by blocking them (ketimine compounds).
The weight average molecular weight of the urea-modified polyester is usually 10,000 or more, preferably 20,000 to 10,000,000, and more preferably 30,000 to 1,000,000. If it is less than 10,000, the hot offset resistance deteriorates. The number average molecular weight of the urea-modified polyester or the like is not particularly limited when the above-mentioned unmodified polyester is used, and may be a number average molecular weight that can be easily obtained to obtain the weight average molecular weight. When the urea-modified polyester is used alone, its number average molecular weight is usually 2000-15000, preferably 2000-10000, more preferably 2000-8000. When it exceeds 20000, the low-temperature fixability and the glossiness when used in a full-color apparatus are deteriorated.

By using the unmodified polyester and the urea-modified polyester in combination, the low-temperature fixability and the gloss when used in the full-color image forming apparatus 100 are improved. Therefore, it is preferable to use the urea-modified polyester alone. In addition, polyester modified by chemical bonds other than urea bonds may be included.
The unmodified polyester and the urea-modified polyester are preferably at least partially compatible with each other in terms of low-temperature fixability and hot offset resistance. Therefore, it is preferable that the unmodified polyester and the urea-modified polyester have a similar composition.

The weight ratio of unmodified polyester to urea-modified polyester is usually 20/80 to 95/5, preferably 70/30 to 95/5, more preferably 75/25 to 95/5, and particularly preferably 80 /. 20-93 / 7. When the weight ratio of the urea-modified polyester is less than 5%, the hot offset resistance is deteriorated, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. The glass transition point (Tg) of the binder resin containing unmodified polyester and urea-modified polyester is usually 45 to 65 ° C, preferably 45 to 60 ° C. If it is less than 45 ° C., the heat resistance of the toner deteriorates, and if it exceeds 65 ° C., the low-temperature fixability becomes insufficient.
In addition, since the urea-modified polyester is likely to be present on the surface of the obtained toner base particles, the heat-resistant storage stability tends to be good even when the glass transition point is low as compared with known polyester-based toners.

(Coloring agent)
As the colorant, all known dyes and pigments can be used. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher , Yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), permanent yellow (NCG), Vulcan fast yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Red Dan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red, Phi Sayred, Parachlor Ortonito Aniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmin Min BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX, Permanent Red F5R , Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Torujin Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thio Indigo Red B, Thioindigo Maroon, Oil Red, Quinacridone Red, Pyrazolone Red Polyazo Red, Chrome Vermillion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), indigo, ultramarine blue, bitumen, anthraquinone blue, fast violet B, methyl violet lake, cobalt purple, manganese purple, dioxane violet, anthraquinone violet, chrome green, zinc green, chromium oxide, pyridian, emerald green, pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Green Lake, Fu Russia Nin green, anthraquinone green, titanium oxide, zinc white, lithopone and mixtures thereof can be used. The content of the colorant is usually 1 to 15% by weight, preferably 3 to 10% by weight, based on the toner.

  The colorant can also be used as a master batch combined with a resin. As a binder resin to be kneaded with the production of the master batch or the master batch, a polymer of styrene such as polystyrene, poly-p-chlorostyrene, polyvinyl toluene or the like, or a copolymer of these and a vinyl compound, Polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, fat Aromatic or alicyclic hydrocarbon resins, aromatic petroleum resins, chlorinated paraffins, paraffin waxes and the like can be mentioned, and these can be used alone or in combination.

(Release agent)
The toner particles used in the toner of the present invention contain a wax as a release agent in order to give the developer release properties. Such a wax as a release agent has a melting point of 40 to 120 ° C., particularly preferably 50 to 110 ° C. When the melting point of the wax is excessive, the fixing property at a low temperature may be insufficient. On the other hand, when the melting point is excessively low, the offset resistance and durability may be decreased. The melting point of the wax can be determined by a differential scanning calorimeter (DSC). That is, the melting peak value when a sample (wax) of several mg is ripened at a constant temperature increase rate, for example, (10 ° C./min) is defined as the melting point. The content of the wax in the toner containing the wax is preferably 1.0 to 15.0% by weight, and more preferably 2.5 to 12.5% by weight.

  Examples of the wax that is a release agent that can be used in the present invention include solid paraffin wax, micro wax, rice wax, fatty acid amide wax, fatty acid wax, aliphatic monoketone, fatty acid metal salt wax, and fatty acid ester. And waxes, partially saponified fatty acid ester waxes, silicone varnishes, higher alcohols and carnauba waxes. Also, polyolefins such as low molecular weight polyethylene and polypropylene can be used. Particularly, a polyolefin having a softening point of 70 to 150 ° C. by the ring and ball method is preferable, and a polyolefin having a softening point of 120 to 150 ° C. is more preferable.

(Charge control agent)
Known charge control agents can be used, such as nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (fluorine-modified 4 Secondary ammonium salts or compounds, tungsten simple substances or compounds, fluorine activators, salicylic acid metal salts, and metal salts of salicylic acid derivatives. Specifically, Bontron 03 of a nigrosine dye, Bontron P-51 of a quaternary ammonium salt, Bontron S-34 of a metal-containing azo dye, E-82 of an oxynaphthoic acid metal complex, E-84 of a salicylic acid metal complex , Phenolic condensate E-89 (above, Orient Chemical Industries, Ltd.), quaternary ammonium salt molybdenum complex TP-302, TP-415 (above, Hodogaya Chemical Co., Ltd.), quaternary ammonium salt copy Charge PSY VP2038, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, LR-147 which is a boron complex (Nippon Carlit) Manufactured), copper phthalocyanine, perylene, quinacridone, azo series Fee, a sulfonic acid group, a carboxyl group, and polymer compounds having a functional group such as quaternary ammonium salts. Of these, substances that control the negative polarity of the toner are particularly preferably used.

  The amount of charge control agent used is determined by the type of binder resin, the presence or absence of additives used as necessary, and the toner production method including the dispersion method, and is not limited to a specific one. Preferably, it is used in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the binder resin. The range of 0.2 to 5 parts by weight is preferable. When the amount exceeds 10 parts by weight, the chargeability of the toner is too high, the effect of the charge control agent is reduced, the electrostatic attraction with the developing roller is increased, the flowability of the developer is lowered, and the image density is lowered. Invite. The charge control agent and the release agent may be melt-kneaded together with the masterbatch and binder resin, or may be added when dissolved and dispersed in an organic solvent.

  Next, a toner manufacturing method will be described. The present invention is not limited to these preferred manufacturing methods.

(Toner production method)
1) A toner material liquid is prepared by dispersing a colorant, unmodified polyester, a polyester prepolymer having an isocyanate group, and a release agent in an organic solvent. The organic solvent is preferably volatile with a boiling point of less than 10 ° C. from the viewpoint of easy removal after toner base particle formation. Specifically, toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, methyl ethyl ketone, Methyl isobutyl ketone and the like can be used alone or in combination of two or more. In particular, aromatic solvents such as toluene and xylene and halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, chloroform, and carbon tetrachloride are preferable. The usage-amount of an organic solvent is 0-300 weight part normally with respect to 100 weight part of polyester prepolymers, Preferably it is 0-100 weight part, More preferably, it is 25-70 weight part.

2) The toner material liquid is emulsified in an aqueous medium in the presence of a surfactant and resin fine particles. The aqueous medium may be water alone or an organic solvent such as alcohol (methanol, isopropyl alcohol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methyl cellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.). It may be included.
The amount of the aqueous medium used relative to 100 parts by weight of the toner material liquid is usually 50 to 2000 parts by weight, preferably 100 to 1000 parts by weight. If the amount is less than 50 parts by weight, the dispersion state of the toner material liquid is poor and toner particles having a predetermined particle diameter cannot be obtained. If it exceeds 20000 parts by weight, it is not economical.

Further, in order to improve the dispersion in the aqueous medium, a dispersing agent such as a surfactant and resin fine particles can be appropriately added.
As surfactants, anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters, alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt types such as imidazoline, Quaternary ammonium salt type cationic surfactants such as alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride, fatty acid amide derivative, polyhydric alcohol Nonionic surfactants such as derivatives, for example, amphoteric surfactants such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl-N, N-dimethylammonium betaine And the like.

Further, by using a surfactant having a fluoroalkyl group, the effect can be obtained in a very small amount. Preferred anionic surfactants having a fluoroalkyl group include fluoroalkylcarboxylic acids having 2 to 10 carbon atoms and metal salts thereof, disodium perfluorooctanesulfonyl glutamate, 3- [ω-fluoroalkyl (C _6- C ₁₁₎ oxy] -1-alkyl _(C 3 -C ₄ (number 3-4 carbons)) sodium sulfonate, 3- [.omega.-fluoroalkanoyl _(C 6 -C ₈ (the number of carbon atoms (number of 6 to 11 carbon atoms) 6-8)) - N-ethylamino] -1-sodium sulfonic acid, fluoroalkyl _(C 11 _{~C 20 (11~20} carbon atoms)) carboxylic acids and metal salts thereof, perfluoroalkyl carboxylic acids _(C 7 ~ C ₁₃ (7 to 13 carbon atoms)) and metal salts thereof, perfluoroalkyl _(C 4 _{~C 12 (4~12} carbon atoms)) sul Acid and metal salts thereof, perfluorooctane sulfonic acid diethanol amine de, N- propyl-N-(2-hydroxyethyl) perfluorooctane sulfonamide, perfluoroalkyl _(C 6 _{~C 10 (6~10} carbon atoms)) sulfonamide propyl trimethyl ammonium salts, perfluoroalkyl _(C 6 _{~C 10 (6~10} carbon atoms)) - N-ethylsulfonyl glycine salts, monoperfluoroalkyl _(C 6 _{~C 16 (6~16} carbon atoms)) Examples thereof include ethyl phosphate.

