JP4819646B2 - Non-magnetic toner - Google Patents

Description

  The present invention relates to a toner used in a recording method using an electrophotographic method, an electrostatic recording method, an electrostatic printing method, or the like.

In recent years, electrophotographic devices such as printer devices have
(1) High definition and high image quality (2) Development of a machine capable of high-speed printing and low running cost while achieving energy saving more than ever is strongly desired.

  Along with this, the properties required for toners are becoming increasingly high and diverse, and developments are being made from various viewpoints.

  From the viewpoint of high definition and high image quality, the direction of finer particles is desired as the toner as the resolution of machines such as 1200 and 2400 dpi increases. As one of the manufacturing methods, a toner manufacturing method by a polymerization method has been proposed. This polymerization method toner includes a method for preparing a toner (emulsion association (aggregation) type toner) obtained by agglomerating and fusing emulsion-aggregated (aggregated) resin particles and colorant particles, and radical polymerization. There is a method of preparing toner particles (suspension polymerization toner) through a step of dispersing a monomer and a colorant, then dispersing the droplets in an aqueous medium or the like so as to obtain a desired toner particle size, and suspension polymerization. (For example, see Patent Documents 1, 2, and 3.)

  In particular, the toner particles produced by applying the suspension polymerization method are not only easy to make fine particles, but also have a sharp particle size distribution, high sphericity, and substantially uniform surface material. Therefore, particles having uniform triboelectric chargeability can be obtained. As a result, a toner having high developability and high transferability can be obtained and is preferably used. In addition, as described above, since the sharp particle size distribution is obtained, the classification process can be simplified. Therefore, cost saving effects such as energy saving, shortening of manufacturing time and improvement of process yield are great, which is desirable from the viewpoint of low running cost.

  Furthermore, colorization is rapidly progressing in the field of electrophotography. In general, a color image is formed by appropriately overlapping and developing four color toners of yellow, magenta, cyan, and black, and therefore, each color toner is required to have higher development characteristics than a single color toner. That is, there is a need for a toner capable of faithfully developing an electrostatic charge image, reliably transferred to a transfer material without scattering, and easily fixed to a transfer material such as paper. The toner produced by law is suitably used also from such a viewpoint.

  From the viewpoint of energy saving, it is desired to develop a toner that can be easily fixed on a transfer material such as paper at a low temperature. At the same time, as the resolution of the image increases, the glossiness of the image must be controlled and, in the case of a color machine, good color mixing and a wide range of color reproducibility are required in order to approach the image quality of photographs and prints. ing. For example, it is required to obtain an image having a high gloss level close to a photographic quality.

  Therefore, it is necessary to lower the glass transition point (Tg) of the toner binder and to lower the average molecular weight of the toner binder. However, if the Tg and average molecular weight of the toner binder are simply lowered, in an extreme case, the storage stability of the toner is impaired and an image cannot be obtained. In particular, in the case of a non-magnetic one-component developing method that is suitably used for a printer that is required to be downsized due to needs such as SOHO while achieving low running cost while developing at a high speed. Due to the decrease in strength, the toner is liable to be crushed, and the member is likely to be contaminated due to toner fusion or wax exudation. As a result, the target of long life and low running cost may not be achieved, and there is a limit to lowering the Tg of the toner binder.

  Various proposals have been made in order to achieve both seemingly contradictory performance such as development stability and high-speed and low-temperature fixability of the toner, and a method for obtaining storage stability by increasing the Tg of the low molecular weight component of the toner binder. Has been proposed (see, for example, Patent Document 4).

However, in the toner manufactured by the pulverization method, a part of the internally added wax comes out on the surface of the toner. Therefore, when it is used in the one-component developing method as described above, there is a problem in the charge rising property of the toner. In some cases, image defects such as a decrease in density, fogging, and image streaks are likely to occur when copying many sheets.
On the other hand, as described above, the polymerization toner preferably used for easily achieving fine particles for the purpose of high definition and high image quality is superior to the pulverization toner in terms of the encapsulation of the wax, and is relatively one component. Although the image stability in the development system is excellent, it is difficult to freely control the molecular weight distribution, so various ideas are required.

  As a means of achieving low temperature fixability while controlling the molecular weight of the binder resin, a vinyl-based low molecular weight polymer is added in advance to the polymerizable monomer, and the monomer composition is granulated in the presence of the polymer. A method for producing a toner by polymerization has been proposed (see, for example, Patent Document 5).

  This improves the low-temperature fixability and storage stability, and improves the development stability to some extent because the wax is more easily encapsulated than the pulverization method, but it has a sufficiently satisfactory glossiness because it uses more crosslinking agent. It can be seen that is not obtained. It is difficult to add a large amount of the high-melting-point wax used in the patent due to the production method, and thus the molecular weight of the binder cannot be sufficiently lowered to ensure offset resistance.

  There has been proposed a technique in which high molecular weight components are reduced to improve glossiness and a large amount of wax ensures offset resistance (for example, see Patent Document 6). According to this, offset resistance is improved by adding a large amount of low melting point ester wax or paraffin wax, and furthermore, by forming a core-shell structure of wax and binder, low temperature fixability, offset resistance and component contamination resistance Is to achieve both. However, as a high-speed developing toner, the charge rising of the toner itself and the toner strength are insufficient.

  In order to improve the development durability, it is necessary to reduce the stress received by the toner in the developing device. However, the rotating blades enter the toner powder phase while rotating, and the rotating blades move in the powder phase. There has been proposed a toner in which the torque or load generated at the time of measurement is measured and the torque value or the load value is controlled within a certain range (see, for example, Patent Document 7). However, this patent aims to improve dot reproducibility from the viewpoint of high image quality, and is insufficient to satisfy high-speed development stability and low-temperature fixability.

  As described above, the required characteristics of the toner are, in particular, high-resolution and high-definition images with fine-particle toners, while achieving both long-term durability stability at high speed and low-temperature fixability, and the gloss of fixed images. In order to satisfy all the demands in a well-balanced manner, such as ensuring sufficient image density and ensuring toner storage stability, the techniques proposed so far are insufficient and there is still room for improvement.

Japanese Patent Publication No. 36-10231 Japanese Examined Patent Publication No. 47-518305 Japanese Patent Publication No. 51-14895 Japanese Patent No. 2630972 Japanese Patent No. 2769870 Japanese Patent No. 3428774 JP 2004-37651 A

The present invention is to solve the above-mentioned problems of the prior art.
(1) That is, an object of the present invention is to provide a fine particle toner capable of obtaining a high resolution and high definition image.
(2) Further, the object of the present invention is to achieve the object of (1) above, having excellent low-temperature fixability, and having an appropriate glossiness and image density necessary to approximate the image quality of photographs and printing. It is to provide a toner capable of obtaining an image.
(3) Furthermore, an object of the present invention is to provide a toner having excellent durability that does not contaminate a member even in image printing under any environment while achieving the object (1).
(4) Furthermore, an object of the present invention is to provide a toner having a uniform charge amount and charge amount distribution, which has a quick rise, and high development and transferability.
(5) Furthermore, an object of the present invention is to provide a toner having excellent storage stability that does not block even when left at high temperatures.
(6) Furthermore, an object of the present invention is to provide a one-component developer capable of achieving the objects (1) to (5).

  As a result of intensive studies, the present inventors have found that the following problems can be solved by the following configuration, and have completed the present invention.

That is, the present invention is as follows.
(1) In a non-magnetic toner having toner particles and inorganic fine powder containing at least a resin, a colorant, and a release agent, the viscosity at 100 ° C. (Pa · s) by a flow tester is
15000 ≦ 100 ° C. viscosity (Pa · s) ≦ 45000
A nonmagnetic toner characterized by satisfying the following relational expressions (1) and (2):
0 ≦ Et100 (mJ) ≦ 500 (1)
1.00 ≦ Et10 / Et100 ≦ 1.60 (2)
[However, Et100 (mJ) is allowed to vertically enter the toner powder layer in the container while rotating the peripheral speed of the outermost edge of the propeller blade at 100 mm / sec, and 100 mm from the bottom surface of the toner powder layer. This represents the sum of the rotational torque and the vertical load obtained when starting measurement from the position and entering the position 10 mm from the bottom, and Et10 (mJ) represents the rotational torque when rotated at 10 mm / sec. Represents the total vertical load. ]
(2) The nonmagnetic toner according to (1), wherein the toner satisfies the following relational expressions (3) and (4).
150 ≦ Et100 (mJ) ≦ 470 (3)
1.20 ≦ Et10 / Et100 ≦ 1.60 (4)
(3) The toner has an average particle diameter and an average circle of particles having an equivalent circle diameter of 2 μm or more and a circularity of 0.70 or more in a scattergram based on the number of circles measured by a flow type particle image measuring apparatus. The degree meets the following range,
4.00 ≦ average particle size (μm) ≦ 6.30
0.950 ≦ average circularity ≦ 0.990
The nonmagnetic toner according to any one of (1) and (2), wherein the 10% particle diameter and the 90% particle diameter satisfy the following relational expression (5).
1.20 ≦ 90% particle size / 10% particle size ≦ 2.00 (5)
(4) The toner has an equivalent circle diameter of 0.60 μm or more and 1.00 μm with respect to the total number of particles having a circularity of 0.70 or more in a scattergram based on the number of circles measured by a flow type particle image measuring apparatus. The non-magnetic toner according to any one of (1) to (3), wherein the abundance A (number%) of toner particles less than 1 satisfies the following range.
0.10 ≦ A (%) ≦ 8.00
(5) The nonmagnetic toner according to any one of (1) to (4), wherein the A (number%) satisfies the following range.
0.10 ≦ A (%) ≦ 5.00
( 6 ) The nonmagnetic toner according to any one of (1) to ( 5 ), wherein the toner is toner particles produced in an aqueous medium.
( 7 ) The nonmagnetic toner according to any one of (1) to ( 6 ), wherein the toner is toner particles produced by suspension polymerization.
( 8 ) The nonmagnetic toner according to any one of (1) to ( 7 ), wherein the toner is a one-component developer.

