JP4649300B2 - Image forming method and process cartridge - Google Patents

Description

  The present invention relates to a toner used for electrophotography, an image forming method for developing an electrostatic image, and a toner used for a toner jet.

  In recent years, devices using electrophotography have begun to be used in printers for output of computers, facsimiles, etc., in addition to copying machines for copying original documents. As a result, smaller, lighter, faster, and more reliable are being sought, and machines are becoming simpler in various ways. As a result, the performance required for the toner becomes higher, and if the improvement in the performance of the toner cannot be achieved, a better machine cannot be realized.

  As a general electrophotographic image forming method, for example, a photoconductive material is used, an electric latent image is formed on an electrostatic latent image carrier by various means, and then the latent image is developed into a developing device. The toner image is visualized by developing it into a toner image, and then, if necessary, the toner image is transferred to a transfer material such as paper, and then fixed by heating, pressure, heating and pressurization or solvent vapor to obtain a toner image. The method is known.

  As a developing device in such an electrophotographic method, a rubber or metal toner regulating blade as a toner layer thickness regulating member for regulating the toner coating amount is generally applied to the surface of a developing sleeve as a toner carrier. Devices that are configured to contact each other are known.

  By the friction between the toner regulating blade and the toner and / or the friction between the developing sleeve and the toner, a positive or negative charge is given to the toner, and further, the developing sleeve in which the toner is thinly applied on the surface by the toner regulating blade, In general, a method of developing by flying and adhering to the electrostatic latent image on the surface of the electrostatic latent image bearing member facing the developing sleeve is performed.

  As the technical direction of image forming apparatuses in recent years, in addition to high definition, high quality, and high image quality, further high speed and long-term high reliability are required. In order to achieve a high-resolution, high-definition development system, development of toners having high development characteristics such as reduction in toner particle size and sharpening of particle size distribution is in progress.

  When such a highly developable toner is applied to a conventional developing device, the toner may be charged up or a thin layer may be coated on the developing sleeve due to differences in chargeability or powder characteristics. Inability to do so tends to result in lack of image definition.

  On the other hand, various attempts have been made to improve the toner regulating blade or the developing sleeve.

  For example, in Patent Document 1, the hardness and deformation rate of the surface of the developer carrier, and the ten-point average roughness (Rz) of the surface of the developer amount regulating blade on the side in contact with the developer carrier are 0. A developing device of 3 to 20 μm has been proposed. In this invention, an example in which non-magnetic black toner is evaluated using this developing device is described, and it is effective for solid image density, unevenness, streaks and the like in each environment. On the other hand, the stability in long-term durability has not been sufficiently studied, and in particular when one-component magnetic toner is used, the durability stability tends to be insufficient.

  Further, in Patent Document 2, the surface roughness of the developer regulating member is a ten-point surface average roughness Rz, which is larger than 2.0 μm, and the maximum height Rmax is smaller than the average particle diameter of the developer. A developer regulating member set as described above is disclosed. As described in the embodiments of the present invention, in the configuration of the metal blade and the non-magnetic toner, although the effect of the roller set is surely exhibited, other than the metal blade, for example, a urethane rubber blade or silicone In particular, when a rubber blade is used, there are cases where the development stability and environmental stability are insufficient.

  Further, Patent Document 3 proposes a toner regulating blade that defines the surface roughness of the surface of the elastic blade member that slides on the developing roller. In the toner regulating blade of this invention, it is disclosed that the monocomponent magnetic toner having an average particle diameter of 8 μm is effective in the character thickening and charging stability in the examples. Although not mentioned, particularly when the toner having the high development characteristics as described above is applied, the durability stability and the environmental stability may be insufficient.

  In addition, Patent Documents 4 to 8 disclose inventions that define the surface roughness of the toner regulating blade.

  In these inventions, the roughness is defined in the vertical direction, but there is no discussion in the lateral direction such as the uneven spacing and convex density, and the performance depends on the environment and durability conditions. May be insufficient, which is essentially different from the idea of the present invention.

  When the above-described toner regulating blade is applied to a high-speed development system that uses a high-capacity cartridge, particularly with a high process speed, the above-described problems may become apparent, leaving room for further study. It is the present situation.

  Patent Documents 9 to 12 disclose a technique for making a toner shape close to a sphere by a manufacturing method such as a spray granulation method, a solution dissolution method, or a polymerization method. However, both of these techniques require large-scale equipment for toner production, which is not preferable in terms of production efficiency, and may be insufficient in image quality such as durability stability of development characteristics and dot reproducibility. It was.

  Patent Document 13 discloses an invention that defines the surface roughness of toner particles. However, the technology of the present invention controls the surface roughness by further attaching fine particles to the toner particles, which is not preferable in terms of production efficiency, and there is still room for improvement in terms of dot reproducibility and scattering. It was.

  Patent Documents 14 to 16 disclose techniques for modifying the shape and surface property of particles of a toner produced by a pulverization method by mechanical impact. However, even if the shape of the toner is modified by these methods, there is still room for improvement in terms of dot reproducibility during development.

Japanese Patent Laid-Open No. 2004-4751 JP 2004-12542 A JP 2000-330376 A Japanese Patent Laid-Open No. 06-186838 JP 2004-117996 A Special Registration No. 2986343 JP 2004-94138 A JP 2004-117919 A Japanese Patent Laid-Open No. 3-84558 JP-A-3-229268 Japanese Patent Laid-Open No. 4-1766 JP-A-4-102862 JP-A-2004-246344 JP-A-10-97095 JP-A-11-149176 JP-A-11-202557

An object of the present invention to provide the above solves the prior art problems were images forming method and a process cartridge.

An object of the present invention is to provide a picture image forming method and a process cartridge that have a superior developing performance.

An object of the present invention is to provide a clothes moth image forming method and a process cartridge that generates a scattering.

An object of the present invention is to provide a picture image forming method and a process cartridge which is excellent in dot reproducibility.

The present invention is an image forming method in which a toner layer thickness on a toner carrier is regulated by a toner regulating blade, and an electrostatic latent image carrier is developed with toner on the toner carrier,
The ten-point average roughness Rz measured with a laser microscope on the surface of the toner regulating blade in contact with the toner carrying member is 5.0 μm or more and 25.0 μm or less, and the toner of the toner regulating blade The ratio of the area of the contact part and the area of the non-contact part when the part in contact with the carrier is brought into contact with the glass plate at a surface pressure of 14.4 Pa is 27/73 to 70/30 ,
The toner is a toner containing toner particles containing at least a binder resin and a magnetic material and inorganic fine particles, and the average surface roughness of the toner particles measured by a scanning probe microscope is 5.0 nm or more and 60 nm. The present invention relates to an image forming method characterized in that the thickness is 0.0 nm or less.

Furthermore, the present invention is a process cartridge in which the toner layer thickness on the toner carrier is regulated by a toner regulating blade, and the electrostatic latent image carrier is developed with the toner on the toner carrier,
The ten-point average roughness Rz measured by a laser microscope on the surface of the toner regulating blade in contact with the toner carrier is 5.0 μm or more and 25.0 μm or less, and the toner of the toner regulating blade The ratio of the area of the contact part and the area of the non-contact part when the part in contact with the carrier is brought into contact with the glass plate at a surface pressure of 14.4 Pa is 27/73 to 70/30 ,
The toner is a toner containing toner particles containing at least a binder resin and a magnetic material and inorganic fine particles, and the average surface roughness of the toner particles measured by a scanning probe microscope is 5.0 nm or more and 60 nm. The present invention relates to a process cartridge having a thickness of 0.0 nm or less.

The images forming method and process cartridge of the present invention, by using the toner of suitably controlled properties toner regulating blade and moderate surface roughness, be reasonably thin coating amount of the toner in the toner bearing member It is possible to achieve good dot reproducibility and reduction of scattering, and even high speed machines can have good developability.

  As a result of intensive studies, the present inventors have made contact with the toner carrying member of the toner regulating blade, the ten-point average roughness Rz measured by a laser microscope on the surface of the portion of the toner regulating blade that is in contact with the toner carrying member. By controlling the ratio of the area of the contact part to the area of the non-contact part when the surface part is brought into contact with the glass plate at a surface pressure of 14.4 Pa, and the surface roughness of the toner particles is controlled. It has been found that the development characteristics can be controlled and good dot reproducibility and scattering can be reduced.

  In the present invention, the ten-point average roughness Rz and the average spacing Sm of the surface of the portion of the toner regulating blade that contacts the toner carrier, the portion of the toner regulating blade that contacts the toner carrier, and the glass plate The ratio of the area of the contact part to the area of the non-contact part when the surface pressure is contacted at a surface pressure of 14.4 Pa is measured by a non-contact measurement method using a laser microscope (VK-8500, manufactured by Keyence Corporation).

  In many conventional inventions, a contact-type surface roughness measuring device is used to adjust the surface roughness of the toner layer thickness regulating member. In contact-type measurement, the tip radius of the stylus is determined according to the measurement force, but the tip radius may be affected by the shape of the irregularities on the surface of the toner regulating blade. However, different cross-sectional curves may be obtained due to the difference in tip radius. The surface roughness adjustment method using a contact-type measuring device is particularly strict about the vertical direction and the planar direction of the unevenness, especially when the density of the unevenness in the planar direction is relatively higher than the roughness in the vertical direction. It was difficult to adjust to the desired surface properties defined.

  Below, the specific example of the non-contact measuring method in this invention is shown.

<Measuring method of ten-point average roughness Rz and average interval Sm of unevenness of toner regulating blade surface>
1) Preparation of sample Cut the toner regulating blade into a size of about 1 cm square. However, as long as there is a sufficient area for irradiating the laser in the observation with a laser microscope, the size to be cut is not particularly limited.
2) Measurement conditions Set parameters for measurement as follows.
Objective lens magnification: 20 × Optical zoom magnification: 1 × Digital zoom magnification: 1 × RUN MODE: Color super depth LASER (gain): 594
LASER (offset): -1328
Camera settings (shutter): 158
Camera setting (white balance): 3200k
Camera setting (gain): 0
3) Setting of the sample The cut toner regulating blade is set on the stage of the laser microscope so that the portion in contact with the toner carrier becomes the observation surface.
4) Measurement The surface of the toner regulating blade is measured with a measurement PITCH of 0.1 μm.
5) Image processing In order to correct the overall distortion and inclination of the image obtained by the measurement, the following processing was performed.