  As commercial names of these anionic surfactants, Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.), Florard FC-93, FC-95, FC-98, FC-129 ( Sumitomo 3M), Unidyne DS-101, DS-102 (Daikin Kogyo), MegaFuck F-110, F-120, F-113, F-191, F-812, F-833 (Dainippon Ink) Xttop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204, (Tochem Products), Footent F-100, F150 (Neos) Etc.

In addition, as the cationic surfactant, aliphatic primary, secondary or secondary amine acid having a fluoroalkyl group, perfluoroalkyl (C ₆ -C ₁₀ (C 6-10)) sulfonamidopropyltrimethylammonium Examples thereof include aliphatic quaternary ammonium salts such as salts, benzalkonium salts, benzethonium chloride, pyridinium salts, imidazolinium salts and the like.

  Commercial names of these cationic surfactants include Surflon S-121 (Asahi Glass Co., Ltd.), Florard FC-135 (Sumitomo 3M Co., Ltd.), Unidyne DS-202 (Daikin Industries Co., Ltd.), MegaFuck F -150, F-824 (manufactured by Dainippon Ink, Inc.), Xtop EF-132 (manufactured by Tochem Products), and footent F-300 (manufactured by Neos).

  As the resin fine particles, the aforementioned substances can be used. In addition, inorganic compound dispersants such as tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, and hydroxyapatite can also be used. As a dispersant that can be used in combination with the above resin fine particles and inorganic compound dispersant, the dispersed droplets may be stabilized by a polymer protective colloid. For example, acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride and other (meth) acrylic monomers containing hydroxyl groups Such as acrylic acid-β-hydroxyethyl, methacrylic acid-β-hydroxyethyl, acrylic acid-β-hydroxypropyl, methacrylic acid-β-hydroxypropyl, acrylic acid-γ-hydroxypropyl, methacrylic acid-γ-hydroxypropyl , 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate Luric acid esters, N-methylol acrylamide, N-methylol methacrylamide, etc., vinyl alcohol or ethers with vinyl alcohol, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, or compounds containing vinyl alcohol and a carboxyl group Esters such as vinyl acetate, vinyl propionate, vinyl butyrate, acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds, acid chlorides such as acrylic acid chloride, methacrylic acid chloride, vinyl pyridine, vinyl pyrrolidone, vinyl Nitrogen compounds such as imidazole and ethyleneimine, or homopolymers or copolymers such as those having a heterocyclic ring thereof, polyoxyethylene, poly Xoxypropylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxy Polyoxyethylenes such as ethylene nonylphenyl ester, celluloses such as methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose can be used.

  The dispersion method is not particularly limited, and known equipment such as a low-speed shear method, a high-speed shear method, a friction method, a high-pressure jet method, and an ultrasonic wave can be applied. Among these, the high-speed shearing method is preferable in order to make the particle size of the dispersion 2 to 20 μm. When a high-speed shearing disperser is used, the rotational speed is not particularly limited, but is usually 1000 to 30000 rpm, preferably 5000 to 20000 rpm. The dispersion time is not particularly limited, but in the case of a batch method, it is usually 0.1 to 5 minutes. The temperature during dispersion is usually 0 to 150 ° C. (under pressure), preferably 40 to 98 ° C.

3) At the same time as the preparation of the emulsion, the amines (B) are added to cause a reaction with the polyester prepolymer (A) having an isocyanate group.
This reaction involves molecular chain crosslinking and / or elongation. The reaction time is selected depending on the reactivity between the isocyanate group structure of the polyester prepolymer (A) and the amines (B), but is usually 10 minutes to 40 hours, preferably 2 to 24 hours. The reaction temperature is generally 0 to 150 ° C, preferably 40 to 98 ° C. Moreover, a well-known catalyst can be used as needed. Specific examples include dibutyltin laurate and dioctyltin laurate.

4) After completion of the reaction, the organic solvent is removed from the emulsified dispersion (reactant), washed and dried to obtain toner base particles.
In order to remove the organic solvent, the temperature of the entire system is gradually raised in a laminar stirring state, and after giving strong stirring in a certain temperature range, the solvent base is removed to produce spindle-shaped toner base particles. . Further, when an acid such as calcium phosphate salt or an alkali-soluble material is used as the dispersion stabilizer, the calcium phosphate salt is dissolved from the toner base particles by a method such as dissolving the calcium phosphate salt with an acid such as hydrochloric acid and washing with water. Remove.
It can also be removed by operations such as enzymatic degradation. Either before or after the washing and solvent-removing steps, a step can be provided in which the emulsified dispersion is allowed to stand at a certain temperature for a certain period of time and the produced toner particles are aged. Thereby, toner particles having a desired particle diameter can be produced. The temperature of the aging step is preferably 25 to 50 ° C., and the time is preferably 10 minutes to 23 hours.

5) A charge control agent is injected into the toner base particles obtained above, and then inorganic fine particles such as silica fine particles and titanium oxide fine particles are externally added to obtain a toner. The injection of the charge control agent and the external addition of the inorganic fine particles are performed by a known method using a mixer or the like.
Thereby, a toner having a small particle size and a sharp particle size distribution can be easily obtained. Furthermore, by giving strong agitation in the process of removing the organic solvent, the shape between the spherical shape and the spindle shape can be controlled, and the surface morphology is also controlled between the smooth shape and the umeboshi shape. Can do.

  The developer of the present invention contains at least the toner of the present invention, and other components such as a carrier selected appropriately. The developer may be a one-component developer or a two-component developer. However, when it is used for a high-speed printer or the like corresponding to the recent improvement in information processing speed, the life is improved. In view of the above, the two-component developer is preferable. In the case of the one-component developer using the toner of the present invention, even if the balance of the toner is performed, there is little fluctuation in the particle diameter of the toner, and the filming of the toner on the developing roller or the toner is made thin. Therefore, the toner is not fused to a member such as a blade, and good and stable developability and images can be obtained even when the developing device is used (stirred) for a long time. Further, in the case of the two-component developer using the toner of the present invention, even if the balance of the toner over a long period of time is performed, the fluctuation of the toner particle diameter in the developer is small, and even in the long-term stirring in the developer, Good and stable developability can be obtained.

  When the toner of the present invention is mixed with a magnetic carrier and used as a two-component developer, the content ratio of the carrier and the toner in the developer is preferably 1 to 10 parts by weight of the toner with respect to 100 parts by weight of the carrier. As the magnetic carrier, conventionally known ones such as iron powder, ferrite powder, magnetite powder, magnetic resin carrier having a particle diameter of about 20 to 100 μm can be used. Examples of the coating material include amino resins such as urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Polyvinyl and polyvinylidene resins such as acrylic resins, polymethyl methacrylate resins, polyacrylonitrile resins, polyvinyl acetate resins, polyvinyl alcohol resins, polyvinyl butyral resins, polystyrene resins and styrene acrylic copolymer resins, Halogenated olefin resins such as vinyl, polyester resins such as polyethylene terephthalate resin and polybutylene terephthalate resin, polycarbonate resins, polyethylene resins, polyvinyl fluoride resins, polyvinylidene fluoride resins, polytrifluoroethylene resins, polyhexafluoro Propylene resin, copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and vinyl fluoride, tetrafluoroethylene and vinylidene fluoride and non- Monomers including a fluoro terpolymers such, and silicone resins.

  Moreover, you may contain electrically conductive powder etc. in coating resin as needed. As the conductive powder, metal powder, carbon black, titanium oxide, tin oxide, zinc oxide or the like can be used. These conductive powders preferably have an average particle diameter of 1 μm or less.

  As a method for forming the resin layer, the resin may be applied to the surface of the carrier core particle by means of a spraying method, a dipping method, or the like, as in the past. Examples include tilting pan by rolling, drum, fluidized bed, movable spray, fluidized bed by aeration (spray drying, vibration, draft pipe, movable draft pipe), spouted bed (jet fluidized bed), rolling fluidized bed (with slits) The carrier core material is coated with resin by a rotating disk) or by stirring and mixing (stirring blade, high-speed shearing, vertical stirring blade, eccentric stirring blade).

  Furthermore, the coated carrier used in the present invention may be one in which a conductive material is dispersed in the coating layer in order to adjust carrier resistance. Specific examples of the conductive material in this case include the following. When the average particle diameter is larger than 1 μm, it becomes difficult to control electric resistance.