  According to the present invention, there is an effect that stress that can be imparted to the toner is reduced and long-term durability is excellent while achieving low-temperature fixability.

  Hereinafter, the present invention will be described in detail with reference to embodiments of the present invention.

The toner of the present invention is a non-magnetic toner having toner particles containing at least a resin, a colorant, a release agent and an inorganic fine powder, and has a viscosity (Pa · s) of 100 ° C. by a flow tester.
15000 ≦ 100 ° C. viscosity (Pa · s) ≦ 45000
The main characteristic is that the toner is a non-magnetic toner satisfying the following relational expressions (1) and (2).
0 ≦ Et100 (mJ) ≦ 500 (1)
1.00 ≦ Et10 / Et100 ≦ 1.60 (2)
[However, Et100 (mJ) is allowed to enter the toner powder layer in the container while rotating the propeller blade counterclockwise at 100 (mm / sec), from a position 100 mm from the bottom of the toner powder layer. Represents the total Et of rotational torque and vertical load obtained when measurement is started and entered to a position 10 mm from the bottom. Et10 (mJ) is the rotation when rotated at 10 (mm / sec) It represents the total Et of torque and vertical load. ]

  As a result of intensive studies, the present inventors have found that the relational expressions (1) and (2) have a high correlation with the stress applied to the toner in the developing device, and thus have a high correlation with the durability of the developer. I found out. Here, the stress that the toner receives is the stress that the toner receives immediately before supplying the toner from the toner application roller to the toner carrier and immediately before the nip portion between the toner carrier to which the toner is applied and the developing blade. Means. In other words, toner accumulation is likely to occur between the toner application roller and the toner carrying member due to the difference in peripheral speed due to the rotation of both members, and the toner coating amount between the toner carrying member and the developing blade due to toner coating amount regulation. In addition, it is considered that stress is applied to the toner due to the force applied by the rotation of the toner application roller and the toner carrier. The measured values Et100 (mJ) and Et10 (mJ) in the relational expressions (1) and (2) are obtained by measuring the energy applied when the propeller blade enters the toner powder layer. The present inventors consider that the toner powder layer corresponds to the toner reservoir, and the propeller blade corresponds to the rotation of the toner application roller and the toner carrier.

In the present invention, by controlling Et100 (mJ) to 500 or less, 100 ° C. viscosity (Pa · s) by a flow tester is
15000 ≦ 100 ° C. viscosity (Pa · s) ≦ 45000
Even in soft toners that can be fixed at low temperatures, such as reducing the stress received by the toner in the developing device, even in high-speed and long-term durable images, member contamination due to wax exudation and embedding of external additives, toner It has been found that toner deterioration such as particle collapse can be suppressed and a stable image can be obtained. In particular, in the case of a non-magnetic one-component developer, the toner coat amount is regulated immediately before the toner is supplied from the toner application roller to the toner carrier, and at the nip portion between the toner carrier to which the toner is applied and the developing blade. Immediately before the toner was collected, the toner could easily accumulate, so that the toner was easily stressed. In particular, in the latter half of the endurance, the deteriorated toner accumulated, and it was easy to cause problems such as fogging and development streaks. Therefore, it is very important to control Et100 (mJ) to 500 or less, and from the same viewpoint, Et100 (mJ) is preferably controlled to 470 or less. More preferably, it is 450 or less.

  Furthermore, Et100 (mJ) is more preferably controlled to 150 or more. As a result, it is possible to apply an appropriate stress to the toner, to charge the toner quickly, uniformly and sharply, and to prevent fogging and scattering due to poor charging.

  Et10 / Et100 is required to be 1.00 or more and 1.60 or less, and more preferably 1.20 or more and 1.60 or less. Et10 / Et100 monitors the dependency of the rotational speed on the stress applied to the toner. When this is applied to the situation in the developing device, when image is printed using gloss paper preferably used for obtaining a photographic image, or when a transparent sheet (OHT) is used, The case where the process speed drops to 1/2 speed or 1/3 speed, which is a means preferably used to achieve higher image quality, is considered to be applicable.

  By suppressing Et10 / Et100 to 1.60 or less, it is possible to reduce the stress applied to the toner even in a situation where the speed is varied, and to achieve a long life.

  On the other hand, by controlling Et10 / Et100 to 1.20 or more, even when the speed is variable, it is possible to apply an appropriate stress to the toner and to charge the toner quickly, uniformly and sharply. It has the effect of preventing fogging and scattering due to defects.

Examples of methods for controlling these Et100 and Et10 / Et100 values include the following methods (A) to (D). These methods may be performed independently, but may be achieved by combining a plurality.
(A) For example, a method of controlling toner particle size distribution by classification or the like, and suppressing the toner packing by causing appropriate fine powder and coarse powder to exist.
(B) For example, a method of increasing the average circularity of the toner and reducing the contact area between the toner particles.
(C) For example, a method in which an appropriate amount of an organic / inorganic fine particle layer treated with a treatment agent having low surface energy and high hydrophobicity is adhered to the toner surface.
(D) For example, by dispersing toner particles in an aqueous medium and flowing steam or the like, the entire system is heated to 100 ° C., thereby eliminating minute irregularities on the toner surface, thereby reducing the surface energy of the toner. Method.

<Measuring method of Et100 (mJ) and Et10 (mJ)>
Et100 (mJ) and Et10 (mJ) in the present invention are measured by using a powder fluidity analyzer, powder rheometer FT-4 (manufactured by Freeman Technology) (hereinafter sometimes abbreviated as FT-4). To do.

  Specifically, the measurement is performed by the following operation. In all operations, the propeller blade is a 48 mm diameter blade dedicated to FT-4 measurement (see FIG. 1; there is a rotation axis in the normal direction at the center of the 48 mm × 10 mm blade plate, The outer edge portion (24 mm from the rotation axis) is smoothly twisted counterclockwise such that the outer edge portion (24 mm from the rotation axis) is 70 °, and the 12 mm portion from the rotation axis is 35 °, and the material is made of SUS. May be abbreviated as blade).

  23 for a cylindrical split container (model number: C203, 82 mm in height from the bottom of the container to the split part. The material is glass. Hereinafter, it may be abbreviated as a container). A toner powder layer is formed by adding 100 g of toner left in a 60 ° C., 60% environment for 3 days or more.

(1) Conditioning operation (a) The rotation speed of the blade in the clockwise direction with respect to the powder layer surface (the direction in which the powder layer is loosened by the rotation of the blade) is the peripheral speed 60 at the outermost edge of the blade. (Mm / sec), the angle between the trajectory drawn by the outermost edge of the moving blade and the surface of the powder layer is the speed of entry into the powder layer in the vertical direction is 5 (deg). In some cases, the angle is abbreviated as “corner”), and the toner is allowed to enter from the surface of the powder layer to a position of 10 mm from the bottom surface of the toner powder layer. Then, in the clockwise rotation direction with respect to the powder layer surface, the rotation speed of the blade is 60 (mm / sec), and the angle that forms the vertical entry speed into the powder layer is 2 (deg). Then, after the operation to enter the position of 1 mm from the bottom surface of the toner powder layer, the rotation speed of the blade is 60 (mm / sec) in the clockwise rotation direction with respect to the powder layer surface. The angle forming the extraction speed from the toner is moved to a position of 100 mm from the bottom surface of the toner powder layer at a speed of 5 (deg), and extraction is performed. When the extraction is completed, the toner attached to the blade is wiped off by rotating the blade alternately in small clockwise and counterclockwise directions.

  (B) By performing the series of operations (1) to (a) five times, the air entrained in the toner powder layer is removed, and a stable toner powder layer is formed.