[1. Tilt correction]
Correction method: Surface correction (automatic)
Process target: Height The following process was performed in order to remove fine noise components in the image obtained by the measurement.

[2. Filter processing]
Process target: Smoothing (height data)
Size: 7x7
Number of executions: 1
File Type: Median

[3. Filter processing]
Process target: Smoothing (height data)
Size: 3x3
Number of executions: 1
File type: Simple average 6) Analysis Height data is used for analysis. A scale is drawn on the obtained height data image, a range of 200 μm × 260 μm is selected, and the ten-point average roughness Rz and the average interval Sm of the irregularities in this range are used as measurement results.

[Ten point average roughness Rz]
The value obtained in the surface roughness measurement mode.

[Average interval Sm of unevenness]
In line roughness measurement mode, draw 5 straight lines in any horizontal direction and 5 straight lines in any vertical direction, and 2 upper and lower limit values out of the average interval Sm of 10 irregularities obtained from a total of 10 straight lines And the average of the remaining 8 points.

<Measurement Method of Ratio of Area of Contact Part and Area of Non-Contact Part When Contacting Part of Toner Regulation Blade with Toner Carrier and Glass Plate at Contact Pressure of 14.4 Pa>
In the developing device used for evaluating the toner of the present invention, as a method of simulating the state in which the toner regulating blade and the toner carrier are in contact with each other, the toner regulating blade is cut out and the toner regulating blade is actually used. A state when a load corresponding to the contact pressure was applied was created and observed. The method is shown below. The surface pressure of 14.4 Pa is a value corresponding to the most preferable surface pressure at the portion of the developing device that is in contact with the toner carrier of the toner regulating blade.
1) Preparation of sample [Preparation of observation sample]
A portion of the cut toner regulating blade that is in contact with the toner carrier is placed on the upper side, and a glass plate is placed thereon. At this time, the center of gravity of the toner regulating blade and the glass plate are made to coincide. Furthermore, the same weight is placed on both sides of the glass plate. The positions of the respective weights are symmetrical with respect to the center of gravity of the toner regulating blade and the glass plate, and do not disturb the approach of the objective lens when observing the toner regulating blade.

[Toner control blade]
Cut the toner regulating blade precisely to a size of 0.8 cm square.

[Glass plate]
The glass plate preferably has a smooth surface. In particular, a slide glass (thickness: 0.9 to 1.2 mm, 76 × 26 mm, manufactured by Matsunami Glass Co., Ltd.) is more preferably used in this measurement.

[Weight for load]
In this measurement, the portion of the toner regulating blade that is in contact with the toner carrier is brought into contact with the glass plate at a surface pressure of 14.4 Pa. To bring the glass plate into contact with the 0.8 cm square toner regulating blade at a surface pressure of 14.4 Pa, a load of 147 g is required. A weight is prepared so that the total of the mass of a glass plate and two weights of the same mass becomes 147 g. Any weight can be used. In this measurement, a method of preparing a weight with a desired mass by putting powder or water having a large specific gravity into a sample bottle is preferable. It is preferable to use iron powder for powder having a large specific gravity. It is preferable to use a screw vial (SV-30 outer diameter: 30 mm, height: 65 mm, wall thickness: 1.5 mm, mouth inner diameter: 19.8 mm, capacity: 30 ml, manufactured by Nidec Rika Glass Co., Ltd.) as the sample bottle.
2) Measurement conditions Set parameters for measurement as follows.
Objective lens magnification: 20x Optical zoom magnification: 1x Digital zoom magnification: 1x RUN MODE: Color super depth LASER (gain): 594
LASER (offset): -1328
Camera settings (shutter): 158
Camera setting (white balance): 3200k
Camera setting (gain): 0
3) Setting of sample A 0.8 cm square toner regulating blade with a load applied is set on the stage of the laser microscope so that the portion in contact with the toner carrier becomes the observation surface.
4) Measurement The measurement is performed so that the PITCH is 0.1 μm and the contact surface between the surface of the toner regulating blade and the glass plate is included.
5) Image processing In order to correct the overall distortion and inclination of the image obtained by the measurement, the following processing was performed.

[1. Tilt correction]
Correction method: Surface correction (automatic)
Process target: Height The following process was performed in order to remove fine noise components in the image obtained by the measurement.

[2. Filter processing]
Process target: Smoothing (height data)
Size: 7x7
Number of executions: 1
File Type: Median

[3. Filter processing]
Process target: Smoothing (height data)
Size: 3x3
Number of executions: 1
File type: Simple average 6) Analysis Height data is used for analysis. In the obtained height data image, the contact portion between the toner regulating blade and the glass plate is clearly displayed in black with respect to the non-contact portion (FIG. 1). By binarizing the area of the contact portion and the non-contact portion due to the difference in color, when the portion of the toner regulating blade that is in contact with the toner carrier is brought into contact with the glass plate at a surface pressure of 14.4 Pa, The ratio of the area of the contact part and the area of the non-contact part can be calculated. As a method for binarizing the areas of the contact part and the non-contact part, an application having an image analysis function is preferably used. As an application, for example, “Image-Pro Plus (Media Cybernetics)” is used. In binarizing the areas of the contact part and the non-contact part, the following operation is performed in order to remove minute noise from the obtained image and to obtain a more accurate value.

  By setting the histogram in the range of 0 to 255 in the color extraction process to the range of 0 to 60, very minute noise is removed. By this operation, the contact portion and the non-contact portion can be divided into two colors.

  The total surface contact area of the contact area is calculated by measuring the area of the measurement item.

  The area ratio between the contact part and the non-contact part is calculated from the area of the entire image and the total area of the contact part.

  Examples of the method for roughening the toner regulating blade in the present invention include, for example, a sandblast method, a shot blast method, a method using a sand paper, and the like as a physical method, and a chemical method as an etching method. And a method of forming a film containing coarse particles.

  Among them, in the present invention, it is preferable to mold using a drum mold such as a centrifugal molding method or a continuous injection molding method. That is, in the process of injecting the toner regulating blade forming liquid into the mold and molding the toner regulating blade while rotating, the mold is rotating, so that the centrifugal force works and the air in the toner regulating blade forming liquid And the like, and the toner regulating blade forming liquid is pressed against the mold surface, so that it is possible to obtain a toner regulating blade in which the irregularities of the mold are accurately transferred without mixing air or the like. At this time, as a method for forming irregularities on the inner peripheral surface of the mold, a method of using a bead blast method with roughened particles on the mold surface, or a mold release layer on the inner peripheral surface of the mold, The surface layer part of the mold layer preferably contains a surface roughening treatment agent such as spherical fluorinated graphite, and the height (depth) and unevenness interval of the uneven parts are controlled by the particle size and content of the roughened particles. can do. For example, as shown in the model diagram of FIG. 2, the toner regulating blade 12 transferred from the die 11 that has been bead-blasted with roughened particles has a convex portion with a smooth rounded arc shape, By adjusting the diameter and the discharge pressure, the ratio (ratio) and depth (height) of the concave and convex portions can be controlled. On the other hand, as shown in the model diagram of FIG. 3, in the toner regulating blade 23 transferred from the mold surface 21 formed with the release layer 22 containing the roughening treatment agent, the convex portion is relatively It becomes a flat shape, and the recess can obtain a relatively deep surface shape. Also in this case, the ratio (ratio) and depth (height) of a recessed part and a convex part are controllable by adjusting the particle size and content of a roughening processing agent. The toner regulation blade is configured so that the uneven surface (mold surface) of the toner regulation blade thus obtained is on the contact surface side with the developing sleeve, thereby regulating the toner layer thickness. Do.

  The toner regulating blade member used in the present invention is not particularly limited. For example, urethane rubber, polyamide resin, polyamide elastomer, silicone rubber, silicone resin, and the like can be used, and the use of urethane rubber is preferable. It is preferable in obtaining. The support member of the toner regulating blade is preferably made of a metal flat plate, a resin flat plate, more specifically, a stainless steel plate, a phosphor bronze plate, an aluminum plate, or the like. An additive such as a conductive material can be added to the main material of the blade member. In addition, the support member and the blade member can be bonded by, for example, an adhesive such as hot melt.

  When a rubber material is used as the toner regulating blade member, the rubber hardness is preferably 40 ° or more and 100 ° or less in (JIS) A in order to control the above-described contact area ratio. More preferably, (JIS) A 45 ° to 95 ° is preferable. More preferably, (JIS) A is 50 ° to 90 °. If the rubber hardness is less than 40 °, the contact pressure with respect to the toner carrier is likely to be insufficient, and the toner may not be sufficiently charged, resulting in poor developability. On the other hand, when the angle exceeds 100 °, the contact pressure becomes too high, causing toner deterioration and easily causing poor charging.

  In the present invention, the average surface roughness of the toner particles is from 5.0 nm to 60.0 nm, preferably from 8.0 nm to 35.0 nm, more preferably from 10.0 nm to 25.0 nm. To do. It is important that the average surface roughness of the toner particle surface is within the above range, and the shape of the toner is not particularly limited. When the toner particles have an appropriate surface roughness, an appropriate gap is created between the toners, the fluidity of the toner can be improved, and better developability can be brought about. When the average surface roughness of the toner particles is less than 5.0 nm, the chargeability increases and electrostatic aggregation easily occurs, so that sufficient fluidity cannot be imparted to the toner, causing charge-up and image density lowering. . When the average surface roughness of the toner particles is larger than 60.0 nm, the voids between the toner particles are excessively increased, so that the toner is insufficiently charged and the fog is deteriorated.