(A) White conductive material ETC-52 (TiO ₂ series) Titanium Industry Co., Ltd. KV400 (TiO ₂ series) Titanium Industry Co., Ltd. ECR-72 (TiO ₂ series) Titanium Industry Co., Ltd. ECTR-82 (TiO ₂ series) Titanium 500 W (TiO ₂ system) manufactured by Kogyo Co., Ltd. 300 W (TiO ₂ system) manufactured by Ishihara Sangyo Co., Ltd. S-1 (TiO ₂ system) manufactured by Ishihara Sangyo Co., Ltd. W-1 (SnO ₂ system) 23 K (ZnO) manufactured by Mitsubishi Metal Corporation ) Conductive zinc white no. 1 (ZnO) Honjo Chemical Co., Ltd., conductive zinc white 2 (ZnO) Honjo Chemical Co., Ltd. W-10 (TiO_ system) Mitsubishi Metals Co., Ltd. Dentor WK-100 (conductive fiber) Otsuka Chemical Co., Ltd. Dentor WK-200 (conductive fiber) Otsuka Chemical Co., Ltd. Dentor WK-300 (conductive fiber) manufactured by Otsuka Chemical Co. MEC300 (SnO ₂ system) Teikoku Kako Co. MEC500 (SnO ₂ system) Teikoku Kako Co.

(B) Carbon Black Pearls 2000, VULCANXC-72 (manufactured by Cabot) Ketjen black EC / DJ500, Ketchen black EC / DJ600 (manufactured by Lion Akzo) Denka black powder, Denka black powder (manufactured by Denki Kagaku Kogyo) CONDUCTEX 975, CONDUCTEX SC (manufactured by Columbia Carbon Co.)

  A coupling agent may be added. The addition of a coupling agent improves the adhesion between the carrier core material and the coating layer, and the layer does not peel off even when the developing part is stirred. In addition, the charge amount can be adjusted. For example, the charge amount is hardly generated under the influence of moisture under high temperature and high humidity conditions, but a good charge amount can be secured by adding a coupling agent.

  Examples of silane coupling agents include trade names: SH6020 (γ- (2-aminoethyl) aminopropyltrimethoxysilane), SZ6023 (γ- (2-aminoethyl) aminopropylmethyldimethoxysilane), SH6026 (aminosilane), SZ6030 (γ-methacryloxypropyltrimethoxysilane), SZ6032 (N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane, hydrochloride), SZ6050 (aminosilane), SZ6040 (γ-glycid) Xipropyltrimethoxysilane), SH6062 (γ-mercaptopropyltrimethoxysilane), SZ6070 (methyltrimethoxysilane), SZ6072 (methyltriethoxysilane), SZ6075 (vinyltriacetoxysilane), SZ 076 (γ-chloropropyltrimethoxysilane), SZ6079 (hexamethyldisilazane), SZ6083 (γ-anilinopropyltrimethoxysilane) and the like are manufactured by Toray Dow Corning Silicone, Inc. KA1003 (vinylchlorosilane), KBC1003 (Vinyltris (βmethoxyethoxy) silane), KBM1003 (vinyltrimethoxysilane), KBE1003 (vinyltriethoxysilane), KBM503 (γ-methacryloxypropyltrimethoxysilane), KBM303 (β- (3,4 epoxy cyclohexyl) ethyl Trimethoxysilane), KBM403 (γ-glycidoxypropyltrimethoxysilane), KBM402 (γ-glycidoxypropylmethylethoxysilane), KBM603 (N-β (aminoethyl) γ -Aminopropyltrimethoxysilane), KBM602 (N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane), KBM903 (γ-aminopropyltriethoxysilane), KBM803 (γ-mercaptopropyltrimethoxysilane), KBM573 ( N-phenyl-γ-aminopropyltrimethoxysilane), KBM703 (γ-chloropropyltrimethoxysilane), etc. manufactured by Shin-Etsu Chemical Co., Ltd., aluminum-based coupling agents, and titanium-based coupling agents may be used.

  Moreover, the same material as the material which coat | covers a carrier core material can be used for a magnetic body dispersion type carrier particle. Examples of the magnetic fine powder include any material exhibiting magnetic sensitivity. For example, metals such as iron, nickel and cobalt, metal oxides, alloys and the like. Often used materials include triiron tetroxide, iron sesquioxide, cobalt-added iron oxide, ferrite, and nickel fine powder. In some cases, the magnetic fine powder may be a colored magnetic substance. In addition, the toner of the present invention can be used as a one-component magnetic toner by containing a magnetic material without using a carrier, or as a non-magnetic toner as a single component without containing a magnetic material.

An image forming apparatus using the toner of the present invention as a developer will be described.
As shown in FIG. 4, it is wound around three support rollers 14 to 16 so as to be able to rotate and convey clockwise in the figure. In this example, an intermediate transfer body cleaning device 17 (not shown) that removes residual toner remaining on the intermediate transfer body 10 after image transfer can be provided on the left of the second support roller 15 among the three. Further, four images of yellow, cyan, magenta, and black are arranged on the intermediate transfer member 10 stretched between the first support roller 14 and the second support roller 15 among the three along the conveyance direction. The tandem image forming apparatus 20 can be configured by arranging the forming units 18 side by side.

  An exposure device 21 can be further provided on the tandem image forming apparatus 20 as shown in FIG. On the other hand, a secondary transfer device 22 can be provided on the side opposite to the tandem image forming apparatus 20 with the intermediate transfer body 10 interposed therebetween. In the illustrated example, the secondary transfer device 22 is configured by spanning a secondary transfer belt 24, which is an endless belt, between two rollers 23 (one roller also serves as a transfer roller). The image on the intermediate transfer body 10 is transferred by the transfer roller 23 via the sheet. A fixing device 25 for fixing the transfer image on the sheet is provided beside the secondary transfer device 22. The fixing device 25 is configured by pressing a pressure roller 27 against a fixing belt (not shown) which is an endless belt.

  The secondary transfer device 22 described above is also provided with a sheet transport function for transporting the image-transferred sheet to the fixing device 25. In the illustrated example, a sheet for reversing the sheet so as to record an image on both sides of a sheet (not shown) is provided below the secondary transfer device 22 and the fixing device 25 in parallel with the tandem image forming device 20 described above. A reversing device 28 is provided.

  When copying using this color electrophotographic apparatus, an original is set on the original table 30 of the automatic original conveying apparatus 400. Alternatively, the automatic document feeder 400 is opened, a document is set on the contact glass 32 of the scanner 300, and the automatic document feeder 400 is closed and pressed by it.

  When a start switch (not shown) is pressed, when the document is set on the automatic document feeder 400, the document is transported and moved onto the contact glass 32, and then the document is set on the contact glass 32. At that time, the scanner 300 is immediately driven to travel the first traveling body 33 and the second traveling body 34. Then, the first traveling body 33 emits light from the light source and further reflects the reflected light from the document surface toward the second traveling body 34, and is reflected by the mirror of the second traveling body 34 and passes through the imaging lens 35. It puts in the reading sensor 36 and reads the contents of the document. When a start switch (not shown) is pressed, one of the support rollers 14 to 16 is rotationally driven by a drive motor (not shown), the other two support rollers are driven to rotate, and the intermediate transfer body 10 is rotated and conveyed. At the same time, the individual image forming means 18 rotates the photoconductor 40 to form black, yellow, magenta, and cyan monochrome images on each photoconductor 40. Then, along with the conveyance of the intermediate transfer member 10, the single color images are sequentially transferred to form a composite color image on the intermediate transfer member 10.

  On the other hand, when a start switch (not shown) is pressed, one of the paper feed rollers 42 of the paper feed table 200 is selectively rotated, and the sheet is fed out from one of the paper feed cassettes 44 provided in multiple stages in the paper bank 43, and the separation roller 45. Then, the sheets are separated one by one into the paper feed path 46, transported by the transport roller 47, guided to the paper feed path 48 in the copying machine main body 100, and abutted against the registration roller 49 and stopped. Alternatively, the sheet feed roller 50 (not shown) is rotated to feed out the sheets on the manual feed tray (not shown), separated one by one by a separation roller (not shown), and put into the manual feed path 53 (not shown). Similarly, it abuts against the registration roller 49 and stops. Then, the registration roller 49 is rotated in synchronization with the composite color image on the intermediate transfer member 10, the sheet is fed between the intermediate transfer member 10 and the secondary transfer device 22, and transferred by the secondary transfer device 22. A color image is recorded on the sheet.

  The image-transferred sheet is conveyed by the secondary transfer device 22 and sent to the fixing device 25. The fixing device 25 applies heat and pressure to fix the transferred image, and then the switching claw 55 (not shown). The sheet is switched and discharged by the discharge roller, and stacked on the discharge tray 57. Alternatively, it is switched by a switching claw (not shown) and put into the sheet reversing device 28, where it is reversed and guided again to the transfer position, and an image is recorded also on the back surface, and then discharged onto the discharge tray 57 by the discharge roller. .

  On the other hand, the intermediate transfer body 10 after the image transfer is removed by the intermediate transfer body cleaning device 17 to remove residual toner remaining on the intermediate transfer body 10 after the image transfer, so that the tandem image forming apparatus 20 can prepare for another image formation. Here, the registration roller 49 is generally used while being grounded, but it is also possible to apply a bias for removing paper dust from the sheet.

  In the present invention, it is preferable to use the image forming apparatus as described above as the image forming method, but it is preferable to carry out the image forming method using such an image forming apparatus. Such an image forming method of the present invention includes a charging step for uniformly charging an electrostatic latent image carrier, an image exposure step for forming a latent image on the uniformly charged electrostatic latent image carrier, A developing step of developing the latent image formed using the developer, a step of transferring the developed image, and a cleaning step of removing the residual developer of the electrostatic latent image carrier after the transfer. . In such an image forming method of the present invention, the above-described one-component developer or the two-component developer composed of the above-described carrier and the toner of the present invention is used as the developer in the above-described development step. In the image forming method of the present invention, the cleaning step is preferably a blade cleaning method.