(2) Split operation A toner powder layer having the same volume is formed by scraping the toner powder layer at the split portion of the above-described cell dedicated to FT-4 measurement and removing the toner on the powder layer.

(3) Measurement operation (i) Measurement of Et100 (a) A conditioning operation similar to (1) to (a) above is performed once. Next, the rotational speed of the blade is 100 (mm / sec) in the counterclockwise direction (the direction in which the powder layer is pushed by the rotation of the blade), and the direction perpendicular to the powder layer is The approach speed is entered at a speed of 5 (deg) from the bottom surface of the toner powder layer to a position of 10 mm. Then, in the clockwise rotation direction with respect to the powder layer surface, the rotation speed of the blade is 60 (mm / sec), and the angle that forms the vertical entry speed into the powder layer is 2 (deg). Then, after performing the operation to enter the position of 1 mm from the bottom of the powder layer, the rotational speed of the blade is 60 (mm / sec) in the clockwise rotation direction with respect to the surface of the powder layer. Extraction is performed from the bottom surface of the powder layer to a position of 100 mm at an angle forming a vertical extraction speed of 5 (deg). When the extraction is completed, the toner attached to the blade is wiped off by rotating the blade alternately in small clockwise and counterclockwise directions.

  (B) The above-described series of operations is repeated seven times, and at the seventh time, the rotation speed of the blade is 100 (mm / sec), the measurement starts from a position 100 mm from the bottom surface of the toner powder layer, and a position 10 mm from the bottom surface. Let Et100 be the total Et of the rotational torque and the vertical load that is obtained when it is made to enter.

(Ii) Measurement of Et10 (a) Using the toner powder layer for which the measurement of Et100 has been completed, the above operations (3)-(i)-(a) are performed once.

  (B) Next, in the series of operations in (3)-(i)-(a), the blade was moved into the toner powder layer at a rotational speed of 100 (mm / sec). / Sec) for measurement.

  (C) Subsequently, the measurement was performed by sequentially reducing the rotational speed to 40 (mm / sec) and 10 (mm / sec) in the same manner as in (3)-(ii)-(b), and the rotational speed was 10 (mm / sec). sec), the measurement Et is started from the position of 100 mm from the bottom surface of the toner powder layer, and the total Et of the rotational torque and the vertical load obtained when the toner powder is moved to the position of 10 mm from the bottom surface is defined as Et10.

The toner of the present invention, a flow-type particle image measuring device "FPIA-2100 Model" was measured (manufactured by Sysmex Corporation), a circle-equivalent diameter based on the number to be measured - the equivalent circle diameter 2μm or more in the circularity scattergram The average particle size of particles having a circularity of 0.70 or more is 4.00 ≦ average particle size (μm) ≦ 6.30. In a copying machine, it is preferable for faithfully developing finer latent image dots and achieving further higher image quality. In addition, the improvement in the hiding power enables the toner consumption to be reduced, leading to a reduction in running cost.

Furthermore, although the reason is not clear, it has also been found that a toner having a finer particle diameter can reduce the value of E100 (mJ), which is an essential requirement of the present invention.

  In a toner having an average particle diameter of less than 4 μm, a large amount of toner remains on the photoreceptor due to a decrease in transfer efficiency. In such a case, when contact charging is performed, it becomes difficult to suppress the photoconductor scraping and toner fusion. Furthermore, in addition to an increase in the entire surface area of the toner, the fluidity and agitation as a powder decrease, and it becomes difficult to uniformly charge individual toner particles, so fog and transferability tend to deteriorate, This is not preferable for the toner used in the present invention because it tends to cause non-uniform image unevenness other than scraping and fusion. When the weight average particle diameter of the toner exceeds 8 μm, characters and line images are likely to be scattered, and it is difficult to obtain a high-resolution image such as fine line reproducibility and halftone roughness.

The toner of the present invention, a flow-type particle image measuring device "FPIA-2100 Model" was measured (manufactured by Sysmex Corporation), a circle-equivalent diameter based on the number to be measured - the equivalent circle diameter 2μm or more in the circularity scattergram The average circularity of particles having a circularity of 0.70 or more is preferably 0.950 ≦ average circularity ≦ 0.990.

If it is less than 0.950, the toner transferability is poor. This is considered to be because the contact area between the toner particles and the photosensitive member is large, and the adhesion force of the toner particles to the photosensitive member due to mirror image force, van der Waals force, or the like increases. As a result, the transfer efficiency is lowered, and as a result, the toner consumption is increased.

  In addition, toner particles having an average circularity of less than 0.950 have many edge portions on the surface, so that charge localization within one particle is likely to occur. It will be easy to cause.

  Moreover, although the reason is not clear, Et10 / Et100, which is an essential requirement of the present invention, tends to increase.

  On the other hand, when the average circularity exceeds 0.990, particularly when used in the non-magnetic one-component development method described later, the toner is insufficiently charged between the developer carrier and the developing blade, causing fogging. It becomes easy. It is expected that the average circularity of the toner is increased, so that the fluidity of the toner is improved and the toner passes between the developer carrying member and the developing blade. In addition, it is difficult to obtain an effect of suppressing poor cleaning of the photoreceptor.

The toner of the present invention, a flow-type particle image measuring device "FPIA-2100 Model" was measured (manufactured by Sysmex Corporation), a circle-equivalent diameter based on the number to be measured - the equivalent circle diameter 2μm or more in the circularity scattergram The value of 90% particle diameter / 10% particle diameter of particles having a circularity of 0.70 or more is preferably 1.20 ≦ 90% particle diameter / 10% particle diameter ≦ 2.00. The 90% particle size / 10% particle size is an index representing the width of the particle size distribution. The smaller the value, the sharper the particle size distribution, and the larger the value, the broader the particle size distribution. It can be said that the toner has toner.

When the 90% particle diameter / 10% particle diameter is less than 1.20, the particles are easy to pack, and it is difficult to achieve Et100 and Et10 / Et100, which are essential requirements of the present invention.

  When the 90% particle diameter / 10% particle diameter exceeds 2.00, the particles are uneven, and it is difficult to uniformly charge the particles. As a result, toners having a low charge to a high toner exist, and the high charge toner may cause fogging or scattering by reversely charging the low charge toner. Although depending on the development conditions, the toner that has remained in the second half of the endurance can not contribute to the development, and in some cases, a low density may occur due to the sequential development from the toner having the appropriate charge. .

The toner of the present invention is measured using a flow type particle image measuring device “FPIA-2100 type” (manufactured by Sysmex Corporation), and the degree of circularity is 0.70 in a number-based equivalent circle diameter -circularity scattergram. The abundance A (%) of particles having an equivalent circle diameter of 0.60 μm or more and less than 1 μm with respect to the total number of particles is preferably 0.10 ≦ A (%) ≦ 8.00, and 0.10 ≦ A ( %) ≦ 5.00.

When A (%) is less than 0.10, it becomes difficult to control Et100 and Et10 / Et100, which are essential requirements of the present invention, within a preferable range.

  When A (%) exceeds 8.00, contamination of members such as a toner carrier, a charging roller, and a developing blade is likely to occur, and image defects such as fogging, scattering, and streaks are likely to occur.

<Measurement Method of Toner Average Particle Diameter, Average Circularity, 90% Particle Diameter, 10% Particle Diameter, A (%)>
The average particle diameter, average circularity, 90% particle diameter, 10% particle diameter, and A (%) of the toner are measured using a flow type particle image measuring apparatus “FPIA-2100 type” (manufactured by Sysmex Corporation). And calculate using the following formula.

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

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

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

  As a specific measurement method, a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersant in a container, and then 0.018 g of a measurement sample is added (in the case of a toner having an average particle size of 5.7 μm). Get familiar with the surfactant. Further, 20 ml of ion-exchanged water from which impure solids are removed in advance is added and dispersed uniformly. As a means to disperse, an ultrasonic disperser “UH-50 type” (manufactured by SMT Co., Ltd.) using a 5Φ titanium alloy chip as a vibrator is used for a dispersion treatment for 5 minutes, and a measurement dispersion liquid And In that case, it cools suitably so that the temperature of this dispersion may not be 40 degreeC or more. The dispersion liquid thus adjusted is preferably adjusted so that the toner particle concentration at the time of measurement is 7000 to 12000 particles / μl, and the toner has a larger average particle diameter than the toner exemplified here. When measuring toner, it is necessary to increase the amount of sample, and when measuring small toner, it is necessary to decrease the amount of sample.

  The toner of the present invention has at least a minimum value and a maximum value, or a minimum value and an inflection point between 1000 and 15000 in the weight average molecular weight Mw determined by gel permeation chromatography of THF-soluble matter. preferable.

  This is effective in obtaining an image having an appropriate glossiness and density necessary for improving the low-temperature fixability of the toner and close to the image quality of photographs and printing. In addition, the viscosity at 100 ° C. (Pa · s) in the flow tester, which is an essential requirement of the present invention, can be easily controlled to 15000 ≦ 100 ° C. viscosity (Pa · s) ≦ 45000.