In the present invention, the average surface roughness of the toner particles and the toner, the maximum height difference of the toner particles, and the surface area are measured using a scanning probe microscope. Below, the example of a measuring method is shown.
Probe station: SPI3800N (manufactured by Seiko Instruments Inc.)
Measuring unit: SPA400
Measurement mode: DFM (resonance mode) shape image Cantilever: SI-DF40P
Resolution: Number of X data 256
Number of Y data 128

In the present invention, the area of 1 μm square of the toner particles and the toner surface is measured. The area to be measured is a 1 μm square area at the center of the toner particles and the toner surface measured with a scanning probe microscope. As the toner particles and toner to be measured, toner particles and toner equal to the weight average particle diameter (D ₄ ) measured by the Coulter counter method are selected at random, and the toner particles and toner are measured. The measured data is subjected to secondary correction. Five or more different toner particles and toners are measured, and the average value of the obtained data is calculated to obtain the average surface roughness of the toner particles and the toner, and the surface area of the toner particles.

In a toner in which an external additive is externally added to the toner particles, when the surface of the toner particles is measured using a scanning probe microscope, it is necessary to remove the external additive. A method is mentioned.
1) Put 45 mg of toner into a sample bottle and add 10 ml of methanol.
2) Disperse the sample for 1 minute with an ultrasonic cleaner to separate the external additive.
3) The toner particles and the external additive are separated by suction filtration (10 μm membrane filter). In the case of a toner containing a magnetic material, the toner particles may be fixed by applying a magnet to the bottom of the sample bottle to separate only the supernatant.
4) The above 2) and 3) are performed three times in total, and the obtained toner particles are sufficiently dried at room temperature in a vacuum dryer.

The toner particles from which the external additive has been removed are observed with a scanning electron microscope, and after confirming that the external additive has disappeared, the surface of the toner particles can be observed with a scanning probe microscope. If the external additive is not sufficiently removed, the surface of the toner particles is observed with a scanning probe microscope after repeating 2) and 3) until the external additive is sufficiently removed.
2) As another method for removing the external additive in place of 3), there is a method of dissolving the external additive with an alkali. As the alkali, an aqueous sodium hydroxide solution is preferred.

Each term is explained below.
・ Average surface roughness (Ra)
The centerline average roughness Ra defined in JIS B0601 is expanded to three dimensions so that it can be applied to the measurement surface. The absolute value of the deviation from the reference plane to the specified plane is averaged and expressed by the following formula.

Ｆ（Ｘ，Ｙ）：全測定データの示す面
Ｓ₀：指定面が理想的にフラットであると仮定したときの面積
Ｚ₀：指定面内のＺデータの平均値
指定面とは、本発明においては１μｍ四方の測定エリアを意味する。
・最大高低差（Ｐ−Ｖ）
指定面内におけるＺデータの最大値と最小値の差。
・表面積（Ｓ）
指定面の表面積。

F (X, Y): Surface S ₀ indicated by all the measurement data: Area Z ₀ when the designated surface is assumed to be ideally flat Z ₀ : Average value designated surface of Z data in the designated surface Means a measurement area of 1 μm square.
・ Maximum height difference (P-V)
The difference between the maximum and minimum values of Z data within the specified plane.
・ Surface area (S)
The surface area of the specified surface.

  Next, a toner particle manufacturing method using a surface modification step will be described as a preferred method for obtaining toner particles characterized by the present invention. In the present invention, surface modification means smoothing the surface of toner particles.

  As the surface modification device, the following devices are used. A pulverizer or the like can also be used as the toner particle surface modifying apparatus of the present invention. Faculty (manufactured by Hosokawa Micron), Mechano-Fusion (manufactured by Hosokawa Micron), Nobilta (manufactured by Hosokawa Micron), Hybridizer (manufactured by Nara Machinery), Inomizer (manufactured by Hosokawa Micron), Examples include mechano mill (Okada Seiko Co., Ltd.), kryptron (Kawasaki Heavy Industries Co., Ltd.), super rotor (Nisshin Engineering Co., Ltd.), turbo mill (Turbo Kogyo Co., Ltd.), and tornado mill (Nikkiso Co., Ltd.). In the surface modification of the toner particles, the treatment may be repeated twice or more in the same apparatus, or two or more kinds of surface modification apparatuses may be combined and processed.

  In the surface modification apparatus, for example, Faculty (manufactured by Hosokawa Micron Corporation) has a function of removing fine powder components simultaneously with the surface modification of toner particles in the toner particle surface modification step. When the surface modification of the toner particles is performed by the surface modification apparatus capable of removing the fine powder component at the same time as the surface modification of the toner particles as described above, the raw material toner particles finely divided in the vicinity of a desired particle diameter in advance are converted into an air flow type. It is preferable to remove the fine powder and coarse powder to some extent using a classifier, and then to modify the surface of the toner particles with a surface modification device. In this case, the toner particles from which fine powder has been removed by the airflow classifier have a cumulative value of the number average distribution of toner particles of less than 4 μm in a particle size distribution measured using a Coulter counter method of 10% or more and less than 50%. It is preferably 15% or more and less than 45%, more preferably 15% or more and less than 40%. Examples of the airflow classifier used in the present invention include elbow jet (manufactured by Nippon Steel Industries Co., Ltd.).

  The inventors of the present invention have a ten-point average roughness Rz of 5.0 μm or more and 25.0 μm or less, preferably 5.0 μm or more, measured with a laser microscope on the surface of the toner regulating blade that is in contact with the toner carrier. 20.0 μm or less, more preferably 5.0 μm or more and 15.0 μm or less, and contact between the portion of the toner regulating blade that is in contact with the toner carrying member and the glass plate at a contact pressure of 14.4 Pa The ratio of the area of the part to the area of the non-contact part is 8/92 to 70/30, preferably 8/92 to 60/40, and the average surface roughness of the toner particles measured with a scanning probe microscope is 5 0.0 nm or more and 60.0 nm or less, preferably 8.0 nm or more and 35.0 nm or less, more preferably 10.0 nm or more and 25.0 nm or less, excellent dot reproducibility and less scattering It found Rukoto.

  The ten-point average roughness Rz measured with a laser microscope on the surface of the toner regulating blade in contact with the toner carrier is 5.0 μm or more and 25.0 μm or less, preferably 5.0 μm or more and 20.0 μm or less. Preferably, it is 5.0 μm or more and 15.0 μm or less, and the area of the contact portion when the surface of the toner regulating blade that is in contact with the toner carrying member is brought into contact with the glass plate at a surface pressure of 14.4 Pa is not contacted. When the area ratio of the part is 8/92 to 70/30, that is, the portion of the toner regulating blade that is in contact with the toner carrying member is roughened, and there are irregularities that fall within the above range. In this case, since the toner regulating blade has an effect of scraping off the toner coated on the toner carrier, it is considered that the coating layer can be thinned.

  At this time, if the average surface roughness of the toner particles is 5.0 nm or more and 60.0 nm or less, preferably 8.0 nm or more and 35.0 nm or less, more preferably 10.0 nm or more and 25.0 nm or less, Since it has fluidity, it is considered that the toner can be easily loosened by scraping off the toner regulating blade, and the coating can be thinned. Furthermore, when the average surface roughness of the toner particles is 5.0 nm or more and 60.0 nm or less, preferably 8.0 nm or more and 35.0 nm or less, more preferably 10.0 nm or more and 25.0 nm or less. Excellent. Since the toner is thinly coated on the toner carrier and further coated with a thin layer, the entire toner can be uniformly charged, and it is considered that dot reproducibility is excellent and scattering is reduced.

  When the average surface roughness of the toner particles is less than 5.0 nm, the surface of the toner particles is so smooth that the toner easily enters the recesses of the toner regulating blade, and the original toner regulating blade scraping effect. May not be fully exhibited. As a result, the coat becomes thick and the toner is excessively developed, so that the dot reproducibility is deteriorated and the scattering is sometimes deteriorated.

  If the average surface roughness of the toner particles is larger than 60.0 nm, the gap between the toners becomes large and the bulk density becomes small, so that the amount taken up on the toner carrier is small and further scraped off by the toner regulating blade. Can be very thin, so the coat can be very thin. For this reason, a sufficient amount of toner cannot be supplied for development, and dot reproducibility may be deteriorated and scattering may be deteriorated.

  Further, the maximum height difference of the toner particles is 50 nm or more and less than 250 nm, preferably 80 nm or more and less than 220 nm, more preferably 100 nm or more and less than 200 nm, and better fluidity can be imparted to the toner. If the maximum height difference of the toner particles is less than 50 nm, sufficient fluidity cannot be imparted to the toner, fading may occur and the image density may decrease. If the maximum height difference of the toner particles is 250 nm or more, the toner may scatter and fog may deteriorate.

Further, the surface area of the toner particles is 1.03 × 10 ⁶ nm ² or more and 1.33 × 10 ⁶ nm ² or less, preferably 1.05 × 10 ⁶ nm ² or more and 1.30 × 10 ⁶ nm ² or less, more preferably. It is preferably 1.07 × 10 ⁶ nm ² or more and 1.28 × 10 ⁶ nm ² or less, and better fluidity can be imparted to the toner particles. When the surface area of the toner particles is less than 1.03 × 10 ⁶ nm ² , sufficient fluidity cannot be imparted to the toner, and the image density may decrease. When the surface area of the toner particles is larger than 1.33 × 10 ⁶ nm ² , scattering may occur.

(Effects and adverse effects with toner)
The toner of the present invention is characterized in that the average surface roughness of the toner is from 10.0 nm to 35.0 nm, preferably from 12.0 nm to 24.0 nm. When the average surface roughness of the toner is 10.0 nm or more and 35.0 nm or less, preferably 12.0 nm or more and 24.0 nm or less, the external additive is uniformly present on the surface of the toner particles, and uniform charging performance is obtained. In addition to having an appropriate fluidity, it is considered that the dot reproducibility is excellent and the scattering is reduced. When the average surface roughness of the toner is less than 10.0 nm, a large number of external additive particles are embedded in the toner recesses, the toner surface becomes non-uniform in charge distribution, and dot reproducibility and scattering are deteriorated. There is a case. When the average surface roughness of the toner is larger than 26.0 nm, the external additive particles on the toner surface are not uniformly coated, and scattering may be deteriorated due to poor charging. As described above, even in the toner, the effect of the present invention can be easily obtained by having an appropriate surface roughness.