  The process cartridge of the present invention integrally supports an image carrier that carries an electrostatic latent image and at least a developing device that is disposed to face the image carrier that carries an electrostatic latent image, thereby forming an image. It is a process cartridge that can be attached to and detached from the apparatus main body, and this process cartridge preferably has the developer described above.

  Examples of the present invention will be given below, but the present invention is not limited to these examples. Here, both parts and% are based on weight.

[Example 1]
(1) Toner particle A
Binder resin: 100 parts of partially crosslinked polyester resin (ethylene oxide addition alcohol of bisphenol A, propylene oxide addition alcohol of bisphenol A, terephthalic acid, trimellitic acid condensation polymer, MW 15000, glass transition temperature = 61 ° C.)
Mold release agent: Carnauba wax 5 parts Charge control agent: Azo complex dye 2 parts Colorant: Carbon black (# 44, manufactured by Mitsubishi Chemical Corporation) 13 parts A two-roll kneader in which the mixture having the above composition was heated to 110 ° C After kneading for 90 minutes, toner base particles A having an average particle size of 7.0 μm were obtained by adjusting pulverization / classification conditions with a mechanical pulverizer / airflow classifier.

(2) Toner particle B
Binder resin: 100 parts of partially crosslinked polyester resin (ethylene oxide addition alcohol of bisphenol A, propylene oxide addition alcohol of bisphenol A, terephthalic acid, trimellitic acid condensation polymer, MW 15000, glass transition temperature: 61 ° C.)
Mold release agent: Carnauba wax 5 parts Charge control agent: Azo complex dye 2 parts Colorant: Carbon black (# 44, manufactured by Mitsubishi Chemical Corporation) 13 parts A two-roll kneader in which a mixture of the above composition was heated to 110 ° C After kneading for 40 minutes, toner particles B having an average particle size of 7.0 μm were obtained by adjusting pulverization / classification conditions with a mechanical pulverizer / airflow classifier.

  Each toner particle A and B is embedded in an epoxy resin, cut into thin sections of about 100 μm, dyed with ruthenium tetroxide, and photographed while observing the cross section of the toner with a transmission electron microscope at a magnification of 10,000 times. Did. As a result of obtaining an average dispersion diameter from 50 waxes in this photograph, the toner particles A were 0.1 μm and the toner particles B were 0.8 μm.

  Premixing is carried out for 1 minute with a Henschel mixer at a ratio of 30 parts of toner particles A and 70 parts of toner particles B. Further, 0.8 parts of silica fine powder (dimethylsiloxane treatment) having an average particle diameter of 0.015 μm was added to the total amount of the premixed toner particles, and mixed with a Henschel mixer. After mixing, [Toner C] was prepared by passing through a 63 μm sieve.

On the other hand, the carrier prepared the coating liquid by the following prescription.
300 parts of silicone resin (SR2411, manufactured by Toray Dow Corning, solid content 20%)
1200 parts of toluene The above coating solution was put in a rotating disk type fluidized bed coating apparatus together with 5 kg of ferrite core material / carrier having an average particle diameter of 50 μm to coat the carrier. Thereafter, the coating was taken out from the apparatus and heated at 250 ° C. for 2 hours to age the film. A developer was prepared by weighing so that the total amount of toner C and carrier was 1000 g so that the toner concentration was 5%.

Evaluation of Fixing Use the fixing part of imgio Neo C455 (Ricoh copier). The conditions are as follows.
(Line speed = 162 mm / sec)
Paper used: Type 6000 (Ricoh)
Unfixed image: A 3 cm × 8 cm solid image having a toner adhesion amount of 0.8 ± 0.1 mg / cm ² is created.
The fixing temperature is increased from 120 ° C. in increments of 5 ° C., and the unfixed image is passed through each time. A fixing lower limit temperature and a hot offset occurrence temperature are obtained from the fixed image.

Measurement of minimum fixing temperature:
A 25 mm x 25 mm white cotton cloth (JIS L0803, cotton No. 3) is placed on the smear tester (friction tester type I, JIS L0823, friction element diameter: φ15), and the fiber direction is parallel to the moving direction of the friction element. After sticking with double-sided tape and rubbing the solid image surface 5 times in a continuous motion, the white cotton cloth is peeled off, and the image density at any three locations on the rubbing trace where the image is adhered The smear ID is measured by measuring using a meter (X-Rite, 938 Spectrodensimeter) and calculating the average value. The smear ID has a value of 0.35 as the minimum fixing temperature.

Measurement of hot offset generation temperature:
The temperature at which the solid image surface is offset by visual observation is recorded.

As a result of the measurement:
The minimum fixing temperature was 130 ° C., and the hot offset generation temperature was 245 ° C. When the developer was set in the machine of imgio Neo 451 (attached with a blade cleaning device / Ricoh copier) and the initial image was output, a good image was obtained. Thereafter, 100,000 continuous sheets of A4 paper were fed in the horizontal direction. The results are shown in Table 2.

[Example 2]
(1) Toner particle D
Binder resin: 100 parts of partially crosslinked polyester resin (ethylene oxide addition alcohol of bisphenol A, propylene oxide addition alcohol of bisphenol A, terephthalic acid, trimellitic acid condensation polymer, MW 15000, glass transition temperature: 61 ° C.)
Mold release agent: Carnauba wax 5 parts Charge control agent: Azo complex dye 2 parts Colorant: Carbon black (# 44, manufactured by Mitsubishi Chemical Corporation) 13 parts A two-roll kneader in which the above composition was heated to 110 ° C After kneading for 70 minutes, [toner particles D] having an average particle size of 7.0 μm were obtained by adjusting the pulverization / classification conditions with a mechanical pulverizer / airflow classifier.

(2) Toner base particle E
Binder resin: 100 parts of partially crosslinked polyester resin (ethylene oxide addition alcohol of bisphenol A, propylene oxide addition alcohol of bisphenol A, terephthalic acid, trimellitic acid condensation polymer, MW 15000, glass transition temperature: 61 ° C.)
Mold release agent: Carnauba wax 5 parts Charge control agent: Azo complex dye 2 parts Colorant: Carbon black (# 44, manufactured by Mitsubishi Chemical Corporation) 13 parts

  The mixture having the above composition was kneaded for 20 minutes in a two-roll kneader heated to 130 ° C., and then pulverized and classified by a mechanical pulverizer / airflow classifier to adjust the average particle size to 7.0 μm [toner Particle E] was obtained.

  Each toner particle was embedded in an epoxy resin, cut into a thin section of about 100 μm, dyed with ruthenium tetroxide, and then photographed while observing the cross section of the toner particle with a transmission electron microscope at a magnification of 10,000 times. . As a result of obtaining an average dispersion diameter from 50 waxes in this photograph, [Toner Particle D] was 0.6 μm and [Toner Particle E] was 3.0 μm.

  95 parts of toner particles D and 5 parts of toner particles E are premixed with a Henschel mixer at 20 m / sec for 1 minute. Further, 0.8 parts of silica fine powder (dimethylsiloxane treatment) having an average particle size of 0.015 μm was added to the total amount of pre-mixed toner base particles, and then mixed. After mixing, it was passed through a 63 μm sieve to prepare [Toner F].

On the other hand, the carrier prepared the coating liquid by the following prescription.
300 parts of silicone resin (SR2411, manufactured by Toray Dow Corning, solid content 20%)
1200 parts of toluene 1500 g of the above liquid was put into a rotating disk type fluidized bed coating apparatus together with 5 kg of a ferrite core material / carrier having an average particle diameter of 50 μm to coat the carrier. Thereafter, the coating was taken out from the apparatus and heated at 250 ° C. for 2 hours to age the film. The developer was prepared by weighing the total amount of toner and carrier to 1000 g so that the toner concentration was 5 (weight)%.

Fixability evaluation (measured in the same manner as in Example 1)
Measurement results: The fixing lower limit temperature is 135 ° C., and the hot offset occurrence temperature is 235 ° C.
When a developer was set in an image of an image Neo Neo 451 (a copying machine manufactured by Ricoh Co., Ltd.) and an initial image was output, a good image was obtained. Thereafter, 100,000 sheets of A4 size paper were fed continuously in the horizontal direction. The results are shown in Table 2.

Example 3
(1) Toner particle G
Binder resin: 100 parts of partially crosslinked polyester resin (ethylene oxide addition alcohol of bisphenol A, propylene oxide addition alcohol of bisphenol A, terephthalic acid, trimellitic acid condensation polymer, MW 15000, glass transition temperature: 61 ° C.)
Mold release agent: Carnauba wax 5 parts Charge control agent: Azo complex dye 2 parts Colorant: Carbon black (# 44, manufactured by Mitsubishi Chemical Corporation) 13 parts A two-roll kneader in which the mixture having the above composition was heated to 120 ° C After kneading for 80 minutes, a pulverizing / classifying condition was adjusted with a mechanical pulverizer / airflow classifier to obtain [Toner Particles G] having an average particle size of 7.0 μm.