  Specifically, for example, it can be obtained by adding a low molecular weight polymer having a weight average molecular weight Mw of 2000 to 5000 in advance and preparing a toner in the presence thereof.

  When the above-mentioned minimum value and maximum value, or the minimum value and the inflection point are less than 1000, the blocking resistance due to leaving at high temperature is inferior, and the storage stability is lowered. If it exceeds 15000, the low-temperature fixability deteriorates and an image having desired glossiness cannot be obtained. As a result, an appropriate image density may not be obtained.

  Examples of the low molecular weight polymer used include styrene such as polystyrene and polyvinyltoluene, and homopolymers of substituted styrene; styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene. -Methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-dimethylaminoethyl acrylate copolymer, styrene-methacrylic acid Methyl copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-dimethylaminoethyl methacrylate copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer Coalescence, styrene-vinyl Styrene copolymers such as tilketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer; polymethyl methacrylate, polybutyl methacrylate , Polyvinyl acetate, polyethylene, polypropylene, polyvinyl butyral, silicone resin, polyester resin, polyamide resin, epoxy resin, polyacrylic resin, rosin, modified rosin, terpene resin, phenol resin, aliphatic or alicyclic hydrocarbon resin, aromatic A group petroleum resin can be used alone or in combination.

  For example, when it is desired to introduce a monomer component containing a hydrophilic functional group such as an amino group, a carboxylic acid group, a hydroxyl group, a sulfonic acid group, a glycidyl group, or a nitrile group into the toner, these and a vinyl compound such as styrene or ethylene And can be used in the form of a random copolymer, a block copolymer, a graft copolymer, and the like.

  Among them, a homopolymer or copolymer obtained by polymerizing at least styrene or a styrene derivative is preferable. In particular, when a toner is manufactured by a suspension granulation method which is a preferable manufacturing method in the present invention, a monomer is used. Therefore, it is possible to produce uniform toner particles in which there is no bias in the amount of low-molecular polymer present between the toner particles. Furthermore, since the resin has a relatively small number of polar groups, the low molecular weight polymer is more likely to be present inside the toner particles than the toner surface layer, and adverse effects such as blocking and member contamination can be prevented.

  The Tg of the low molecular weight polymer to be added is preferably 50 ° C. to 100 ° C. If the Tg is less than 50 ° C., the strength of the entire toner particles is lowered, and the transferability and development characteristics are liable to be lowered during a multi-endurance test. Furthermore, toner particles aggregate in a high-temperature and high-humidity environment, resulting in a problem that storage stability is lowered. On the other hand, when the glass transition point is 100 ° C. or higher, the problem of poor fixing tends to occur.

  The addition amount of the low molecular polymer is preferably 1 to 75 parts by mass in 100 parts by mass of the binder resin in the toner particles. If it is less than 1 part by mass, the effect of adding the resin is small. If it exceeds 75 parts, the toner has poor storage stability and poor blocking resistance.

<GPC measurement method for toner>
The molecular weight of the resin component soluble in THF by GPC of the toner of the present invention was measured as follows.

A solution obtained by allowing the toner to stand in THF at room temperature for 24 hours and dissolving it is filtered through a solvent-resistant membrane filter having a pore diameter of 0.2 μm to obtain a sample solution, and measurement is performed under the following conditions. In addition, sample preparation adjusts the quantity of THF so that the density | concentration of the component soluble in THF may be 0.4-0.6 mass%.
Equipment: High-speed GPC “HLC8120 GPC” (manufactured by Tosoh Corporation)
Column: Seven series of Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko KK)
Eluent: THF
Flow rate: 1.0 ml / min
Oven temperature: 40.0 ° C
Sample injection volume: 0.10 ml

  In calculating the molecular weight of the sample, standard polystyrene resin (TSO standard polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F- manufactured by Tosoh Corporation) was used. 10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500).

The toner of the present invention preferably has a BET specific surface area of 2.5 to 4.0 (m ² / g) in order to control Et100 and Et10 / Et100, which are essential requirements of the present invention, within a preferable range. The BET specific surface area is almost determined by the particle size and particle size distribution of the toner and the specific surface area and amount of inorganic fine powder added as an external additive. If the BET specific surface area of the toner is less than 2.5 (m ² / g), the amount of external additive added is not sufficient, resulting in a toner with insufficient fluidity, slow rise of charge, and fogging. There is a possibility that. Furthermore, when the amount of the external additive added is insufficient, a good image cannot be stably output over a long period of time, and the durability may be inferior. If the specific surface area of the external additive itself is small, this may be considered to be almost the same as the particle size of the external additive being large. However, in this case, the adhesion force of the external additive to the toner particles is weakened, so the toner particles Therefore, there is a possibility that the toner may be inferior in durability due to the deterioration of the toner due to the easy release of the external additive and the contamination of the member.

When the BET specific surface area of the toner exceeds 4.0 (m ² / g), it is considered that the additive amount of the external additive is excessive. Since the amount of the external additive particles that can adhere to the toner particles is determined by the surface area of each other, an excessive amount of the external additive is present in the toner as a free external additive. As a result, fogging may occur due to contamination of the developing roller member. In addition, since the fluidity of the toner is improved too much, the degree of aggregation is lowered, and a CLN defect may occur.

Further, when the specific surface area of the external additive itself is large, this may be considered to be almost the same as the small particle size of the external additive, but even in this case, the BET specific surface area of the toner is 4.0 (m ² / g). Fine external additives can adhere strongly to the toner particles. However, there are cases where external additive particles are embedded in the toner particles due to stress applied to the toner, and the roles that the external additive should originally play, such as imparting fluidity to the toner particles and quick charge rising, are fully exhibited. In some cases, the toner may not be durable.

<Method for measuring BET specific surface area of toner>
The measurement of the BET specific surface area is performed by sufficiently degassing the sample by degassing the sample for 10 hours or more by using a known device such as degassing device Bacuprep 061 (manufactured by Shimadzu Corporation). It can be obtained by using a known measuring device such as a surface area measuring device tristar 3000 (manufactured by Shimadzu Corporation) by the BET method by nitrogen gas adsorption. In addition, the BET specific surface area in this invention is a value of a multipoint method BET specific surface area.

  The weight average particle diameter of the toner of the present invention is preferably 4 to 8 μm.

  The weight average particle diameter (D4) of the toner of the present invention can be measured by various methods such as Coulter Counter TA-II type or Coulter Multisizer (manufactured by Coulter Co.). Specifically, it can be measured as follows. Using a Coulter Multisizer (manufactured by Coulter), an interface (manufactured by Nikka) and a PC 9801 personal computer (manufactured by NEC) are connected to output the number distribution and volume distribution. As the electrolytic solution, a 1% NaCl aqueous solution prepared using primary sodium chloride can be used. For example, ISOTON R-II (manufactured by Coulter Scientific Japan) can be used. The measurement procedure is as follows.

  100 to 150 ml of the electrolytic aqueous solution is added, and 2 to 20 mg of a measurement sample is further added. The electrolyte 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 μm or more are measured with the Coulter Multisizer using a 100 μm aperture. Calculate the distribution. From this, the weight average particle diameter (D4) is determined.

  In order to obtain a good fixed image, the toner of the present invention preferably contains 0.5 to 50 parts by mass, preferably 3 to 30 parts by mass of a release agent with respect to 100 parts by mass of the binder resin. . More preferably, it is 5-20 mass parts. If it is less than 0.5 parts by mass, the effect of suppressing low temperature offset is poor, and if it exceeds 50 parts by mass, the long-term storage stability is deteriorated, the dispersibility of other toner materials is deteriorated, and the fluidity of the toner is reduced. It leads to deterioration of image characteristics.

  Examples of release agents that can be used in the toner according to the present invention include petroleum waxes such as paraffin wax, microcrystalline wax, petrolactam and derivatives thereof, montan wax and derivatives thereof, hydrocarbon waxes by Fischer-Tropsch method and Derivatives, polyolefin waxes represented by polyethylene and derivatives thereof, natural waxes such as carnauba wax and candelilla wax, and derivatives thereof. These derivatives include oxides, block copolymers with vinyl monomers, and graft modified products. Furthermore, higher fatty alcohols, fatty acids such as stearic acid and palmitic acid, or compounds thereof, acid amide waxes, ester waxes, ketones, hydrogenated castor oil and derivatives thereof, plant waxes, animal waxes and the like can be mentioned. Among these waxes, those having an endothermic peak in differential thermal analysis of 40 ° C. to 110 ° C. are preferred, and those having a temperature of 45 ° C. to 90 ° C. are more preferred.

  The toner preferably has a maximum endothermic peak due to the melting point of the wax at 70 to 120 ° C. of the DSC curve measured by a scanning scanning calorimeter.