  Further, if the ten-point average roughness Rz of the surface of the toner regulating blade that is in contact with the toner carrier is less than 5.0 μm, the toner scraping effect is not sufficiently exerted, and the coat tends to be thick. Dot reproducibility tends to be poor. When the ten-point average roughness Rz is larger than 25.0 μm, the coat becomes extremely thin, charge-up is likely to occur, and the image density is lowered.

  Further, the ratio of the area of the contact part to the area of the non-contact part when the part of the toner regulating blade in contact with the toner carrier and the glass plate is brought into contact with the surface pressure of 14.4 Pa is less than 8/92. In this case, there is sufficient space for the toner to move between the irregularities of the toner regulating blade, but the toner cannot be uniformly coated because the ratio between the convex and concave portions of the toner regulating blade is not appropriate. Unevenness is likely to occur, and vertical stripes may occur in the image. If the ratio of the contact area to the non-contact area is greater than 70/30, there is not enough space for the toner to move between the irregularities of the toner regulating blade, so that the toner scraping effect is sufficiently exerted. In other words, the toner is excessively developed, so that the coat becomes thick, and dot reproducibility is deteriorated and scattering is sometimes deteriorated.

  Also, if the average spacing Sm of the irregularities on the surface of the toner regulating blade that is in contact with the toner carrier is less than 5.0 μm, there is not enough space for the toner to move between the irregularities. The scraping effect is not sufficiently exhibited, the coat becomes thick, the dot reproducibility is deteriorated and the scattering may be deteriorated. When the average interval Sm of the unevenness is larger than 200.0 μm, the toner is in between the unevenness of the toner regulating blade. There is enough space to move the toner, but the distance between the irregularities of the toner regulating blade becomes longer, the toner cannot be uniformly coated, and uneven coating due to the irregularities of the toner regulating blade is likely to occur, Vertical streaks may occur in the image.

  In the present invention, when the wettability of toner particles with respect to a methanol / water mixed solvent is measured by the transmittance of light having a wavelength of 780 nm, the methanol concentration when the transmittance is 80% and the methanol concentration when the transmittance is 50% are obtained. It is preferable to be within the range of 35 to 75% by volume, preferably 40 to 70% by volume, and more preferably 45 to 65% by volume. Toner particles having such methanol concentration-transmittance characteristics can be obtained by setting the surface modification treatment conditions to appropriate conditions using the surface modification apparatus characterized by the present invention. The exposure ratio of the raw materials is appropriate, the fluidity is excellent, and a moderate and sharp chargeability can be brought to the toner particles. As described above, the toner having good fluidity and a sharp charge amount distribution allows the toner to be uniformly and highly charged in the toner container, and obtains a good and stable image density even in long-term use. And an image having excellent dot reproducibility can be obtained.

  When the methanol concentration when the transmittance of toner particles is 80% and the methanol concentration when the transmittance is 50% is lower than 35% by volume, the chargeability of the toner becomes insufficient and the image density becomes inferior. There is. Further, if the methanol concentration when the transmittance is 80% and the methanol concentration when the transmittance is 50% exceeds 75% by volume, the toner has high cohesiveness, and sufficient fluidity cannot be obtained. The reproducibility becomes worse.

  Further, the difference in concentration between the methanol concentration when the transmittance is 80% and the methanol concentration when the transmittance is 50% is 10% or less, preferably 7% or less, more preferably 5% or less. Is preferable, and better developability can be imparted to the toner. When the density difference exceeds 10%, the surface state of the toner becomes non-uniform, and dot reproducibility and scattering are deteriorated.

  In the present invention, the wettability, that is, the hydrophobic property of the toner particles is measured using a methanol dropping transmittance curve. Specifically, as the measuring device, for example, a powder wettability tester WET-100P manufactured by Reska Co., Ltd. is used, and a methanol dropping transmittance curve measured under the following conditions and procedures is used. First, 70 ml of a water-containing methanol solution composed of 20 to 50% by volume of methanol and 50 to 80% by volume of water is placed in a container, and 0.1 g of toner particles as a sample are precisely weighed and added to the container. Prepare a sample solution for measuring hydrophobic properties. Next, transmittance was measured with light having a wavelength of 780 nm while continuously adding methanol to the measurement sample solution at a dropping rate of 1.3 ml / min, and the methanol dropping transmittance as shown in FIG. Create a curve. In this case, methanol is used as the titration solvent because the influence of elution of dyes, pigments, charge control agents and the like contained in the toner particles is small, and the surface state of the toner particles can be observed more accurately.

  As the types of binder resins used in the present invention, styrene resins, styrene copolymer resins, polyester resins, polyol resins, polyvinyl chloride resins, phenol resins, natural modified phenol resins, natural resin modified maleic resins, Examples thereof include acrylic resin, methacrylic resin, polyvinyl acetate, silicone resin, polyurethane resin, polyamide resin, furan resin, epoxy resin, xylene resin, polyvinyl butyral, terpene resin, coumarone indene resin, and petroleum resin.

  As a comonomer for the styrene monomer of the styrene copolymer, a styrene derivative such as vinyltoluene; acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, acrylic Acrylic acid ester such as phenyl acid; Methacrylic acid ester such as methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate; Maleic acid; Double such as butyl maleate, methyl maleate, dimethyl maleate Dicarboxylic acid ester having a bond; acrylamide, acrylonitrile, methacrylonitrile, butadiene; vinyl ester such as vinyl chloride, vinyl acetate, vinyl benzoate; ethylene, propylene, butylene Such ethylenic olefins, vinyl methyl ketone, such as vinyl vinyl hexyl ketone, vinyl methyl ether, vinyl ethyl ether, vinyl propionate ether. These vinyl monomers are used alone or in combination of two or more.

  In the present invention, a styrene-acrylic acid ester-acrylic acid copolymer, a styrene-acrylic acid ester copolymer, and a styrene-acrylic acid ester-methacrylic acid copolymer are used as a particularly preferable binder resin, whereby toner It becomes easy to control the surface roughness of the particles to an appropriate value.

  The binder resin used in the present invention has a glass transition temperature (Tg) of 45 to 80 ° C, preferably 50 to 70 ° C, from the viewpoint of storage stability. When Tg is lower than 45 ° C., it tends to cause toner deterioration under a high temperature atmosphere and offset during fixing. On the other hand, when Tg exceeds 80 ° C., fixability tends to decrease.

  The measuring method of Tg is performed according to ASTM D3418-82 using Q-1000 manufactured by TA Instruments. The DSC curve used in the present invention is a DSC curve that is measured when the temperature is raised at a rate of 10 ° C./min after raising and lowering the temperature once and taking a previous history. The definition is as follows.

Glass transition point (Tg)
The temperature at the intersection of the DSC curve and the line connecting the midpoints of the baseline before and after the change in specific heat appears in the DSC curve during temperature rise.

  The peak molecular weight of the binder resin is preferably 3000 to 30000, preferably 5000 to 25000, and more preferably 8000 to 20000, so that the toner particles have an appropriate hardness, and the surface of the toner particles It becomes easier to perform modification.

  In the present invention, the molecular weight distribution of the binder resin by GPC using THF (tetrahydrofuran) as a solvent is measured under the following conditions.

The column is stabilized in a 40 ° C. heat chamber. Tetrahydrofuran (THF) is allowed to flow through the column at this temperature as a solvent at a flow rate of 1 ml per minute, and about 100 μl of a sample THF solution is injected and measured. In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the number of counts. As a standard polystyrene sample for preparing a calibration curve, for example, one having a molecular weight of about 10 ² to 10 ⁷ manufactured by Tosoh Corporation or Showa Denko KK, and at least about 10 standard polystyrene samples is suitable. is there. An RI (refractive index) detector is used as the detector. As the column, it is preferable to combine a plurality of commercially available polystyrene gel columns. For example, combinations of shodex GPC KF-801, 802, 803, 804, 805, 806, 807, 800P manufactured by Showa Denko KK, TSKgel G1000H (H _XL ), G2000H (H _XL ), G3000H (H _XL ) manufactured by Tosoh Corporation , G4000H (H _XL ), G5000H (H _XL ), G6000H ( _XL ), G7000H (H _XL ), and TSK guard column.

  The sample is prepared as follows.

  Put the sample in THF, let stand for several hours, then shake well and mix well with THF (until the sample is no longer united) and let stand for more than 12 hours. At this time, the sample is left in THF for 24 hours or longer. Thereafter, a sample processing filter (pore size 0.45-0.5 μm, for example, Mysori Disc H-25-5 manufactured by Tosoh Corp., Excro Disc 25CR manufactured by Gelman Science Japan Co., Ltd., etc.) can be used, A measurement sample for GPC is used. The sample concentration is adjusted so that the resin component is 0.5 to 5 mg / ml.

  Examples of the polymerization method of the binder resin of the present invention include a solution polymerization method, an emulsion polymerization method and a suspension polymerization method.

  The binder resin used in the present invention is preferably produced by using a polyfunctional polymerization initiator alone or in combination with a monofunctional polymerization initiator as exemplified below.

  Specific examples of the polyfunctional polymerization initiator having a polyfunctional structure include 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane, 1,3-bis- (t-butylperoxy Isopropyl) benzene, 2,5-dimethyl-2,5- (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di- (t-butylperoxy) hexane, tris- (t-butyl) Peroxy) triazine, 1,1-di-t-butylperoxycyclohexane, 2,2-di-t-butylperoxybutane, 4,4-di-t-butylperoxyvaleric acid-n-butyl ester , Di-t-butylperoxyhexahydroterephthalate, di-t-butylperoxyazelate, di-t-butylperoxytrimethyladipate, 2,2-bis- ( , 4-di-t-butylperoxycyclohexyl) propane, 2,2-t-butylperoxyoctane and functional groups having a polymerization initiation function such as two or more peroxide groups in one molecule of various polymer oxides. A polyfunctional polymerization initiator having a peroxide group in one molecule such as diallyl peroxydicarbonate, t-butylperoxymaleic acid, t-butylperoxyallylcarbonate and t-butylperoxyisopropyl fumarate. Such a polyfunctional polymerization initiator having both a functional group having a polymerization initiating function and a polymerizable unsaturated group is selected.