(2) Toner particle H
Binder resin: 100 parts of partially crosslinked polyester resin (ethylene oxide addition alcohol of bisphenol A, propylene oxide addition alcohol of bisphenol A, terephthalic acid, trimellitic acid condensation polymer, MW 15000, glass transition temperature: 61 ° C.)
Release agent: Carnauba wax 5 parts Charge control agent: Azo complex dye 2 parts Colorant: Carbon black (# 44, manufactured by Mitsubishi Chemical Corporation) 13 parts A two-roll kneader in which the mixture having the above composition was heated to 120 ° C After kneading for 20 minutes, [toner particles H] having an average particle size of 7.0 μm were obtained by adjusting the pulverization / classification conditions with a mechanical pulverizer / airflow classifier.

  Premixing is performed for 1 minute at a ratio of 60 parts of toner particles G and 40 parts of toner particles H. Further, the premixed toner further includes 0.8 parts of silica fine powder (dimethylsiloxane treatment) having an average particle diameter of 0.015 μm as an external additive and titanium fine powder having a particle diameter of 0.015 μm treated with isobutyltrimethoxysilane. The body was mixed after adding 0.5 parts. After mixing, [Toner I] was prepared by passing through a 63 μm sieve. When the carrier was tested in the same manner as in Example 1 using the carrier of Example 1, the same result as in Example 1 was obtained.

Example 4
Using toner particles A, B, D, E and H of Examples 1 to 3, the ratio of the wax dispersion diameter (DWB) in the toner particles is changed, and the external addition is performed in the same manner as in Example 3. Mixing of the agents was performed. Table 1 shows the ratio of DWB generated when the toner hot offset is 195 ° C. or higher. In Table 1, (DWA × DWB) and the ratio of DWB have a relationship as shown in FIG.

  Among the toners shown in Table 1, the toners 1 to 6 are good toners with no hot offset at 195 ° C. or lower. As shown in FIG. 1, in a toner obtained by mixing toner particles each having a combination of DWA = 0.5 μm and DWB = 2.0 μm, the toner using toner particles containing 50 parts of DWB amount When the offset generation temperature is reached, it is difficult to cause a winding around the fixing unit in an actual machine. However, since the toner fluidity is not good, it becomes difficult for the developer to be pumped up to the developing sleeve, the image density becomes low, and the image quality becomes extremely unstable due to background stains. In addition, filming on the latent image carrier and toner storage are problematic. In addition, in a toner obtained by mixing toner particles each having a combination of DWA = 0.5 μm and DWB = 2.0 μm, if the toner uses toner particles containing 10 parts of DWB, the temperature at which offset occurs is lowered. As a result, the actual machine becomes a factor that causes winding around the fixing unit. In the toners 1 to 6 shown in Table 1, when the offset generation temperature is used in an actual machine, the fixing unit can withstand use even if the temperature control, the use environment change, the type of transfer paper, the toner adhesion amount, and the like vary.

Example 5
In Example 1, a toner and a carrier were prepared in the same manner as in Example 1 except that the charge control agent of the toner was changed from an azo metal complex dye to a metal zinc salicylate derivative (E-84: manufactured by Orient Chemical Co., Ltd.) When tested in the same manner as in Example 1, the same result as in Example 1 was obtained.

Example 6
In Example 1, a toner and a carrier were prepared in the same manner as in Example 1 except that the charge control agent of the toner was changed from an azo metal complex dye to a fluorine-containing quaternary ammonium salt (copy charge NXVP434: manufactured by Hoechst). When tested in the same manner as in Example 1, the same result as in Example 1 was obtained.

Example 7
In Example 1, the toner particle size was pulverized from 7.0 μm to 4.1 μm. And when it tested like Example 1 except having added 0.8 parts of silica fine powder (dimethylsiloxane process) with an average particle diameter of 0.015 micrometer as follows, it is good like Example 1. Results were obtained.
1.1 parts of silica fine powder (dimethylsiloxane treatment) having an average particle diameter of 0.015 μm, and 0.1 part of titanium fine powder having a particle diameter of 0.015 μm treated with isobutyltrimethoxysilane. 7 parts.

Example 8
In Example 1, the toner particle size was pulverized from 7.0 μm to 9.1 μm. And when it tested like Example 1 except having added 0.8 parts of silica fine powder (dimethylsiloxane process) with an average particle diameter of 0.015 micrometer as follows, it is good like Example 1. Results were obtained.
0.6 parts of silica fine powder (dimethylsiloxane treatment) having an average particle diameter of 0.015 μm, and 0.4 parts of titanium fine powder having a particle diameter of 0.015 μm treated with isobutyltrimethoxysilane.

Example 9
Next, examples of color toners are shown.
(1) Production of masterbatch pigment Production example 1 of yellow toner masterbatch
Binder resin: 50 parts of polyester resin A (polyester resin synthesized from ethylene oxide adduct of bisphenol A, terephthalic acid, fumaric acid, softening point: 95 ° C.)
Colorant 50 parts (Imidazolone yellow pigment: CI Pigment Yellow 180)
30 parts of water The above raw materials were mixed with a Henschel mixer, and then kneaded for 45 minutes with two rolls set at a roll surface temperature of 130 ° C. to obtain a master batch pigment A.

2. Production example 2 of magenta toner master batch
Binder resin: 50 parts of polyester resin A (polyester resin synthesized from ethylene oxide adduct of bisphenol A, terephthalic acid, fumaric acid, softening point: 95 ° C.)
50 parts of colorant (quinacridone magenta pigment: CI Pigment Red 122)
30 parts of water The above raw materials were mixed with a Henschel mixer, and then kneaded for 45 minutes with two rolls set at a roll surface temperature of 130 ° C. to obtain a master batch pigment B.

3. Cyan toner master batch production example 3
Binder resin: 50 parts of polyester resin A (polyester resin synthesized from ethylene oxide adduct of bisphenol A, terephthalic acid, fumaric acid, softening point: 95 ° C.)
50 parts of colorant (copper phthalocyanine cyan pigment: CI Pigment Blue 15: 3)
30 parts of water The above raw materials were mixed using a Henschel mixer, and then kneaded for 45 minutes with two rolls set at a roll surface temperature of 130 ° C. to obtain master batch pigment C.

4). Black toner masterbatch production example 4
Binder resin: 50 parts of polyester resin A (polyester resin synthesized from ethylene oxide adduct of bisphenol A, terephthalic acid, fumaric acid, softening point: 95 ° C.)
Colorant 50 parts (carbon black pigment: CI Pigment Bullack 1)
30 parts of water The above raw materials were mixed with a Henschel mixer, and then kneaded for 45 minutes with two rolls set at a roll surface temperature of 130 ° C. to obtain a master batch pigment D.

(2) Preparation of toner A yellow toner, a magenta toner, a cyan toner and a black toner were prepared according to the following formulation using each of the master batch pigments A, B, C and D.
Binder resin: 100 parts of polyester resin A (polyester resin synthesized from ethylene oxide adduct of bisphenol A, terephthalic acid, fumaric acid, softening point: 95 ° C.)
Colorant: Masterbatch pigment (each A to D) 15 parts Release agent (Carnauba wax: melting point 92 ° C., Mw / Mn = 1.1) 5 parts Charge control agent (salicylic acid derivative zinc salt) 2.5 parts The raw materials were mixed using a Henschel mixer and then melt-kneaded for 60 minutes with a three-roll kneader set at 110 ° C. The kneaded product is cooled with water, coarsely pulverized with a cutter mill, pulverized with a fine pulverizer using a jet stream, and then used with an air classifier to form a yellow base particle J, magenta base particle L, and cyan base particle with a particle size of 6.5 μm. Each toner base particle of N and black base particles P was prepared.
Furthermore, the raw materials were mixed using a Henschel mixer and then melt-kneaded for 20 minutes with a three-roll kneader set at 130 ° C. The kneaded product is cooled with water, coarsely pulverized with a cutter mill, pulverized with a fine pulverizer using a jet stream, and then used with an air classifier to make yellow base particles K, magenta base particles M, and cyan base particles with a particle size of 6.5 μm. Toner base particles of O and black base particles Q were prepared. The toner base particles of each color are embedded in an epoxy resin, cut into thin sections of about 100 μm, dyed with ruthenium tetroxide, and then observed with a transmission electron microscope at a magnification of 10,000 times. While taking a photo.
As a result of obtaining the average dispersion diameter of the wax from 50 waxes in this photograph, the average dispersion diameters of the yellow toner base particles J, the magenta toner base particles L, the cyan toner base particles N, and the black toner base particles P are respectively It was 0.4 μm. The average dispersion diameters of the yellow toner base particles K, the magenta toner base particles M, the cyan toner base particles O, and the black toner base particles Q were 1.5 μm, respectively.

(Creation of yellow toner R)
50 parts of yellow toner particles J and 50 parts of yellow toner particles K are mixed with a Henschel mixer. Further, 1.0 part of silica fine powder (dimethylsiloxane treatment) having an average particle diameter of 0.015 μm and 0.7 part of titanium fine powder having a particle diameter of 0.015 μm treated with isobutyltrimethoxysilane were added and mixed. . After mixing, it was passed through a 63 μm sieve to produce [Yellow Toner R].