  The DSC curve was measured according to ASTM D3418-82 using a differential thermal analysis measuring device (DSC measuring device), DSC-7 (manufactured by Perkin Elmer).

  The sample to be measured is precisely weighed 5 to 20 mg, preferably 10 mg.

  This is put in an aluminum pan, and an empty aluminum pan is used as a reference, and measurement is performed at a temperature rise rate of 10 ° C./min at room temperature and normal humidity within a measurement temperature range of 30 to 200 ° C.

  An endothermic peak of the main peak is obtained in this temperature rising process.

  In the present invention, it is preferable to add a charge control agent to the toner particles for the purpose of controlling the chargeability of the toner. Examples of these charge control agents include, as positive charge control agents, nigrosine dyes, triphenylmethane dyes, quaternary ammonium salts, guanidine derivatives, imidazole derivatives, amine compounds, and the like. Examples of negative charge control agents include metal-containing salicylic acid compounds, metal-containing monoazo compounds, urea derivatives, styrene-acrylic acid copolymers, styrene-methacrylic acid copolymers, and styrene-acrylamide sulfonic acid copolymers. . Among these, metal-containing salicylic acid compounds, metal-containing monoazo compounds, and copolymers of styrene-acrylamide sulfonic acids are particularly preferably used. The addition amount of these charge control agents is preferably 0.1 to 10% by weight of the binder resin or polymer monomer.

  Furthermore, styrene-acrylamide sulfonic acids having a weight average molecular weight Mw of 10,000 to 50,000 (hereinafter sometimes referred to as “resin A”) are particularly preferably used. When the weight average molecular weight Mw is 10,000 or less, the fluidity of the toner under high temperature and high humidity deteriorates, and the halftone uniformity decreases. If it exceeds 50,000, it takes time to dissolve in the monomer, and the oozing out of the wax becomes slow, so that the winding offset at the time of fixing is deteriorated and the charge amount distribution is widened.

  The number average molecular weight of the resin A is preferably 5000 or more and 20000 or less. The reason is that if it is less than 5000, the amount of the oligomer component of the toner increases, and the fluidity of the toner under high temperature and high humidity deteriorates. If it exceeds 20000, the compatibility with the binder resin decreases, so the charge amount distribution is reduced. This is because they tend to be broad.

  The peak molecular weight of the resin A is preferably 18000 or more and 30000 or less. The reason is that if it is less than 18000, the amount of the oligomer component of the toner increases and the fluidity of the toner under high temperature and high humidity deteriorates, and if it exceeds 30000, the fixability tends to be adversely affected.

  The peak molecular weight of the resin A is preferably 18000 or more and 30000 or less. The reason is that if it is less than 18000, the amount of the oligomer component of the toner increases and the fluidity of the toner under high temperature and high humidity deteriorates, and if it exceeds 30000, the fixability tends to be adversely affected.

  Furthermore, the acid value of the resin A is preferably 5 or more and 24 or less. If it is less than 5, the uniformity of halftone under a high temperature and high humidity environment is lost, and if it exceeds 24, the stability of a halftone image under a low temperature and low humidity environment tends to be lost.

  In the present invention, the acid value of the resin A was measured according to JIS K0070: 1992.

  As the sulfur-containing monomer for producing the resin A according to the present invention, styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylamide-2-methylpropanesulfonic acid, vinylsulfonic acid, There are methacrylsulfonic acid and the like, or maleic acid amide derivatives, maleimide derivatives, and styrene derivatives having the following structures.

  The resin A according to the present invention may be a homopolymer of the above monomer, but may be a copolymer of the above monomer and another monomer. As a monomer that forms a copolymer with the above monomer, there is a vinyl polymerizable monomer, and a monofunctional polymerizable monomer or a polyfunctional polymerizable monomer can be used.

  Of the above monomers, sulfonic acid group-containing (meth) acrylamide is more preferable in obtaining the chargeability suitable for the toner of the present invention.

  The amount of vinyl monomer containing a sulfonic acid group used when polymerizing the resin A of the present invention is in the range of 2 to 8% by mass, achieving a suitable charge amount in the toner, and improving the image quality of the halftone image. It is preferable for stable supply without being affected by the environment.

  Monofunctional polymerizable monomers include styrene; α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butyl. Styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p -Styrene derivatives such as phenylstyrene; methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2 -Ethylhexyl acrylate , N-octyl acrylate, n-nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, 2-benzoyloxyethyl acrylate Methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl Methacrylate, n-nonyl methacrylate, diethyl phosphate ethyl methacrylate Methacrylic polymerizable monomers such as dibutyl phosphate ethyl methacrylate; methylene aliphatic monocarboxylic acid esters; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, vinyl formate; vinyl methyl ether Vinyl ether such as vinyl ethyl ether and vinyl isobutyl ether; vinyl ketone such as vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropyl ketone.

  As polyfunctional polymerizable monomers, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol Diacrylate, polypropylene glycol diacrylate, 2,2′-bis (4- (acryloxydiethoxy) phenyl) propane, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol Dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol Dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2'-bis (4- (methacryloxy-diethoxy) phenyl) propane, 2,2′-bis (4-methacryloxy / polyethoxy) phenyl) propane, trimethylolpropane trimethacrylate, tetramethylolmethane tetramethacrylate, divinylbenzene, divinylnaphthalene, divinyl ether, and the like.

  In the resin A, as a monomer that can be used in combination with a vinyl monomer containing a sulfonic acid group, the above-described monomers can be used, but styrene or a styrene derivative is an essential monomer. This is because it is indispensable for controlling the charge amount of the resin A in order to stably maintain the image quality of the halftone image. Furthermore, (meth) acrylic acid ester must exist as an essential component in controlling the glass transition temperature described later.

  The production method of the resin A includes bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization, ionic polymerization, etc., but solution polymerization is preferable from the viewpoint of operability.

As resin A, the polymer which has a sulfonic acid group which has the following structure can also be illustrated.
X (SO ₃ ⁻ ) n · mY ^{k +}
(X represents a polymer site derived from the polymerizable monomer, Y ^{k +} represents a counter ion, k is a valence of the counter ion, m and n are integers, and n = k × m is there.)

  In this case, the counter ions are preferably hydrogen ions, sodium ions, potassium ions, calcium ions, ammonium ions, and the like.

  The resin A is preferably contained in an amount of 0.5 to 10 parts by mass per 100 parts by mass of the binder resin. 1 to 8 parts by mass is preferable.

  When the content of the resin A is less than 0.5 parts by mass, it is difficult to obtain a sufficient charge control action as mentioned in the present invention. It tends to cause deterioration of transferability and transferability.

  The content of the resin A in the toner can be measured using a capillary electrophoresis method or the like.

  The resin A must have a glass transition temperature (Tg) of 77 ° C. or higher, and preferably 100 ° C. or lower. When the glass transition temperature is less than 77 ° C., it tends to be difficult to stably output a halftone image at a high temperature. When the glass transition temperature is less than 77 ° C., the external charge is easily embedded in the charge control agent portion existing on the surface, so that the triboelectric chargeability is lowered. On the other hand, when the glass transition temperature exceeds 100 ° C., the charge-up in a low-temperature and low-humidity environment tends to deteriorate, and the fixability at the time of an image having a high toner printing rate is poor.

  Resin A preferably has a volatile content of 0.01 to 2.0%. In order to reduce the volatile content to less than 0.01%, the volatile content removal process becomes complicated, and when the volatile content exceeds 2.0%, charging under high temperature and high humidity, especially charging after standing. It tends to be inferior. The polymer volatile content is the ratio of the weight that decreases when heated at high temperature (135 ° C.) for 1 hour.

  In the measurement of the molecular weight and glass transition point of the resin A, when the resin is extracted from the toner, the extraction method is not particularly limited, and any method can be used.

  The toner of the present invention is preferably added with a polyester resin (hereinafter sometimes referred to as “resin P”) with the aim of further improving developability, storage stability and fixability.

  The weight average molecular weight Mw (P) of the polyester resin is preferably 5000 ≦ Mw (P) ≦ 25000, and when it is less than 5000, high temperature offset at the time of fixing deteriorates or filming on the photoconductor occurs. Sometimes When it exceeds 25000, it becomes impossible to obtain a low-temperature fixing and glossy image. Moreover, it becomes difficult to control the average circularity within a preferable range.