  Of these, more preferred are 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane, 1,1-di-t-butylperoxycyclohexane, di-t-butylperoxy. Hexahydroterephthalate, di-t-butylperoxyazelate, 2,2-bis- (4,4-di-t-butylperoxycyclohexyl) propane, and t-butylperoxyallyl carbonate.

  These polyfunctional polymerization initiators are preferably used in combination with a monofunctional polymerization initiator in order to satisfy various performances required as a binder for toner. In particular, it is preferable to use in combination with a polymerization initiator having a half-life of 10 hours lower than the decomposition temperature for obtaining a half-life of 10 hours of the polyfunctional polymerization initiator.

  Specifically, benzoyl peroxide, 1,1-di (t-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4,4-di (t-butylperoxy) valerate, dichroic Organic peroxides such as milperoxide, α, α'-bis (t-butylperoxydiisopropyl) benzene, t-butylperoxycumene, di-t-butylperoxide; azobisisobutyronitrile, diazoamino Examples include azo and diazo compounds such as azobenzene.

  These monofunctional polymerization initiators may be added to the monomer at the same time as the polyfunctional polymerization initiator, but in order to keep the efficiency of the polyfunctional polymerization initiator appropriate, in the polymerization step, It is preferably added after the half-life indicated by the polyfunctional polymerization initiator has elapsed.

  These polymerization initiators are preferably used in an amount of 0.05 to 2 parts by mass with respect to 100 parts by mass of the monomer from the viewpoint of efficiency.

  It is also preferable that the binder resin is crosslinked with a crosslinking monomer.

  As the crosslinkable monomer, a monomer having two or more polymerizable double bonds is mainly used. Specific examples include aromatic divinyl compounds (eg, divinylbenzene, divinylnaphthalene, etc.); diacrylate compounds linked by alkyl chains (eg, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4 -Butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, and acrylates of the above compounds replaced with methacrylate); alkyl chain containing an ether bond Diacrylate compounds (eg, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, Ethylene glycol # 600 diacrylate, dipropylene glycol diacrylate, and acrylates of the above compounds in place of methacrylate); diacrylate compounds linked by a chain containing an aromatic group and an ether bond (eg, polyoxyethylene) (2) -2,2-bis (4-hydroxyphenyl) propane diacrylate, polyoxyethylene (4) -2,2-bis (4-hydroxyphenyl) propane diacrylate, and methacrylates of the above compounds Furthermore, polyester-type diacrylate compounds (for example, trade name MANDA (Nippon Kayaku)) are mentioned. As polyfunctional crosslinking agents, pentaerythritol acrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate, and acrylates of the above compounds are replaced with methacrylate. Triallyl cyanurate, triallyl trimellitate; and the like.

  These crosslinking agents are preferably used in the range of 0.00001 to 1 part by mass, preferably 0.001 to 0.05 part by mass, with respect to 100 parts by mass of the other monomer components.

In the present invention, it is more preferable to contain a bond formed by a reaction between a carboxyl group and an epoxy group as a crosslinked structure. The epoxy group in the present invention is a functional group in which an oxygen atom is bonded to different carbon atoms in the same molecule to form a cyclic ether structure.
Examples of the monomer having an epoxy group that can be used in the present invention include the following.

  Examples include glycidyl acrylate, glycidyl methacrylate, β-methyl glycidyl acrylate, β-methyl glycidyl methacrylate, allyl glycidyl ether, and allyl β-methyl glycidyl ether. Moreover, the glycidyl monomer represented by general formula (A) is used preferably.

  The bond formed by the reaction between the carboxyl group and the epoxy group is, for example, when a compound having a glycidyl group as an epoxy group is used.

となり、架橋構造を形成するものである。
（（ａ）において、Ｒ₁、Ｒ₂及びＲ₃は、水素原子、又は、アルキル基、アリール基、アラルキル基、カルボキシル基及びアルコシキカルボニル基からなるグループより選ばれる官能基を示す。）

Thus, a crosslinked structure is formed.
(In (a), R ₁ , R ₂ and R ₃ represent a hydrogen atom or a functional group selected from the group consisting of an alkyl group, an aryl group, an aralkyl group, a carboxyl group and an alkoxycarbonyl group.)

  In the present invention, as means for obtaining a vinyl resin having a bond formed by a reaction between a carboxyl group and an epoxy group as a cross-linked structure, 1) a vinyl resin having a carboxyl group and a vinyl resin having an epoxy group in a solution state. Mix and cause cross-linking reaction by applying heat in the reaction kettle. 2) Take out the vinyl resin with carboxyl group and the vinyl resin with epoxy group from the reaction kettle, respectively, and dry blend with a Henschel mixer. A reaction between a carboxyl group and an epoxy group may be caused to crosslink by hot melt kneading with a twin screw extruder or the like. Similarly, when a vinyl resin having a carboxyl group and an epoxy group is used, the carboxyl group and the epoxy group can be reacted by hot melt kneading with a biaxial extruder or the like.

  The vinyl resin having an epoxy group is preferably used in an amount of 0.03 or more and 1 equivalent or less, preferably 0.03 or more and 0.5 equivalent or less, per 1 equivalent of a carboxyl group.

  In the present invention, the vinyl resin having a cross-linked structure formed by the reaction of a carboxyl group and an epoxy group has an acid value of 1 to 50 mgKOH / g, more preferably 1 to 40 mgKOH / g, and still more preferably Is 2-40 mg KOH / g. With such an acid value, the toner is excellent in chargeability when made into a toner, and the effects of the present invention can be easily obtained.

  In the present invention, the acid value (JIS acid value) of the binder resin is determined by the following method.

Basic operation conforms to JIS K-0070.
(1) In the sample, the tetrahydrofuran-insoluble component of the binder resin is removed in advance, and the tetrahydrofuran-soluble component is used as the sample. The pulverized sample 0.5 to 2.0 (g) is precisely weighed, and the weight of the soluble component is defined as W (g).
(2) A sample is put into a 300 ml beaker, and 150 ml of a toluene / ethanol (4/1) mixed solution is added and dissolved.
(3) Titration using a potentiometric titration apparatus with an ethanol solution of 0.1 mol / l KOH (for example, potentiometric titration apparatus AT-400 (winworkstation) manufactured by Kyoto Electronics Co., Ltd. and ABP-410 electric burette Automatic titration with can be used.)
(4) The amount of KOH solution used at this time is S [ml]. At the same time, a blank test without using a sample is performed, and the amount of KOH solution used at this time is B [ml].
(5) The acid value is calculated by the following formula. f is a factor of KOH.
Acid value (mgKOH / g) = {(SB) × f × 5.61} / W

  As a method for producing a binder resin composition, a high-molecular weight polymer and a low-molecular weight polymer are separately synthesized by a solution polymerization method, mixed in a solution state, and then desolvated, and an extruder. The resin composition is prepared by dissolving in a monomer constituting a high molecular weight polymer obtained by dissolving a low molecular weight polymer obtained by a melt blending method such as a melt blending method, a solution polymerization method, etc., and performing suspension polymerization, washing and drying. And a two-stage polymerization method for obtaining However, the dry blend method has a point to be improved in terms of uniform dispersion and compatibility. The two-stage polymerization method has many advantages such as uniform dispersibility, but the low molecular weight can be increased to higher than the high molecular weight, and a high molecular weight polymer with a large molecular weight can be synthesized. The solution blending method is most suitable because there are few problems that coalescence is formed as a by-product. In addition, when a predetermined acid value is introduced into the low molecular weight polymer component, solution polymerization in which the acid value can be easily set as compared with the polymerization method using an aqueous medium is preferable.

  Examples of the composition of the polyester resin used as the binder resin in the present invention are shown below.

  Examples of the divalent alcohol component include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1, 6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, and bisphenol represented by formula (A) and derivatives thereof;

（式中、Ｒはエチレンまたはプロピレン基であり、ｘ及びｙはそれぞれ０以上の整数であり、かつ、ｘ＋ｙの平均値は０〜１０である。）

(In the formula, R is an ethylene or propylene group, x and y are each an integer of 0 or more, and the average value of x + y is 0 to 10.)

  Diols represented by formula (B);

が挙げられる。

Is mentioned.

  Divalent acid components include benzene dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, and phthalic anhydride, or anhydrides thereof, lower alkyl esters; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, and azelaic acid. Or an anhydride or a lower alkyl ester thereof; an alkenyl succinic acid or an alkyl succinic acid such as n-dodecenyl succinic acid or n-dodecyl succinic acid, or an anhydride or a lower alkyl ester thereof; fumaric acid, maleic acid, citraconic acid, itacone Examples thereof include unsaturated dicarboxylic acids such as acids or anhydrides thereof, or lower alkyl esters;

  Moreover, it is preferable to use together the trihydric or more alcohol component and trivalent or more acid component which work as a crosslinking component.

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

  The trivalent or higher polyvalent carboxylic acid component in the present invention includes trimellitic acid, pyromellitic acid, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 2,5,7. -Naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxy Propane, tetra (methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid, empole trimer acid, and their anhydrides, lower alkyl esters;

（式中、Ｘは炭素数３以上の側鎖を１個以上有する炭素数５〜３０のアルキレン基又はアルケニレン基である。）
で表わされるテトラカルボン酸、及びこれらの無水物、又は低級アルキルエステルの如き多価カルボン酸類及びその誘導体が挙げられる。

(In the formula, X is an alkylene group or alkenylene group having 5 to 30 carbon atoms having one or more side chains having 3 or more carbon atoms.)
And polycarboxylic acids such as tetracarboxylic acids and their anhydrides or lower alkyl esters and derivatives thereof.

  The alcohol component is 40 to 60 mol%, preferably 45 to 55 mol%, and the acid component is 60 to 40 mol%, preferably 55 to 45 mol%.

  Moreover, it is preferable that the polyvalent component more than trivalence is 5-60 mol% in all the components. The polyester resin can also be obtained by a generally known condensation polymerization.

  The polyester resin preferably has an acid value of 1 to 50 mgKOH / g, preferably 1 to 40 mgKOH / g, more preferably 1 to 30 mgKOH / g.