(Magenta toner S creation)
50 parts of magenta toner particles L and 50 parts of magenta toner particles M are mixed with a Henschel mixer. Further, 1.0 part of silica fine powder (dimethylsiloxane treatment) having an average particle diameter of 0.015 μm, and 0.1 part of titanium fine powder having a particle diameter of 0.015 μm treated with isobutyltrimethoxysilane. 7 parts were added and mixed. After mixing, the mixture was passed through a 63 μm sieve to prepare [Magenta Toner S].

(Cyan toner T creation)
50 parts of cyan toner particles N and 50 parts of cyan toner particles O are mixed with a Henschel mixer. Further, 1.0 part of silica fine powder (dimethylsiloxane treatment) having an average particle diameter of 0.015 μm and 0.7 part of titanium fine powder having a particle diameter of 0.015 μm treated with isobutyltrimethoxysilane were added and mixed. . After mixing, [Cyan Toner T] was prepared by passing through a 63 μm sieve.

(Create Black Rack Toner U)
50 parts of black toner particles P and 50 parts of black toner particles Q are mixed with a Henschel mixer. Further, 1.0 part of silica fine powder (dimethylsiloxane treatment) having an average particle diameter of 0.015 μm and 0.7 part of titanium fine powder having a particle diameter of 0.015 μm treated with isobutyltrimethoxysilane were added and mixed. . After mixing, it was passed through a 63 μm sieve to prepare [Black Toner U].

On the other hand, the carrier prepared the coating liquid by the following prescription.
300 parts of silicone resin (SR2411, manufactured by Toray Dow Corning, solid content 20%)
Silane coupling agent 10 parts (γ- (2-aminoethyl) aminopropyltrimethoxysilane)
1200 parts of toluene 1510 g of the coating solution was put in a rotating disk type fluidized bed coating apparatus together with 5 kg of a ferrite core material carrier having an average particle diameter of 50 μm to coat the carrier. The resulting coating was then removed from the apparatus and heated at 250 ° C. for 2 hours to age the film. The developer was prepared by weighing the total amount of toner and carrier to 1000 g so that the toner concentration was 6.5%.

Fixability evaluation (measured in the same manner as in Example 1)
Measurement results: The yellowing, magenta toner, cyan toner, and black toner have a fixing lower limit temperature of 135 ° C., and the yellow toner, magenta toner, cyan toner, and black toner have a hot offset occurrence temperature of 230 ° C.
When each color developer was set in an imagio Neo C285 (with blade cleaning device / Ricoh copier) machine and an initial image was printed, a good image was obtained. Thereafter, 100,000 sheets of A4 size paper were continuously fed by horizontal feeding. The results are shown in Table 2.

Example 10
(Example of toner production by at least one of a crosslinking reaction and an elongation reaction)
1. Black toner production example-Synthesis of organic fine particle emulsion-
In a reaction vessel equipped with a stir bar and a thermometer, 683 parts of water, 11 parts of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30; manufactured by Sanyo Chemical Industries), 166 parts of methacrylic acid, butyl acrylate When 110 parts and 1 part of ammonium persulfate were charged and stirred at a rotational speed of 3,800 rpm for 30 minutes, a white emulsion was obtained. The emulsion was heated to raise the system temperature to 75 ° C. and reacted for 4 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 6 hours to obtain an aqueous vinyl resin (methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt copolymer). A dispersion [fine particle dispersion 1] was obtained.
The obtained [Fine Particle Dispersion 1] was measured with a laser diffraction particle size distribution analyzer (LA-920; manufactured by Shimadzu Corporation), and its volume average particle size was 110 nm. A portion of [Fine Particle Dispersion 1] was dried to isolate the resin component. The isolated resin had a Tg of 58 ° C. and a weight average molecular weight of 130,000 (in terms of styrene).

-Adjustment of aqueous phase-
990 parts of water, 83 parts of [fine particle dispersion 1], 37 parts of 48.3% aqueous solution of sodium dodecyldiphenyl ether disulfonate (Eleminol MON-7; manufactured by Sanyo Chemical Industries) and 90 parts of ethyl acetate are mixed and stirred. A milky white liquid was obtained. This liquid is designated as [Aqueous Phase 1].

~ Synthesis of low molecular weight polyester ~
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 229 parts of bisphenol A ethylene oxide 2-mole adduct, 529 parts of bisphenol A propylene oxide 3-mole adduct, 208 parts terephthalic acid, 46 parts adipic acid and dibutyl 2 parts of tin oxide was added and reacted at normal pressure and 230 ° C. for 7 hours. Further, after 5 hours of reaction under reduced pressure of 10 to 15 mmHg, 44 parts of trimellitic anhydride was added to the reaction vessel at normal pressure and 180 ° C. For 3 hours to obtain [Low molecular polyester 1]. The obtained [Low molecular weight polyester 1] had a number average molecular weight of 2300, a weight average molecular weight of 6700, Tg of 43 ° C., and an acid value of 25 mgKOH / g.

~ Synthesis of intermediate polyester ~
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction tube, 682 parts of bisphenol A ethylene oxide 2-mole adduct, 81 parts of bisphenol A propylene oxide 2-mole adduct, 283 parts of terephthalic acid, 22 parts of trimellitic anhydride Then, 2 parts of dibutyltin oxide was added, reacted at 230 ° C. under normal pressure for 7 hours, and further reacted under reduced pressure of 10 to 15 mmHg for 5 hours to obtain [Intermediate Polyester 1]. The obtained [Intermediate polyester 1] had a number average molecular weight of 2200, a weight average molecular weight of 9700, Tg of 54 ° C., an acid value of 0.5 mgKOH / g, and a hydroxyl value of 525 mgKOH / g.
Next, 410 parts of [intermediate polyester 1], 89 parts of isophorone diisocyanate, and 500 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours. [Prepolymer 1] was obtained. This [Prepolymer 1] had a free isocyanate (%) of 1.53%.

~ Synthesis of ketimine ~
In a reaction vessel equipped with a stir bar and a thermometer, 170 parts of isophoronediamine and 75 parts of methyl ethyl ketone were charged and reacted at 50 ° C. for 4 and a half hours to obtain [ketimine compound 1]. The amine value of the obtained [ketimine compound 1] was 417 mgKOH / g.

~ Master batch synthesis ~
Add 1200 parts of water, 540 parts of carbon black (Printex35; manufactured by Dexa, DBP oil absorption = 42 ml / 100 mg, pH = 9.5) and 1200 parts of polyester resin, and mix using a Henschel mixer (made by Mitsui Mining). Then, the obtained mixture was kneaded at 130 ° C. for 1 hour using two rolls, rolled and cooled, and pulverized with a pulverizer to obtain [Masterbatch 1].

~ Preparation of oil phase ~
378 parts of [low molecular weight polyester 1], 100 parts of carnauba wax and 947 parts of ethyl acetate are charged in a container equipped with a stir bar and a thermometer, and the temperature is raised to 80 ° C. with stirring, while maintaining 80 ° C. After holding for 5 hours, it was cooled to 30 ° C. in 1 hour. Next, 500 parts of [Master batch 1] and 500 parts of ethyl acetate were charged in a container and mixed for 1 hour to obtain [Raw material solution 1].
[Raw Material Solution 1] 1324 parts were transferred to a container, and using a bead mill (Ultra Visco Mill; manufactured by Imex Co., Ltd.), a liquid feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 0.5 mm zirconia beads were 80% by volume. After filling, the carbon black and the wax were dispersed under conditions of 3 passes. Next, 1324 parts of a 65% ethyl acetate solution of [low molecular weight polyester 1] was added, followed by two passes with a bead mill under the above conditions to obtain [Pigment / Wax Dispersion 1]. The resulting [Pigment / Wax Dispersion 1] had a solid content concentration (130 ° C., 30 minutes) of 50%.

~ Emulsification, solvent removal ~
[Pigment / Wax Dispersion 1] 749 parts, [Prepolymer 1] 115 parts, and [Ketimine Compound 1] 2.9 parts are put in a container, and 2 times at 5,000 rpm with a TK homomixer (manufactured by Tokushu Kika). After mixing for 1 minute, 1200 parts of [Aqueous Phase 1] was added to the container and mixed with a TK homomixer at 13,000 rpm for 25 minutes to obtain [Emulsified Slurry 1].
[Emulsion slurry 1] was put into a container equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C for 8 hours, aging was carried out at 45 ° C for 7 hours to obtain [Dispersion slurry 1].

~ Washing, drying ~
100 parts of [Dispersion Slurry 1] was filtered under reduced pressure, and the following was performed.
(1) 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), and then filtered.
(2) 100 parts of a 10% sodium hydroxide aqueous solution was added to the filter cake of (1), mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure.
(3) 100 parts of 10% hydrochloric acid was added to the filter cake of (2), mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered.
(4) Add 300 parts of ion exchanged water to the filter cake obtained in (3), mix with a TK homomixer (10 minutes at 12,000 rpm) and then filter twice [Filter cake 1] Got.

[Filter cake 1] was dried at 45 ° C. for 48 hours with a circulating dryer. 100 parts of this [filter cake 1] were mixed with a mixer at a ratio of 0.6 parts of zinc salicylate (E-84; manufactured by Orient Chemical Co., Ltd.). And sieved with a mesh of 75 μm, weight average particle size (D4) 6.1 μm, number average particle size (Dn) 5.5 μm, D4 / Dn = 1.11, average circularity 0.97, shape factor SF− 1 = 135, shape factor SF-2 = 118, minor axis (r2) / major axis (r1) = 0.8, thickness (r3) / minor axis (r2) = 0.9 [Black toner particles JJ] Got.
Also, during the preparation of the oil phase, [black toner particles KK] were obtained in the same manner as the black toner particles JJ, except that carbon black and wax were dispersed under one-pass conditions.
As a result of obtaining the average dispersion diameter in the same manner as in Example 9, the black toner particles JJ were 0.5 μm and the black toner particles KK were 1.2 μm.