  The resin P used in the present invention, for example, controls one or both of a saturated polyester resin and an unsaturated polyester resin in controlling physical properties such as chargeability, durability, and fixability of toner obtained from toner particles. It is possible to select and use as appropriate. The alcohol component and acid component which comprise the polyester resin used for this invention are illustrated below. As alcohol components, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexane Diol, neopentyl glycol, 2-ethyl-1,3-hexanediol, cyclohexanedimethanol, butenediol, octenediol, cyclohexenedimethanol, hydrogenated bisphenol A, and bisphenol derivatives represented by the following general formula (III):

［式中、Ｒはエチレンまたはプロピレン基であり、ｘ，ｙはそれぞれ１以上の整数であり、かつｘ＋ｙの平均値は２〜１０である。］
あるいは一般式（ＩＩＩ）の化合物の水添物、また、下記一般式（ＩＶ）で示されるジオール、

[Wherein, R is an ethylene or propylene group, x and y are each an integer of 1 or more, and the average value of x + y is 2 to 10. ]
Or a hydrogenated product of the compound of the general formula (III), a diol represented by the following general formula (IV),

あるいは式（ＩＶ）の化合物の水添物のジオール、さらには、グリセリン、ペンタエリスリトール、ソルビット、ソルビタン、ノボラック型フェノール樹脂のオキシアルキレンエーテルの如き多価アルコール等、が挙げられる。

Or the diol of the hydrogenated compound of the compound of Formula (IV), Furthermore, polyhydric alcohol like glycerin, pentaerythritol, sorbit, sorbitan, oxyalkylene ether of a novolak-type phenol resin, etc. are mentioned.

  As the divalent carboxylic acid, benzene dicarboxylic acid such as phthalic acid, terephthalic acid, isophthalic acid, phthalic anhydride or its anhydride, alkyl dicarboxylic acid such as succinic acid, adipic acid, sebacic acid, azelaic acid or its anhydride, Furthermore, succinic acid substituted with an alkyl or alkenyl group having 6 to 18 carbon atoms or anhydride thereof, unsaturated dicarboxylic acid such as fumaric acid, maleic acid, citraconic acid, itaconic acid or anhydride thereof, and further trimellit And polyvalent carboxylic acids such as acid, pyromellitic acid, 1,2,3,4-butanetetracarboxylic acid and benzophenonetetracarboxylic acid, and anhydrides thereof.

  The resin P is present on the surface of the toner particles in the production method of the present invention, and the obtained toner particles have an acid value of 0.1 to 50 mg KOH / resin 1 g in order to develop stable chargeability. It is preferable. If it is less than 0.1 mg KOH / resin 1 g, the abundance on the toner particle surface may be absolutely insufficient, and if it exceeds 50 mg KOH / resin 1 g, the chargeability of the toner particles may be adversely affected. Furthermore, in the present invention, the acid value range of 5 to 35 mg KOH / resin 1 g is more preferable.

  As addition amount of these resin P, 1-20 mass parts is preferable with respect to 100 mass parts of polymerizable monomers. If the amount is less than 1 part by mass, the effect of addition is small. On the other hand, if it exceeds 20 parts by mass, it becomes difficult to design various physical properties in the production of the polymerized toner.

  The toner according to the present invention can be produced by polymerizing toner particles.

  By using the polymerization method, it is easy to obtain a toner satisfying the requirement that the average circularity is 0.950 to 0.990, and in turn, the value of Et10 / Et100 can be easily controlled within the range of the present invention. .

  Furthermore, since the uniformity among toner particles is high and the distribution of the charge amount is relatively uniform, the toner particles have high developability and high transferability.

  Further, since a release agent such as wax preferably used in the toner can be encapsulated without being exposed on the toner surface, the image quality is hardly deteriorated due to contamination of the member.

  These features are particularly preferable when used in a one-component development system that is suitably used for a printer from the viewpoint of miniaturization and low cost.

  Examples of the toner production method by polymerization include a direct polymerization method, a suspension polymerization method, an emulsion polymerization method, an emulsion association polymerization method, and a seed polymerization method. Among these, the balance between the particle size and the particle shape is balanced. In view of easiness, it is particularly preferable to produce by suspension polymerization. In this suspension polymerization method, a monomer composition is prepared by uniformly dissolving or dispersing a colorant (and, if necessary, a polymerization initiator, a crosslinking agent, a charge control agent, and other additives) in the polymerizable monomer. Then, the monomer composition is dispersed in a continuous layer containing a dispersion stabilizer (for example, an aqueous phase) by using an appropriate stirrer, and a polymerization reaction is performed to have a desired particle size. Toner is obtained.

  The toner of the present invention contains a colorant as an essential component in order to impart coloring power. Examples of the organic pigment or dye preferably used in the present invention include the following.

  As a colorant suitable for cyan, a pigment or a dye can be used. I. Pigment Blue 1, 7, 15, 15; 1, 15; 2, 15; 3, 15; 4, 16, 17, 60, 62, 66, etc., C.I. I. Bat Blue 6, C.I. I. Acid Blue 45 and the dye include C.I. I. Solvent blue 25, 36, 60, 70, 93, 95 etc. are mentioned, These can be used individually or in combination of 2 or more types.

  As a colorant suitable for the magenta color, a pigment or a dye can be used. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 48; 2, 48; 3, 48; 4, 49, 50, 51, 52, 53, 54, 55, 57, 57; 1, 58, 60, 63, 64, 68, 81, 81; 1, 83, 87, 88, 89, 90, 112, 114, 122, 123, 144, 146, 150, 163, 166, 169, 177, 184, 185, 202, 206, 207, 209, 220, 221, 238, 254, 269, etc., C.I. I. Pigment violet 19; C.I. I. Examples of magenta dyes such as Vat Red 1, 2, 10, 13, 15, 23, 29, and 35 include C.I. I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 52, 58, 63, 81, 82, 83, 84, 100, 109, 111, 121, 122, etc. I. Disper thread 9, C.I. I. Solvent Violet 8, 13, 14, 21, 27 etc., C.I. I. Oil-soluble dyes such as disperse violet 1, C.I. I. Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40, etc. I. Basic violet 1,3,7,10,14,15,21,25,26,27,28 etc. are mentioned, These dyes can be used alone or in combination of two or more.

  As the colorant suitable for the yellow color, a pigment or a dye can be used. Specifically, examples of the pigment include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 17, 23, 62, 65, 73, 74, 81, 83, 93, 94, 95, 97, 98, 109, 110, 111, 117, 120, 127, 128, 129, 137, 138, 139, 147, 151, 154, 155, 167, 168, 173, 174, 176, 180, 181, 183, 191, C.I. I. Vat yellow 1, 3, 20 etc. I. Solvent Yellow 19, 44, 77, 79, 81, 162 These can be used alone or in combination of two or more.

  These colorants can be used alone or mixed and further used in the form of a solid solution. The colorant used in the toner of the present invention is selected from the viewpoints of hue angle, saturation, brightness, light resistance, OHP transparency, and dispersibility in the toner.

  The colorant is added in an amount of 1 to 20 parts by mass with respect to 100 parts by mass of the binder resin.

  As the black pigment, for example, carbon black such as furnace black, channel black, acetylene black, thermal black and lamp black is used, and magnetic powder such as magnetite and ferrite is also used. It is also possible to use a black-toned one using the yellow / magenta / cyan colorant.

  When a magnetic material is used as the black colorant, it is used by adding 30 to 200 parts by mass with respect to 100 parts by mass of the resin, unlike other colorants.

Examples of the magnetic material include metal oxides containing elements such as iron, cobalt, nickel, copper, magnesium, manganese, aluminum, and silicon. Among them, those containing iron oxide as a main component, such as triiron tetroxide and γ-iron oxide, are preferable. Further, from the viewpoint of toner chargeability control, other metal elements such as silicon element or aluminum element may be contained. These magnetic particles, BET specific surface area by nitrogen adsorption method 2~30m ² / g, particularly preferably 3~28m ² / g, further Mohs hardness magnetic powder 5-7 is preferred.

  Magnetic materials include octahedrons, hexahedrons, spheres, needles, scales, and the like. In the present invention, there are few anisotropies such as octahedrons, hexahedrons, spheres, and irregular shapes. Those for increasing the image density are preferable. The average particle size of the magnetic material is preferably 0.05 to 1.0 μm, more preferably 0.1 to 0.6 μm, and further preferably 0.1 to 0.3 μm.

  In the present invention, when a toner is obtained using a polymerization method, it is necessary to pay attention to the polymerization inhibitory property and water phase transfer property of the colorant, and preferably a material that does not inhibit surface modification, for example, polymerization inhibition. It is better to apply a hydrophobizing treatment. In particular, since dye-based colorants and carbon black often have polymerization inhibition properties, care must be taken when using them. A preferable method for surface-treating the dye-based colorant includes a method in which a polymerizable monomer is polymerized in the presence of these dyes in advance, and the obtained colored polymer is added to the monomer system.

  Carbon black may be treated with a substance that reacts with the surface functional group of carbon black, such as polyorganosiloxane, in addition to the same treatment as the dye-based colorant.

  Next, a method for producing toner particles by a suspension polymerization method for suitably expressing the toner of the present invention will be described.

  When the toner particles of the present invention are produced by a suspension polymerization method, examples of the polymerizable monomer constituting the polymerizable monomer system used include the following.