  The toner of the present invention preferably contains a charge control agent.

  Examples of the toner that controls the negative charge include the following compounds.

  For example, organometallic complexes and chelate compounds are effective, and there are monoazo metal complexes, acetylacetone metal complexes, aromatic hydroxycarboxylic acids, and aromatic dicarboxylic acid metal complexes. Others include aromatic hydroxycarboxylic acids, aromatic mono and polycarboxylic acids and their metal salts, anhydrides, esters, and phenol derivatives such as bisphenol.

  Among these, an azo metal complex represented by the following general formula (1) is preferable.

  In particular, the central metal is preferably Fe, the substituent is preferably a halogen, an alkyl group or an anilide group, and the counter ion is preferably hydrogen, an alkali metal, ammonium or aliphatic ammonium. A mixture of complex salts having different counter ions is also preferably used.

  Alternatively, a basic organic acid metal complex represented by the following general formula (2) is also preferable as a charge control agent that imparts negative chargeability.

  In particular, Fe, Cr, Si, Zn or Al is preferred as the central metal, alkyl groups, anilide groups, aryl groups and halogens are preferred as substituents, and hydrogen, ammonium and aliphatic ammonium are preferred as counter ions.

  The following compounds are used to control the toner to be positively charged.

  Modified products with nigrosine and fatty acid metal salts; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, and onium salts such as phosphonium salts thereof. And lake pigments thereof, triphenylmethane dyes and lake pigments thereof (as rake agents, phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, ferrocyanide) Metal salts of higher fatty acids; diorganotin oxides such as dibutyltin oxide, dioctyltin oxide, dicyclohexyltin oxide; dibutyltin borate, dioctyltin borate, dicyclohexyl Such diorgano tin borate of Suzuboreto; guanidine compounds, imidazole compounds. These can be used alone or in combination of two or more. Among these, triphenylmethane compounds and quaternary ammonium salts whose counter ions are not halogen are preferably used. Moreover, general formula (3)

［式中、Ｒ₁はＨ又はＣＨ₃を示し、Ｒ₂及びＲ₃は置換または未置換のアルキル基（好ましくはＣ₁〜Ｃ₄）を示す。］
で表わされるモノマーの単重合体：前述したスチレン、アクリル酸エステル、メタクリル酸エステルの如き重合性モノマーとの共重合体を正荷電性制御剤として用いることができる。この場合これらの荷電制御剤は、結着樹脂（の全部または一部）としての作用をも有する。

[Wherein R ₁ represents H or CH ₃ , and R ₂ and R ₃ represent a substituted or unsubstituted alkyl group (preferably C _{1 to} C ₄ ). ]
Monomers of monomers represented by: A copolymer with a polymerizable monomer such as styrene, acrylic acid ester or methacrylic acid ester described above can be used as a positive charge control agent. In this case, these charge control agents also have an action as a binder resin (all or a part thereof).

  In particular, a compound represented by the following general formula (4) is preferred as the positive charge control agent of the present invention.

  As a method for incorporating the charge control agent into the toner, there are a method of adding it inside the toner particles and a method of adding it outside the toner particles. The amount of use of these charge control agents is determined by the toner production method including the type of binder resin, the presence or absence of other additives, and the dispersion method, and is not uniquely limited. Preferably, it is used in the range of 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the binder resin.

  The toner of the present invention may contain a wax. The waxes used in the present invention include the following. For example, paraffin wax and derivatives thereof, montan wax and derivatives thereof, microcrystalline wax and derivatives thereof, Fischer-Tropsch wax and derivatives thereof, polyolefin wax and derivatives thereof, carnauba wax and derivatives thereof, and the like. Derivatives include oxides, block copolymers with vinyl monomers, and graft modified products.

  In the toner of the present invention, the total content of these waxes is 0.1 to 15 parts by mass, preferably 0.5 to 12 parts by mass with respect to 100 parts by mass of the binder resin. It is.

  These waxes have a melting point of 65 ° C. or higher and lower than 130 ° C., preferably 70 ° or higher and lower than 120 ° C., more preferably 70 ° C. or higher and lower than 110 ° C., more preferably measured using a differential thermal analyzer (DSC). It is preferable that it is 75 degreeC or more and less than 100 degreeC. The wax having such a melting point in the toner particles has an appropriate hardness, and toner particles having a desired surface roughness and particle size distribution can be effectively obtained in the toner particle surface modification step. . When the melting point of the wax is less than 65 degrees, the storage stability of the toner may be deteriorated. When the melting point of the wax exceeds 130 ° C., the toner particles become too hard and the productivity of the surface-modified toner may deteriorate.

In the present invention, the melting point of the wax is determined by the following method.
Sample: 0.5-2 mg, preferably 1 mg
Measurement method: Place the sample in an aluminum pan, and use an empty aluminum pan as a reference.
Temperature curve: Temperature increase I (20 ° C. to 180 ° C., temperature increase rate 10 ° C./min)
Temperature drop I (180 ° C. to 10 ° C., temperature drop rate 10 ° C./min)
Temperature increase II (10 ° C to 180 ° C, temperature increase rate 10 ° C / min)

  The endothermic peak temperature measured at the temperature elevation II in the temperature curve is defined as the melting point.

  The toner of the present invention contains a magnetic material. The magnetic material can also serve as a colorant. Magnetic materials used in the toner include iron oxides such as magnetite, hematite, and ferrite; metals such as iron, cobalt, and nickel or these metals and aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, Examples include alloys with metals such as beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium, and mixtures thereof.

These magnetic materials preferably have a number average particle diameter of 0.05 to 1.0 μm, more preferably 0.1 to 0.5 μm. A magnetic substance having a BET specific surface area of ² to 40 m ² / g (more preferably 4 to 20 m ² / g) is preferably used. There is no restriction | limiting in particular in a shape, The thing of arbitrary shapes is used. As magnetic characteristics, a saturation magnetization is 10 to 200 Am ² / kg (more preferably 70 to 100 Am ² / kg) under a magnetic field of 795.8 kA / m, and a residual magnetization is 1 to 100 Am ² / kg (more preferably ² to 20 Am). ² / kg) and a coercive force of 1 to 30 kA / m (more preferably 2 to 15 kA / m) are preferably used. These magnetic materials are used in an amount of 20 to 200 parts by mass with respect to 100 parts by mass of the binder resin. Preferably it is used at 40 to 150 parts by mass.

  The number average diameter can be obtained by measuring a photograph taken with a transmission electron microscope or the like with a digitizer or the like. The magnetic properties of the magnetic material can be measured under an external magnetic field of 795.8 kA / m using a “vibrating sample magnetometer VSM-3S-15” (manufactured by Toei Kogyo Co., Ltd.). The specific surface area can be calculated by using the BET multipoint method by adsorbing nitrogen gas to the sample surface using a specific surface area measuring device Auto Soap 1 (manufactured by Yuasa Ionics Co., Ltd.) according to the BET method.

  Other colorants that can be used in the toner of the present invention include any suitable pigment or dye. Examples of the pigment include carbon black, aniline black, acetylene black, naphthol yellow, Hansa yellow, rhodamine lake, alizarin lake, Bengala, phthalocyanine blue, and indanthrene blue. These are used in an amount necessary and sufficient to maintain the optical density of the fixed image, and an addition amount of 0.1 to 20 parts by mass, preferably 0.2 to 10 parts by mass is good with respect to 100 parts by mass of the binder resin. . Examples of the dye include azo dyes, anthraquinone dyes, xanthene dyes, and methine dyes. The addition amount of the dye is 0.1 to 20 parts by mass, preferably 0.3 to 10 parts by mass with respect to 100 parts by mass of the binder resin.

  The toner particles of the present invention are preferably externally added with inorganic fine powder or hydrophobic inorganic fine powder. For example, silica fine powder, titanium oxide fine powder, or a hydrophobized product thereof can be used. They are preferably used alone or in combination.

  Examples of the silica fine powder include both a dry process produced by vapor phase oxidation of a silicon halogen compound or dry silica called fumed silica, and wet silica produced from water glass or the like. Dry silica with fewer silanol groups on the surface and inside and no production residue is preferred.

  Further, the silica fine powder is preferably hydrophobized. The hydrophobizing treatment is applied by chemically treating with an organosilicon compound that reacts or physically adsorbs with silica fine powder. Preferable methods include a method in which a dry silica fine powder produced by vapor phase oxidation of a silicon halogen compound is treated with a silane compound or with a silane compound and simultaneously with an organosilicon compound such as silicone oil.

  The silane compounds used for the hydrophobization treatment include hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethyl. Chlorosilane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilane mercaptan, trimethylsilyl mercaptan, triorganosilyl acrylate, vinyldimethylacetoxysilane, dimethylethoxysilane , Dimethyldimethoxysilane, diphenyldiethoxysilane, hexamethyldisiloxane, 1,3-divinyltetramethyldi Examples thereof include siloxane and 1,3-diphenyltetramethyldisiloxane.

Examples of the organosilicon compound include silicone oil. As a preferable silicone oil, one having a viscosity at 25 ° C. of about 30 to 1,000 mm ² / s is used. For example, dimethyl silicone oil, methylphenyl silicone oil, α-methylstyrene modified silicone oil, chlorophenyl silicone oil, and fluorine modified silicone oil are preferred.

  Silicone oil treatment can be performed by directly mixing silica powder treated with a silane compound and silicone oil using a mixer such as a Henschel mixer, or spraying silicone oil onto the base silica. It may be by the method. Alternatively, the silicone oil may be dissolved or dispersed in an appropriate solvent, and then mixed with the base silica fine powder to remove the solvent.

  As a preferable hydrophobizing treatment of the silica fine powder, there is a method of preparing by treating with hexamethyldisilazane and then treating with silicone oil.

Treat silica fine powder with a silane compound as described above, then oil-treat later
Is preferable because it can effectively increase the degree of hydrophobicity.

  The silica fine powder is preferably subjected to a hydrophobization treatment, and further, an oil treatment applied to the titanium oxide fine powder, similarly to the silica-based one.

  To the toner particles of the present invention, additives other than silica fine powder or titanium oxide fine powder may be externally added as necessary.