2. Example of production of yellow toner In the synthesis of the masterbatch, C.I. I. [Yellow toner AA] was produced in the same manner as in the black toner production example, except that CI Pigment Yellow 180 (PV Fast Yellow HG; manufactured by Clariant) was used.
The yellow toner particles AA have a weight average particle diameter (D4) of 6.0 μm, a number average particle diameter (Dn) of 5.4 μm, D4 / Dn = 1.11, an average circularity of 0.97, and a shape factor SF-1 = 132. , Shape factor SF-2 = 115, minor axis (r2) / major axis (r1) = 0.8, thickness (r3) / minor axis (r2) = 0.9.
In addition, a yellow toner BB was obtained in the same manner as the yellow toner AA except that the yellow colorant and the wax were dispersed under the conditions of one pass during the preparation of the oil phase. When the average dispersion diameter was determined in the same manner as in Example 9, the yellow toner particles AA were 0.5 μm and the yellow toner particles BB were 1.2 μm.

3. Production example of magenta toner In the synthesis of the masterbatch, C.I. I. [Magenta toner DD] was produced in the same manner as in the black toner production example except that CI Pigment Red 122 (Hostaperm Pink E; manufactured by Clariant) was used.
The physical properties of the magenta toner particles DD were as follows.
Weight average particle diameter (D4) 6.5 μm, number average particle diameter (Dn) 5.6 μm, D4 / Dn = 1.16, average circularity 0.96, shape factor SF-1 = 137, shape factor SF-2 = 117, minor axis (r2) / major axis (r1) = 0.8, thickness (r3) / minor axis (r2) = 0.9
Also, [Magenta Toner EE] was obtained in the same manner as Magenta Toner DD except that during the preparation of the oil phase, the magenta colorant and the wax were dispersed under the conditions of one pass. As a result of obtaining the average dispersion diameter in the same manner as in Example 9, the magenta toner particles DD were 0.5 μm and the magenta toner particles EE were 1.2 μm.

4). Example of Cyan Toner Production In the synthesis of a masterbatch, C.I. I. [Cyan toner GG] was produced in the same manner as in the black toner production example, except that CI Pigment Blue 15: 3 (Lionol Blue HG-7351; manufactured by Toyo Ink Co., Ltd.) was used.
The physical properties of the cyan toner particles GG were as follows.
Weight average particle diameter (D4) 6.2 μm, number average particle diameter (Dn) 5.5 μm, D4 / Dn = 1.13, average circularity 0.97, shape factor SF-1 = 134, shape factor SF-2 = 115, short axis (r2) / long axis (r1) = 0.8, thickness (r3) / short axis (r2) = 0.9
[Cyan Toner HH] was obtained in the same manner as Cyan Toner GG, except that during the preparation of the oil phase, the cyan colorant and the wax were dispersed under the conditions of one pass. As a result of obtaining the average dispersion diameter in the same manner as in Example 9, the cyan toner particles GG were 0.5 μm and the cyan toner particles HH were 1.2 μm.

~ External additive treatment ~
50 parts of yellow toner particles AA, 50 parts of yellow toner particles BB, and 5 parts of a zinc salicylate metal complex (E-84, manufactured by Orient Chemical Industries) were mixed with a Henschel mixer. Furthermore, 1.0 part of silica fine powder (dimethylsiloxane treatment) having an average particle diameter of 0.015 μm and 0.7 part of titanium fine powder having a particle diameter of 0.015 μm treated with isobutyltrimethoxysilane were added and mixed. did. After mixing, it was passed through a 63 μm sieve to produce [Yellow Toner Particles CC].

  50 parts of magenta toner particles DD, 50 parts of magenta toner particles EE, and 5 parts of a zinc salicylate metal complex (E-84, manufactured by Orient Chemical Industry Co., Ltd.) were mixed with a Henschel mixer. Further, 1.0 part of silica fine powder (dimethylsiloxane treatment) having an average particle diameter of 0.015 μm and 0.7 part of titanium fine powder having a particle diameter of 0.015 μm treated with isobutyltrimethoxysilane were added and mixed. did. After mixing, the mixture was passed through a 63 μm sieve to prepare [Magenta Toner FF].

  50 parts of cyan toner particles GG, 50 parts of cyan toner particles HH, and 5 parts of a zinc salicylate-based metal complex (E-84, manufactured by Orient Chemical Industry Co., Ltd.) were mixed with a Henschel mixer. Furthermore, 1.0 part of silica fine powder (dimethylsiloxane treatment) having an average particle diameter of 0.015 μm and 0.7 part of titanium fine powder having a particle diameter of 0.015 μm treated with isobutyltrimethoxysilane were added and mixed. did. After mixing, it was passed through a 63 μm sieve to prepare [Cyan Toner II].

  50 parts of black toner particles JJ, 50 parts of black toner particles KK, and 5 parts of a zinc salicylate metal complex (E-84, manufactured by Orient Chemical Industry Co., Ltd.) were mixed with a Henschel mixer. Furthermore, 1.0 part of silica fine powder (dimethylsiloxane treatment) having an average particle diameter of 0.015 μm and 0.7 part of titanium fine powder having a particle diameter of 0.015 μm treated with isobutyltrimethoxysilane were added and mixed. did. After mixing, it was passed through a 63 μm sieve to prepare [Black Toner LL].

On the other hand, the carrier prepared the coating liquid by the following prescription.
Silicone resin: 300 parts (SR2411, manufactured by Toray Dow Corning, solid content 20%)
Silane coupling agent: 10 parts (γ- (2-aminoethyl) aminopropyltrimethoxysilane)
Toluene 1200 parts The above coating liquid 1510 g was put into a rotating disk type fluidized bed coating apparatus together with 5 kg of ferrite core material / carrier having an average particle diameter of 50 μm to coat the carrier. Thereafter, the coating was taken out from the apparatus and heated at 250 ° C. for 2 hours to age the film. A developer was prepared by weighing the toner and carrier so that the toner concentration was 6% and the total amount of toner and carrier was 1000 g.

Physical property evaluation (measured in the same manner as in Example 1)
Measurement results: The yellowing, magenta, cyan, and black toners have a fixing minimum temperature of 135 ° C., and the yellow toner, magenta toner, cyan toner, and black toner all have a hot offset occurrence temperature of 230 ° C.
When each color developer was set in an imagio Neo C285 (Ricoh copier with blade cleaning device) machine and an initial image was printed, a good image was obtained. Thereafter, 100,000 sheets of A4 size paper were continuously fed in a horizontal feed. The results are shown in Table 2.

Example 11
(Example of toner production by suspension polymerization)
(1) Black toner LL
40 parts of styrene monomer, 20 parts of carbon black (MA100, manufactured by Mitsubishi Kasei Co., Ltd.) and 0.5 part of 2,2′-azobisisobutyronitrile as a polymerization initiator, a three-one motor driven stirring blade, cooler, gas The flask was placed in a 500 ml four-necked separable flask equipped with an introduction tube and a thermometer, and stirred at room temperature for 30 minutes under a nitrogen stream to replace the inside of the flask with nitrogen. Then, it stirred at 60 rpm in a 70 degreeC hot water bath for 6 hours, and graft carbon black was obtained.
The following mixture was dispersed with a ball mill for 10 hours to prepare a dispersion.
Styrene monomer 50.0 parts n-Butyl methacrylate 14.5 parts 1,3-butanediol dimethacrylate 0.5 parts t-butylacrylamide sulfonic acid 3.0 parts Low molecular weight polyethylene 2.0 parts (Mitsui Petrochemical Co., Ltd. Mitsui High Wax 210P)
Graft carbon black 30.0 parts

One part each of 2,2′-azobisisobutyronitrile and sodium nitrite was dissolved in the obtained dispersion, and then added to 250 parts of a 2% aqueous solution of polyvinyl alcohol, and added to a TK homomixer (Special Machine Industries Co., Ltd.). The mixture was stirred at 6000 rpm for 10 minutes to obtain a suspension.
The suspension was put into a 500 ml four-necked separable flask equipped with a three-one motor-driven stirring blade, a cooler, a gas introduction tube, and a thermometer, and stirred for 30 minutes at room temperature under a nitrogen stream. Oxygen was replaced with nitrogen. Thereafter, the mixture was stirred in a hot water bath at 70 ° C. for 8 hours at 90 rpm to complete the polymerization, thereby producing suspension polymerization particles. 100 parts of the prepared particles were redispersed in a water / methanol = 1/1 (weight ratio) mixed solution so as to have a solid content of 30%, and 3 parts by weight of zinc ditertiary butylsalicylate was added as a charge control agent. After stirring, it was filtered and dried to obtain [Black Toner LL] having an average particle size of 6.1 μm.