Examples of the polymerizable monomer include styrene monomers such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, and p-ethylstyrene; methyl acrylate, ethyl acrylate, Acrylic esters such as n-butyl acrylate, isobutyl acrylate, n-propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate Class: Methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenolic methacrylate , Dimethylaminoethyl methacrylate, such as methacrylic acid esters of diethylaminoethyl methacrylate; and other acrylonitrile, methacrylonitrile, and such monomers of acrylamide.

  These polymerizable monomers can be used alone or in combination. Among the polymerizable monomers described above, styrene or a styrene derivative is preferably used alone or in combination with other polymerizable monomers from the viewpoint of developing characteristics and durability of the toner.

  As the polymerization initiator used in the production of the suspension polymerization toner according to the present invention, a polymerization initiator having a half-life of 0.5 to 30 hours at the reaction temperature during the polymerization reaction is preferably used. Moreover, when a polymerization reaction is carried out at an addition amount of 0.5 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer, a polymer having a maximum between 10,000 and 100,000 is usually obtained. A toner having strength and melting characteristics can be obtained. Examples of polymerization initiators include 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile) Azo or diazo polymerization initiators such as 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile; benzoyl peroxide, t-butylperoxy 2-ethylhexa Noate, t-butyl peroxypivalate, t-butyl peroxyisobutyrate, t-butyl peroxyneodecanoate, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl Peroxide polymerization such as peroxide and lauroyl peroxide Agents.

  When producing the suspension polymerization toner according to the present invention, a crosslinking agent may be added, and a preferable addition amount is 0.001 to 15 parts by mass with respect to 100 parts by mass of the polymerizable monomer. . Examples of the crosslinking agent include divinylbenzene.

  When the suspension polymerization toner according to the present invention is produced, a molecular weight adjusting agent can be used. Examples of the molecular weight modifier include mercaptans such as t-dodecyl mercaptan, n-dodecyl mercaptan and n-octyl mercaptan; halogenated hydrocarbons such as carbon tetrachloride and carbon tetrabromide; α-methylstyrene dimer, and the like. Can be mentioned. These molecular weight regulators can be added before the polymerization starts or during the polymerization. The molecular weight modifier is usually used in a proportion of 0.01 to 10 parts by mass, preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the polymerizable monomer.

  In the method for producing a suspension polymerization toner according to the present invention, a colorant, a release agent, and a polymer having a sulfur atom, a magnetic powder, a plasticizer, a charge control agent, if necessary, in a polymerizable monomer, Add a cross-linking agent, an organic solvent, a high molecular weight polymer, a dispersing agent, etc. to reduce the viscosity of the polymer produced by the polymerization reaction, and use a homogenizer, ball mill, colloid mill, ultrasonic disperser, etc. A polymerizable monomer system is prepared by dissolving or dispersing in a water solution, and the resultant is dropped into an aqueous medium containing a dispersion stabilizer, and suspended and granulated. At this time, the particle size of the obtained toner particles becomes sharper by using a high-speed disperser such as a high-speed stirrer or an ultrasonic disperser to obtain a desired toner particle size at a stretch. The polymerization initiator may be added at the same time when other additives are added to the polymerizable monomer, or may be added immediately before the polymerizable monomer system is suspended and granulated in an aqueous medium. Also good. Alternatively, it can be added during suspension granulation. Also, a polymerization initiator dissolved in a polymerizable monomer or solvent can be added immediately after granulation and before starting the polymerization reaction.

  After granulation, stirring may be performed using a normal stirrer to such an extent that the particle state is maintained and the particles are prevented from floating and settling.

  When the suspension polymerization toner according to the present invention is produced, a known surfactant or an organic or inorganic dispersant can be used as a dispersion stabilizer. In particular, when an inorganic dispersant is used, it is difficult to produce ultrafine powder, and since the inorganic dispersant is generally large in size, dispersion stability is obtained due to steric hindrance, so it is stable even when the reaction temperature is changed. It is difficult to lose its properties and is easy to clean. Therefore, an inorganic dispersant can be used more preferably. Examples of such inorganic dispersants include polyvalent metal phosphates such as calcium phosphate, magnesium phosphate, aluminum phosphate and zinc phosphate; carbonates such as calcium carbonate and magnesium carbonate; calcium metaoxalate, calcium sulfate and sulfuric acid. Inorganic salts such as barium; inorganic oxides such as calcium hydroxide, magnesium hydroxide, aluminum hydroxide, silica, bentonite and alumina.

  These inorganic dispersants may be used alone in an amount of 0.2 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer, and 0.001 to 0.1 parts by mass for the purpose of adjusting the particle size distribution. These surfactants may be used in combination. Examples of the surfactant include sodium dodecylbenzene sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, sodium stearate, potassium stearate and the like.

  The inorganic dispersant can be almost completely removed by dissolution with an acid or alkali after the polymerization.

  In the polymerization step, the polymerization is performed at a polymerization temperature of 40 ° C. or higher, generally 50 to 90 ° C. When the polymerization is carried out in this temperature range, the release agents to be sealed inside are precipitated by phase separation, and encapsulation is more sure. In order to consume the remaining polymerizable monomer, the reaction temperature may be raised to 90 to 150 ° C. at the end of the polymerization reaction.

  When toner particles having a viscosity of 100 ° C. (Pa · s), which is an essential requirement of the present application, are reacted at a temperature of 100 ° C., fine irregularities on the surface of the toner particles are eliminated, without causing other image adverse effects, It becomes easy to control Et100 (mJ) and Et10 / Et100 within the scope of the present invention.

  The polymerized toner particles are filtered, washed, and dried by a known method after the polymerization is completed, and the toner can be obtained by mixing and adhering the inorganic fine powder to the surface. Moreover, a classification process may be put into a manufacturing process and coarse powder and fine powder may be cut.

  To the toner of the present invention, inorganic fine powder is added in order to improve the fluidity of the toner and make the charge uniform.

  In the inorganic fine powder, the average primary particle size is preferably 4 to 300 nm.

  When the average primary particle size of the inorganic fine powder is larger than 300 nm, the fluidity of the toner cannot be sufficiently improved, the adhesion to the toner particles tends to be non-uniform, and the triboelectric charging property under low humidity is low. Since this leads to non-uniformity, problems such as an increase in fog, a decrease in image density, or a decrease in durability are likely to occur. When the average primary particle size of the inorganic fine powder is smaller than 4 nm, the agglomeration property of the inorganic fine particles becomes stronger, and it behaves as an agglomerate with a wide particle size distribution that is not primary particles but has strong agglomeration properties that are difficult to break even by crushing treatment. Image defects are likely to occur when the aggregate is developed or the image carrier or the toner carrier is damaged. In order to make the charge amount distribution of the toner particles more uniform, the average primary particle size of the inorganic fine powder is preferably 6 to 100 nm, and more preferably 8 to 35 nm.

  The average primary particle size of the inorganic fine powder is a photograph of the toner magnified by a scanning electron microscope, and is further mapped by the element contained in the inorganic fine powder by an elemental analysis means such as XMA attached to the scanning electron microscope. It can be measured by measuring 100 or more primary particles of the inorganic fine powder present on the toner surface while adhering to or separating from the toner image, and determining the number average particle diameter.

  Further, the content of the inorganic fine powder can be quantified using a calibration curve prepared from a standard sample using fluorescent X-ray analysis.

  As the inorganic fine powder to be added to the toner of the present invention, silica, titanium oxide, alumina, hydrotalcite, or a double oxide thereof can be used.

For example, as the silica, both a so-called dry method produced by vapor phase oxidation of silicon halide or dry silica called fumed silica, and so-called wet silica produced from water glass or the like can be used. Dry silica is preferred because it has less silanol groups on the surface and in the silica fine powder and less production residue such as Na ₂ O, SO ₃ ^2- . In dry silica, it is also possible to obtain composite fine powders of silica and other metal oxides by using other metal halogen compounds such as aluminum chloride and titanium chloride together with silicon halogen compounds in the production process. Is also included.

  The addition amount of the inorganic fine powder is preferably 0.1 to 4.0 parts by mass with respect to 100 parts by mass of the toner particles, and if the addition amount is less than 0.1 parts by mass, the effect is not sufficient. If it exceeds 0 part by mass, the fixability tends to be lowered. In the inorganic fine powder, the average primary particle size is preferably 4 to 80 nm.

  The inorganic fine powder is preferably hydrophobized from the viewpoint of improving characteristics in a high humidity environment. When the inorganic fine powder added to the toner absorbs moisture, the charge amount as the toner is remarkably reduced, and the developability and transferability are easily lowered.

  As treatment agents for hydrophobization treatment, treatment agents such as silicone varnish, various modified silicone varnishes, silicone oil, various modified silicone oils, silane compounds, silane coupling agents, other organic silicon compounds, and organic titanium compounds may be used alone or in combination. And may be processed.