  Examples thereof include resin fine particles and inorganic fine particles that act as charging aids, conductivity imparting agents, fluidity imparting agents, anti-caking agents, mold release agents at the time of hot roll fixing, lubricants, and abrasives.

  The fine resin particles preferably have an average particle size of 0.03 to 1.0 μm. As the polymerizable monomer constituting the resin, styrene; o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-ethylstyrene derivatives; acrylic acid; methacrylic acid; methyl acrylate , Ethyl acrylate, n-butyl acrylate, isobutyl acrylate, n-propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate Acrylic acid esters such as: methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, Lil, phenyl methacrylate, dimethylaminoethyl methacrylate, such as methacrylic acid esters of diethylaminoethyl methacrylate; acrylonitrile, methacrylonitrile, and the like monomers acrylamide.

  Examples of the polymerization method include suspension polymerization, emulsion polymerization, and soap-free polymerization. More preferably, particles obtained by soap-free polymerization are good.

  Other fine particles include lubricants such as polyethylene fluoride, zinc stearate, and polyvinylidene fluoride (polyvinylidene fluoride is preferred); abrasives such as cerium oxide, silicon carbide, and strontium titanate (especially strontium titanate). Preferred); fluidity-imparting agents such as titanium oxide and aluminum oxide (especially hydrophobic ones are preferred); anti-caking agents; conductivity-imparting agents such as carbon black, zinc oxide, antimony oxide and tin oxide. . Further, a small amount of white fine particles and black fine particles having a polarity opposite to that of the toner may be used as a developability improver.

  The resin fine particles, inorganic fine powder or hydrophobic inorganic fine powder mixed with the toner is preferably used in an amount of 0.01 to 5 parts by mass (preferably 0.01 to 3 parts by mass) with respect to 100 parts by mass of the toner. The toner of the present invention preferably exhibits a sufficient effect when the weight average particle diameter is 2.5 to 10.0 μm, preferably 5.0 to 9.0 μm, more preferably 6.0 to 8.0 μm. And preferred.

  The weight average particle diameter and particle size distribution of the toner are determined using a Coulter counter method. For example, a Coulter Multisizer (manufactured by Coulter Inc.) can be used. As the electrolytic solution, a 1% NaCl aqueous solution is prepared using primary sodium chloride. For example, ISOTON R-II (manufactured by Coulter Scientific Japan) can be used. As a measurement method, 0.1 to 5 ml of a surfactant (preferably alkylbenzene sulfonate) is added as a dispersant to 100 to 150 ml of the electrolytic aqueous solution, and 2 to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the volume and number of toner particles of 2.00 μm or more are measured using the 100 μm aperture as the aperture by the measuring device. Volume distribution and number distribution are calculated. Then, the weight-based weight average particle diameter (D4) obtained from the volume distribution according to the present invention is calculated. 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; Use 13 channels less than 40 μm; 25.40 to less than 32.00 μm; 32.00 to less than 40.30 μm.

  The toner of the present invention can be used as a two-component developer in combination with a carrier. As the carrier for use in the two-component development method, a conventionally known carrier can be used. Specifically, particles having an average particle diameter of 20 to 300 μm formed of surface oxidized or unoxidized metal such as iron, nickel, cobalt, manganese, chromium, rare earth, and alloys or oxides thereof are used as carrier particles. The The surface of the carrier particles is preferably coated with a substance such as styrene resin, acrylic resin, silicone resin, fluorine resin, or polyester resin.

  In order to produce the toner according to the present invention, the toner constituent materials as described above are sufficiently mixed by a ball mill or other mixer, and then kneaded well using a heat kneader such as a hot roll, a kneader or an extruder, and cooled. A method in which after the solidification and coarse pulverization, fine pulverization and classification, and then surface modification of the toner particles using a surface modification device is preferable. Furthermore, the toner according to the present invention can be produced by sufficiently mixing the desired additives with a mixer such as a Henschel mixer, if necessary.

  For example, as a mixer, Henschel mixer (Mitsui Mining Co., Ltd.); Super mixer (Kawata Co., Ltd.); Ribocorn (Okawara Seisakusho Co., Ltd.); Nauter mixer, Turbulizer, Cyclomix (Hosokawa Micron Co., Ltd.); Spiral pin mixer (Manufactured by Taiheiyo Kiko Co., Ltd.); Ladige mixer (manufactured by Matsubo Co., Ltd.), and kneaders: KRC kneader (manufactured by Kurimoto Iron Works Co.); bus co kneader (manufactured by Buss); (Manufactured by Toshiba Machine Co., Ltd.); TEX twin-screw kneader (manufactured by Nippon Steel Works); PCM kneader (manufactured by Ikegai Iron Works Co., Ltd.); Mining company); MS pressure kneader, Nider Ruder (Moriyama Seisakusho); Banbury mixer (Kobe Steel) It is below.

  As a fine pulverizer after kneading, cooling and solidifying and then coarsely pulverizing, a counter jet mill, a micron jet, an inomizer (manufactured by Hosokawa Micron); an IDS type mill, a PJM jet pulverizer (manufactured by Nippon Pneumatic Industrial Co., Ltd.) Cross jet mill (manufactured by Kurimoto Iron Works); Urmax (manufactured by Nisso Engineering Co., Ltd.); SK Jet Oh Mill (manufactured by Seishin Enterprise Co., Ltd.); Cryptron (manufactured by Kawasaki Heavy Industries, Ltd.); ); Super rotor (manufactured by Nisshin Engineering Co., Ltd.).

Classifiers include: Classy, Micron Classifier, Spedick Classifier (manufactured by Seishin Enterprise); Turbo Classifier (manufactured by Nisshin Engineering); Micron Separator, Turbo Flex (ATP), TSP Separator (manufactured by Hosokawa Micron) An elbow jet (manufactured by Nippon Steel & Mining Co., Ltd.), a dispersion separator (manufactured by Nippon Pneumatic Industrial Co., Ltd.);
Ultrasonic (Made by Sakae Sangyo Co., Ltd.); Resona sieve, Gyroshifter (Deoksugaku Kojo Co., Ltd.); Vibrasonic system (Made by Dalton); Soniclean (Shinto) (Industry company); Turbo screener (Turbo industry company); Micro shifter (Ogino industry company); Circular vibration sieve, etc.

  Hereinafter, the present invention will be described with reference to specific examples, but the present invention is not limited thereto.

  Table 1 shows the binder resin used, Table 2 shows the magnetic material, and Table 3 shows the wax.

[Preparation of Toner 1]
-Binder resin 1 100 parts by mass-Magnetic substance 1 95 parts by mass-Monoazo iron complex 2 parts by mass-Wax 1 4 parts by mass After the above mixture was premixed with a Henschel mixer, it was melted with a biaxial extruder heated to 110 ° C. The kneaded and cooled kneaded product was coarsely pulverized with a hammer mill to obtain a coarsely pulverized toner product. The obtained coarsely pulverized product was coated with a mechanical pulverizer turbo mill (manufactured by Turbo Kogyo Co., Ltd .; coated with chromium alloy plating containing chromium carbide on the rotor and stator surfaces (plating thickness 150 μm, surface hardness HV1050)). Then, based on the condition table of Table 4-1, the air temperature at the inlet and outlet is adjusted and mechanically pulverized to finely pulverize, and the resulting finely pulverized product is divided into multi-division classifiers utilizing the Coanda effect (Nitterite ore). The fine powder and coarse powder were simultaneously classified and removed by an elbow jet classifier manufactured by Sangyo Co., Ltd. The weight average particle diameter (D ₄ ) measured by the Coulter counter method of the obtained raw material toner particles was 6.6 μm, and the cumulative value of the number average distribution of toner particles of less than 4 μm was 25.2%.

The raw toner particles were subjected to surface modification and fine powder removal using a surface modification device faculty (manufactured by Hosokawa Micron). At that time, the rotational peripheral speed of the dispersion rotor is 140 m / sec, the amount of finely pulverized product is 300 kg, and the surface modification time (= cycle time, the time from the end of the raw material supply until the discharge valve opens) 45 sec. The temperature when discharging the toner particles was 30 ° C. Through the above steps, the negatively chargeable toner particles 1 having a cumulative value of the number average distribution of toner particles having a weight average particle diameter (D ₄ ) of 6.8 μm and less than 4 μm measured by the Coulter counter method of 18.1% are obtained. Obtained. Table 5 shows the methanol concentration value and the scanning probe microscope measurement value of the toner particle 1 with respect to the transmittance of light having a wavelength of 780 nm.

100 parts by weight of the toner particles and 1.2 parts by weight of hydrophobic silica fine powder treated with hexamethyldisilazane and then treated with dimethylsilicone oil were mixed with a Henschel mixer to prepare negatively charged toner 1. .
The average surface roughness of the toner 1 measured with a scanning probe microscope was 19.1 nm.

[Preparation of Toners 2 to 4]
The binder resin, magnetic material, and wax to be used are changed as shown in Table 4-1, and the fine grinding conditions of the turbo mill are changed as shown in Table 4-1, the classification conditions in the multi-division classifier are changed, and Toners 2 to 4 were obtained in the same manner as in Toner 1 except that the conditions of the surface modification device Faculty (manufactured by Hosokawa Micron Corporation) were as shown in Table 4-1. Table 5 shows the methanol concentration value and the scanning probe microscope measurement value of the toner particles 2 to 4 with respect to the transmittance of light having a wavelength of 780 nm.

[Preparation of Toner 5]
The binder resin, magnetic material, and wax to be used are changed as shown in Table 4-1, and the fine grinding conditions of the turbo mill are changed as shown in Table 4-1, the classification conditions in the multi-division classifier are changed, and A toner 5 was obtained in the same manner as the toner 1 except that the surface modification by the surface modification apparatus was not performed. Table 5 shows the methanol concentration value and the scanning probe microscope measurement value of the toner particles 5 with respect to the transmittance of light having a wavelength of 780 nm.