(2) Black toner MM
40 parts of styrene monomer, 20 parts of carbon black (MA100, manufactured by Mitsubishi Kasei Co., Ltd.), 0.5 part of 2,2′-azobisisobutyronitrile as a polymerization initiator, a three-one motor driven stirring blade, a cooler, The flask was placed in a 500 ml four-necked separable flask equipped with a gas inlet tube and a thermometer, and stirred at room temperature for 30 minutes under a nitrogen stream to replace the inside of the flask with nitrogen. Thereafter, the mixture was stirred in a hot water bath at 70 ° C. for 6 hours at 60 rpm to obtain graft carbon black.

The following mixture was dispersed on a ball mill for 10 hours.
Styrene monomer 50.0 parts n-Butyl methacrylate 14.5 parts 1,3-butanediol dimethacrylate 0.5 parts t-butylacrylamide sulfonic acid 3.0 parts Low molecular weight polyethylene 2.0 parts (Mitsui Petrochemical Co., Ltd. Mitsui High Wax 210P)
Graft carbon black 30.0 parts

  After dissolving 1 part each of 2,2′-azobisisobutyronitrile and sodium nitrite in this dispersion, it was added to 250 parts of a 2% aqueous solution of polyvinyl alcohol, and TK homomixer (manufactured by Tokushu Kika Co., Ltd.) Was stirred at 3500 rpm for 10 minutes to obtain a suspension.

The suspension was put into a 500 ml four-necked separable flask equipped with a three-one motor-driven stirring blade, a cooler, a gas introduction tube, and a thermometer, and stirred for 30 minutes at room temperature under a nitrogen stream. Oxygen was replaced with nitrogen. Thereafter, the mixture was stirred in a 70 ° C. hot water bath at 90 rpm for 8 hours to complete the polymerization, thereby producing suspension polymerization particles.
100 parts of these particles were redispersed in a water / methanol = 1/1 (weight ratio) mixture so as to have a solid content of 30%, and 3 parts of ditertiary butylsalicylic acid zinc salt was added as a charge control agent. Filtration drying was performed to obtain [Black Toner Particles MM] having an average particle diameter of 6.7 μm.

  Each toner particle is embedded in an epoxy resin, cut into a thin section of about 100 μm, dyed with ruthenium tetroxide, and photographed while observing the cross section of the toner base particle with a transmission electron microscope at a magnification of 10,000 times. I took a picture. As a result of obtaining the average dispersion diameter from 50 waxes in this photograph, the average dispersion diameter of the wax of [Black Toner Particles LL] is 0.6 μm, and the average dispersion diameter of the wax of [Black Toner Particles MM] is 1 It was 5 μm.

  Premixing was carried out for 1 minute with a Henschel mixer at a ratio of 55 parts of toner particles LL and 45 parts of toner particles MM. Further, 0.9 parts of silica fine powder (dimethylsiloxane treatment) with an average particle diameter of 0.015 μm and titanium fine powder with a particle diameter of 0.015 μm treated with isobutyltrimethoxysilane with respect to the total amount of premixed toner particles Was added and mixed. After mixing, it was passed through a 63 μm sieve to produce [Black Toner Particles NN]. When the carrier was tested in the same manner as in Example 1 using the carrier of Example 1, the same result as in Example 1 was obtained.

[Comparative Example 1]
Toner and carrier in the same manner as in Example 1, except that the mixing ratio of 30 parts / 70 parts of toner particles A and toner particles B is changed to 100 parts of toner particles A / 0 parts of toner particles B in Example 1. When the same test as in Example 1 was performed, the following result was obtained.
(I) Measurement results: The fixing lower limit temperature was 135 ° C., and the hot offset occurrence temperature was 160 ° C.
(Ii) When the developer was set in an imagio Neo451 (a copying machine manufactured by Ricoh Co., Ltd.) and the initial image was output, a good image was obtained. After that, when A4 size paper was continuously fed by horizontal feeding, hot offset was severely generated and 1,000 sheets were stopped. The results are shown in Table 2.

[Comparative Example 2]
In Example 1, except that the mixing ratio of 30 parts / 70 parts of toner particles A and toner particles B is changed to 0 parts of toner particles A / 100 parts of toner particles B, toner and carrier are used in the same manner as in Example 1. When it was prepared and tested in the same manner as in Example 1, it was as follows.
(I) Measurement results: The fixing lower limit temperature was 130 ° C., and the hot offset occurrence temperature was 245 ° C.
(Ii) When a developer was set in an imgio Neo451 (a copying machine manufactured by Ricoh Co.) and an initial image was produced, an image with a low image density was obtained. After that, when A4 size paper was continuously fed by horizontal feeding, the development unevenness was severe, the image density was low, and 1,000 sheets were stopped. When the developing portion was taken out and the developing sleeve was observed, it was confirmed that the developer was not evenly pumped up to the developing sleeve. The results are shown in Table 2.

The average dispersed particle size of the release agent per particle in the first toner particles is DWA (μm), and the average dispersed particle size of the release agent per particle in the second toner particles is DWB (μm). FIG. 4 is a graph showing the relationship between the average dispersed particle diameter and the ratio (XB) (wt%) of the second toner particles in the toner. In the figure, R ² = 0.9534 and R ² = 0.9729 are x (variable relating to the horizontal axis: DWA × DWB) and y (variable relating to the axis: DWB in the toner particles expressed by weight%). 2 and the ratio of the toner particle) is 1 and is 1 when x and y are in a linear relationship (y = ax + b: a, b are constants). It is a figure for demonstrating shape factor SF-1 and SF-2 of the toner of this invention. It is a figure which shows typically the shape of the toner of this invention. It is a figure which shows an example of the image forming apparatus of this invention.

Explanation of symbols

100 Copying machine main body (image forming device main body)
200 Paper feed table 300 Scanner 400 Automatic document feeder (ADF)
DESCRIPTION OF SYMBOLS 10 Intermediate transfer body 14 Support roller 15 Support roller 16 Support roller 17 Intermediate transfer body cleaning apparatus 18 Image forming means 20 Tandem type image forming apparatus
21 exposure means 22 secondary transfer device 23 roller 24 secondary transfer belt 25 fixing device 26 fixing belt 27 pressure roller 28 sheet reversing device 30 document table 32 contact glass 33 first traveling body 34 second traveling body 35 imaging lens 36 Reading sensor 40 Photoconductor 42 Paper feed roller 43 Paper bank 44 Paper feed cassette 45 Separating roller 46 Paper feed path 47 Transport roller 48 Paper feed path 49 Registration roller 50 Paper feed roller 51 Manual feed tray 52 Separating roller 53 Paper feed path 55 Switching claw 56 discharge roller 57 discharge tray 60 charging device 61 developing device 62 primary transfer device 63 photoconductor cleaning device 64 static eliminating device

Claims (12)

A toner comprising at least a binder resin, a colorant, a release agent, and a charge control agent, the toner comprising first toner particles and second toner particles,
The release agent in the first toner particles has an average dispersed particle size per particle in the range of 0.1 to 0.6 μm,
The release agent in the second toner particles has an average dispersed particle size per particle in the range of 0.8 to 3.0 μm.
Toner characterized by the above. The average dispersed particle diameter of the release agent per particle in the first toner particles is DWA (μm), and the average dispersed particle size of the release agent per particle in the second toner particles is DWB (μm). 2. The toner according to claim 1, wherein a ratio (XB) (% by weight) of the second toner particles in the toner has a relationship represented by the following formula (1):
−30.8 (DWA × DWB) + 68.3 ≧ XB ≧ −23.5 (DWA × DWB) +43.4 (1)   The toner according to claim 1, wherein the charge control agent is at least one selected from an azo metal complex compound, a quaternary ammonium salt, a fluorine-containing quaternary ammonium salt, and a salicylic acid metal complex compound.   The first and second toner particles have a weight average particle diameter in the range of 4.0 to 9.5 μm, and a ratio (D4 / Dn) between the weight average particle diameter (D4) and the number average particle diameter (Dn). The toner according to claim 1, wherein the toner is in the range of 1.00 to 1.40.   The first and second toner particles each have a shape factor SF-1 in the range of 100 to 180 and a shape factor SF-2 in the range of 100 to 180. Toner according to.   The toner according to claim 1, wherein the binder resin in the first and second toner particles is obtained by a polymerization method.   The first and second toner particles are substantially spherical, and the shape is defined by a major axis r1, a minor axis r2, and a thickness r3 (provided that r1 ≧ r2 ≧ r3), and the minor axis r2 The ratio (r2 / r1) to the major axis r1 is in the range of 0.5 to 1.0, and the ratio (r3 / r2) of the thickness r3 to the minor axis r2 is 0.7 to 1.0. The toner according to claim 1, wherein the toner falls within the range of   A developer for developing an electrostatic latent image on an image carrier, wherein the developer contains the toner according to any one of claims 1 to 7 and a carrier made of a magnetic material. Developer.   The developer according to claim 8, wherein the magnetic body is a magnetic carrier coated with a resin. In the developing device arranged to face the image carrier that carries the electrostatic latent image,
The developing device using the developer according to claim 8 or 9. In a process cartridge that integrally supports an image carrier that carries an electrostatic latent image and at least a developing device that is disposed to face the image carrier, and is detachable from the image forming apparatus main body,
The process cartridge includes the developing device according to claim 10. In an image forming apparatus comprising at least an image carrier that carries an electrostatic latent image, and a developing device that is disposed to face the image carrier.
An image forming apparatus using the developing device according to claim 10.

Images