[Preparation of Toner 6]
The binder resin, magnetic material, and wax to be used are changed as shown in Table 4-2, and the finely pulverizing conditions of the turbo mill are changed as shown in Table 4-2, and the classification conditions in the multi-division classifier are changed. Surface modification was performed with a reformer hybridizer (manufactured by Nara Machinery Co., Ltd.). The discharged toner particles were repeatedly processed once for a processing time of 5 minutes, and the processing was performed 5 times in total for 5 minutes. Through the above steps, the weight average particle diameter (D ₄ ) measured by the Coulter counter method. The negatively chargeable toner particles 6 having a cumulative value of 16.1% of the number average distribution of toner particles of 7.0 μm and less than 4 μm were obtained. Table 5 shows the methanol concentration value and the scanning probe microscope measurement value of the toner particles 7 with respect to the transmittance of light having a wavelength of 780 nm.

  The average surface roughness of the toner 6 measured with a scanning probe microscope was 7.4 nm.

[Preparation of Toner 7]
The binder resin, magnetic material, and wax to be used are changed as shown in Table 4-2, and the pulverization conditions of the turbo mill are changed as shown in Table 4-2, and the classification conditions in the multi-division classifier are changed. Toner 7 was obtained in the same manner as toner 6 except that the conditions of the surface reformer hybridizer (manufactured by Nara Machinery Co., Ltd.) were as shown in Table 4-2. Table 5 shows the methanol concentration value and the scanning probe microscope measurement value of the toner particles 7 with respect to the transmittance of light having a wavelength of 780 nm.

[Preparation of Toner 8]
The binder resin, magnetic substance, and wax used are as shown in Table 4-3, and a multi-division classifier is used by using an IDS type mill (manufactured by Nippon Pneumatic Kogyo Co., Ltd.) without using a mechanical pulverizer. The toner 8 was obtained in the same manner as the toner 1 except that the classification conditions were changed and the surface modification by the surface modification device was not performed. Table 5 shows the methanol concentration value and the scanning probe microscope measurement value of the toner particles 8 with respect to the transmittance of light having a wavelength of 780 nm.

  Table 6 shows the properties of the toner regulating blade used.

[Toner regulating blade manufacturing method]
(Toner regulating blade manufacturing method 1)
While the centrifugal mold heated to 140 ° C. is rotated at a rotation speed of 800 rpm, a thermosetting resin liquid (epoxy resin heat-resistant temperature 150 ° C.) is poured into the centrifugal mold and sufficiently cured by heating. Thus, a holding layer (eccentricity compensation layer) having a thickness of 1.0 mm was provided. Next, in the process of forming a release layer of silicone rubber to a thickness of 2.0 mm on the inner peripheral surface of the holding layer, the inner peripheral surface is in toluene before the release layer is completely cured. The surface-roughening agent (graphite fluoride weight average particle size 8.0 μm, standard deviation 1.53) dispersed in was sprayed. The urethane forming liquid is poured into the release layer formed as described above, Rz = 10.2 μm, Sm = 35.1, and the glass plate is brought into contact with the surface pressure of 14.4 Pa. A toner regulating blade 1 having an area ratio of 0.40 was obtained. This toner regulating blade had a rubber hardness of 65 ° and a thickness of 1.17 mm. The toner regulating blade 1 thus obtained was press-cut to a desired size, and the toner regulating blade 1 bonded to a metal toner regulating blade support member with an adhesive was used for evaluation.

(Toner regulating blade manufacturing method 2)
A toner regulating blade 2 was obtained in the same manner as in the toner regulating blade manufacturing method 1 except that graphite fluoride having an average particle diameter of 15.2 μm and a standard deviation of 5.23 was used.

(Toner regulating blade manufacturing method 3)
The inner peripheral surface of the centrifugal mold was blasted by spraying # 60 glass bead particles with an air pressure of 4.5 kg / cm ² . When the urethane forming liquid is poured into the centrifugal mold, Rz is 24.5 μm, Sm is 120.3, and the glass plate is brought into contact with the surface pressure of 14.4 Pa, the area ratio of the entire contact portion is A toner regulating blade 3 of 0.27 was obtained. This toner regulating blade had a rubber hardness of 65 ° and a thickness of 1.17 mm. The toner regulating blade 3 obtained as described above was press-cut to a desired size, and the toner regulating blade 3 bonded to a metal toner regulating blade support member with an adhesive was used for evaluation.

(Toner regulating blade manufacturing method 4)
Except for spraying fluorinated graphite having an average particle size of 15.2 μm and a standard deviation of 5.23 and then spraying fluorinated graphite having an average particle size of 4.1 μm and a standard deviation of 1.35, the same as in the toner regulating blade manufacturing method 1 Thus, a toner regulating blade 4 was obtained.

(Toner regulating blade manufacturing method 5)
A toner regulating blade 5 was obtained in the same manner as in the toner regulating blade manufacturing method 1 except that fluorinated graphite having an average particle size of 4.1 μm and a standard deviation of 1.35 was used.

(Toner regulating blade manufacturing method 6)
A toner regulating blade 6 was obtained in the same manner as in the toner regulating blade manufacturing method 5 except that the amount of the roughening treatment agent applied was reduced.

(Toner regulating blade manufacturing method 7)
A toner regulating blade 7 was obtained in the same manner as in the toner regulating blade manufacturing method 3 except that the amount of glass bead particles sprayed was less than that of the toner regulating blade manufacturing method 3.

(Toner regulating blade manufacturing method 8)
The toner control blade is the same as the toner control blade manufacturing method 7 except that the glass bead particles of # 180 are used, the spraying amount is smaller than that of the toner control blade manufacturing method 7, and the obtained toner control blade is cured. 8 was obtained.

[Examples 1-7, Comparative Examples 1-3]
Next, the prepared toner was used for evaluation by the following method.

  A laser beam printer Laser Jet4350n manufactured by Hewlett-Packard Co. was modified to obtain A4 size 60 sheets / minute (process speed 380 mm / sec), and the following evaluation was performed. Table 7 shows the evaluation results.

(1) Image density, fog Under normal temperature and humidity (23 ° C., 60% RH), 2 sheets / 10 seconds printing speed, 5% printing ratio (A4 size: 75g / m ² ) was subjected to an image print test of 9000 sheets, and left for a day to perform image print tests of 9000 sheets again, for a total of 18000 sheets, and the image density and fog at 18000 sheets were measured. The results are shown in Table 7.

  For the image density, a “Macbeth reflection densitometer” (manufactured by Macbeth) was used to measure a relative density with respect to a printout image of a white background portion having an original density of 0.00.

  The fog was calculated from a comparison between the whiteness of the transfer paper measured by a reflectometer (manufactured by Tokyo Denshoku Co., Ltd.) and the whiteness of the transfer paper after printing solid white.

(2) Dot reproducibility The dot reproducibility is a printout of the 80 μm × 50 μm checker pattern shown in FIG. 5 in a normal temperature and humidity environment (23 ° C., 60% RH). Observed and evaluated. The results are shown in Table 7.
A: 2 or less defects in 100 B: 3 to 5 defects in 100 C: 6 to 10 defects in 100 D: 11 or less defects in 100

(3) Spattering Durability in a normal temperature and humidity environment (23 ° C, 60% RH), a grid pattern (1 cm interval) on a 100 µm (latent image) line is printed on 18,000 sheets, and the scattering is measured using an optical microscope. And visually evaluated. The results are shown in Table 7.
A: The line is very sharp and hardly splattered. B: The line is comparatively sharp with a slight splattering. C: Slightly splattering makes the line feel dull. D: Less than C level

(4) Vertical stripes Halftones were printed out in an environment of normal temperature and humidity (23 ° C., 60% RH), the number of vertical stripes in the sample was counted, and ranked as follows. The results are shown in Table 7.
A: No occurrence B: 1 to 3 vertical stripes C: 4 or more vertical stripes

It is a state where the contact part and the non-contact part when the toner regulating blade and the glass plate are brought into contact are binarized. A contact part (black) and a non-contact part (white). In this method, the toner regulating blade is roughened using a die blasted with roughened particles. In this method, the toner regulating blade is roughened by using a mold layer on which a release layer containing a roughening treatment agent is formed. It is the graph which showed the transmittance | permeability with respect to methanol concentration. It is explanatory drawing of the checker pattern used for dot reproducibility evaluation.

Claims (4)

An image forming method in which the toner layer thickness on the toner carrier is regulated by a toner regulating blade, and the electrostatic latent image carrier is developed with the toner on the toner carrier,
The ten-point average roughness Rz measured with a laser microscope on the surface of the toner regulating blade in contact with the toner carrying member is 5.0 μm or more and 25.0 μm or less, and the toner of the toner regulating blade The ratio of the area of the contact part and the area of the non-contact part when the part in contact with the carrier is brought into contact with the glass plate at a surface pressure of 14.4 Pa is 27/73 to 70/30 ,
The toner is a toner containing toner particles containing at least a binder resin and a magnetic material and inorganic fine particles, and the average surface roughness of the toner particles measured by a scanning probe microscope is 5.0 nm or more and 60 nm. An image forming method, wherein the image forming method is 0.0 nm or less. According to claim 1, wherein the average interval Sm of irregularities to be measured with a laser microscope side surface to be in contact with the said toner carrying member of said toner regulating blade is equal to or less than 200.0μm than 5.0μm Image forming method. A process cartridge that regulates a toner layer thickness on a toner carrier by a toner regulating blade and develops the electrostatic latent image carrier with toner on the toner carrier;
The ten-point average roughness Rz measured with a laser microscope on the surface of the toner regulating blade in contact with the toner carrying member is 5.0 μm or more and 25.0 μm or less, and the toner of the toner regulating blade The ratio of the area of the contact part and the area of the non-contact part when the part in contact with the carrier is brought into contact with the glass plate at a surface pressure of 14.4 Pa is 27/73 to 70/30 ,
The toner is a toner containing toner particles containing at least a binder resin and a magnetic material and inorganic fine particles, and the average surface roughness of the toner particles measured by a scanning probe microscope is 5.0 nm or more and 60 nm. A process cartridge having a thickness of 0.0 nm or less. According to claim 3, mean spacing Sm of asperities as measured by a laser microscope side surface to be in contact with the said toner carrying member of said toner regulating blade is equal to or less than 200.0μm than 5.0μm Process cartridge.

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