  Among these, those treated with silicone oil are preferable, and more preferably, the inorganic fine powder is treated with silicone oil at the same time or after treatment to maintain the charge amount of toner particles high even in a high humidity environment. In view of suppressing selective development, it is preferable.

  The processing conditions of the inorganic fine powder include, for example, a silylation reaction as the first stage reaction to eliminate active hydrogen groups on the surface by chemical bonds, and then a hydrophobic thin film is formed on the surface with silicone oil as the second stage reaction. can do. As a usage-amount of a silylating agent, 5-50 mass parts is preferable with respect to 100 mass parts of inorganic fine powder. If it is less than 5 parts by mass, it is not sufficient to eliminate the active hydrogen groups on the surface of the inorganic fine particles, and if it exceeds 50 parts by mass, the siloxane compound produced by the reaction of the excess silylating agent serves as a paste to serve as the inorganic fine particles. Aggregation occurs and image defects are likely to occur.

The silicone oil preferably has a viscosity at 25 ° C. of 10 to 200,000 mm ² / s, and more preferably 3,000 to 80,000 mm ² / s. If it is less than 10 mm ² / s, the inorganic fine powder is not stable and the image quality tends to deteriorate due to heat and mechanical stress. If it exceeds 200,000 mm ² / s, uniform processing tends to be difficult.

  As a method for treating silicone oil, for example, inorganic fine powder treated with a silane compound and silicone oil may be directly mixed using a mixer such as a Henschel mixer, or a method of spraying silicone oil on inorganic fine powder. May be used. Alternatively, after dissolving or dispersing silicone oil in an appropriate solvent, inorganic fine powder may be added and mixed to remove the solvent. A method using a sprayer is more preferable in that the formation of inorganic fine powder aggregates is relatively small.

  The treatment amount of the silicone oil is 1 to 23 parts by mass, preferably 5 to 20 parts by mass with respect to 100 parts by mass of the inorganic fine powder. If the amount of the silicone oil is too small, good hydrophobicity cannot be obtained, and if it is too large, aggregation of inorganic fine particles tends to occur.

The toner of the present invention preferably contains a hydrotalcite compound represented by the following general formula as an inorganic fine powder.
General formula (1)
M1 _y1 · M2 _y2 ··· Mj _yj · L1 _x1 · L2 _x2 ··· Lk _xk · (OH) ₂ · A _{x / n} · mH ₂ O

  In the hydrotalcite compound powder according to the present invention, M1 to Mj in the general formula (1) are different divalent metal ions, specifically, Mg, Zn, Ca, Ba, Ni, Sr. , Cu and Fe can be appropriately selected. Among these, Mg is preferable, and it is preferable that the content (molar fraction) of metal ions other than Mg satisfies the relationship of 0.001 ≦ y2 +... + Yj ≦ 0.05.

  In addition, L1 to Lk in the general formula (1) are different trivalent metal ions, and specifically, can be appropriately selected from the group consisting of Al, B, Ga, Fe, Co, and In. Among these, Al is preferable, and it is preferable that the content (molar fraction) of metal ions other than Al satisfies the relationship of 0.0003 ≦ x2 +... + Xk ≦ 0.02.

  Furthermore, it is preferable that two or more kinds of the above divalent metal ions and trivalent metal ions exist.

As A (n-valent anion) of the above general formula (1) of the hydrotalcite compound powder according to the present invention, CO ₃ ²⁻ , OH ⁻ , Cl ⁻ , I ⁻ , F ⁻ , Br ⁻ , SO _{4 can be used. ^{-, HCO 3 -, CH 3}} COO -, NO 3 -, salicylate, citrate, ^{_{tartrate, (OOC-COO) 2 -}} , [Fe (CN) 6] 4 - are exemplified, alone, or a plurality Species may be present.

  Further, in the above general formula (1) of the hydrotalcite compound powder according to the present invention, m ≧ 0, but from the viewpoint of stabilization of charging property, crystal water is previously contained in the molecule. Is preferable, and 0.1 <m <0.6 is more preferable.

The powder properties of the hydrotalcite compound powder according to the present invention, BET specific surface area of 1.0 m ² / g or more, more preferably a 5.0~100m ² / g, and an average secondary particle diameter Is preferably 10 μm or less.

  The average secondary particle size of the hydrotalcite compound powder is measured by, for example, using an image processing device “Luzex III” (manufactured by Nireco) after taking an enlarged photograph with a transmission electron microscope (TEM). .

  The hydrotalcite compound powder according to the present invention is preferably hydrophobized with a surface treating agent from the viewpoint of charging stability and durability of the toner. As the surface treatment agent, higher fatty acids, coupling agents, esters, and silicone oil oils can be used. Among these, higher fatty acids are preferably used, and specific examples include stearic acid, oleic acid, lauric acid and the like.

  As the surface treatment method of the hydrotalcite compound powder with the surface treatment agent as described above, a conventionally known method can be used. For example, the surface treatment agent is dissolved and mixed in a solvent, or heated and dissolved to form a liquid. And a method of wet mixing with untreated hydrotalcite compound powder, and a method of mechanically dry-mixing a fine powdered surface treatment agent and hydrotalcite compound powder after surface treatment. If necessary, for example, means such as washing, dehydration, drying, pulverization, and classification can be appropriately selected to obtain a hydrotalcite compound powder subjected to surface treatment.

  The amount of the hydrotalcite compound powder added to the toner particles is preferably 0.03 to 3 parts by mass, more preferably 0.1 to 1 part by mass with respect to 100 parts by mass of the toner particles.

  Next, image formation using the toner of the present invention will be described.

  The conditions of the development step in the image forming method to which the toner of the present invention can be applied may be that the toner carrier and the surface of the photosensitive body as the electrostatic latent image carrier are in contact or non-contact. . Here, the case where it contacts is demonstrated.

As the toner carrying member, an elastic roller can be used, and a method can be used in which toner is coated on the surface of the elastic roller or the like and developed by bringing it into contact with the surface of the photoreceptor. As the elastic roller, one having an elastic layer having an ASKER-C hardness of 30 to 60 degrees is preferably used. When the development is performed by bringing the toner carrier into contact with the surface of the photoreceptor, the development is performed by an electric field acting between the photoreceptor and the elastic roller facing the surface of the photoreceptor via the toner. Therefore, the surface of the elastic roller or the vicinity of the surface has an electric potential, and it is necessary to have an electric field in a narrow gap between the surface of the photoreceptor and the toner carrying surface. Therefore, the elastic rubber of the elastic roller is resistance-controlled in the middle resistance region, and the electric field is maintained while preventing conduction with the surface of the photoreceptor, or a thin insulating layer is provided on the surface layer of the conductive roller Can also be used. Further, there is also a configuration in which a conductive layer is provided on the side not facing the photoconductor with a resin-coated conductive sleeve in which the side facing the surface of the photoconductor is coated with an insulating material (resin) on the conductive roller. Is possible. Further, it is possible to employ a configuration in which a rigid roller is used as the toner carrying member and the photosensitive member is a flexible material such as a belt. The resistance of the toner carrier is preferably in the range of 10 ² to 10 ⁹ Ω · cm. If it is lower than 10 ² Ω · cm, for example, if there is a pinhole on the surface of the photoconductor, an overcurrent may flow. On the other hand, if it is higher than 10 ⁹ Ω · cm, the toner is likely to be charged up by frictional charging, and the image density is likely to be lowered.

  If the surface roughness Ra (μm) of the toner carrier is set to 0.2 to 3.0, both high image quality and high durability can be achieved. The surface roughness Ra correlates with the toner conveying ability and the toner charging ability. When the surface roughness Ra of the toner carrier exceeds 3.0, not only the toner layer on the toner carrier becomes difficult to be thinned but also the toner charging uniformity deteriorates and the halftone uniformity is reduced. We cannot expect improvement of image quality such as deterioration. Since the toner carrying ability on the surface of the toner carrier is suppressed by setting it to 3.0 or less, the toner layer on the toner carrier is thinned, and the number of contact between the toner carrier and the toner increases. Since the chargeability of the toner is also improved, the image quality is synergistically improved. On the other hand, when the surface roughness Ra is smaller than 0.2, it becomes difficult to control the toner coat amount.

The toner coat amount on the toner carrier is preferably 0.1 to 1.5 mg / cm ² . When the amount is less than 0.1 mg / cm ^2, it is difficult to obtain a sufficient image density. When the amount is more than 1.5 mg / cm ^2, it becomes difficult to uniformly charge all of the individual toner particles, causing fogging. Become. Furthermore, 0.2 to 0.9 mg / cm ² is more preferable. In the present invention, the surface roughness Ra of the toner carrier is measured using a surface roughness measuring instrument (Surfcoder SE-30H, manufactured by Kosaka Laboratory Co., Ltd.) based on JIS surface roughness “JIS B 0601”. This corresponds to the centerline average roughness. Specifically, a 2.5 mm portion as the measurement length a is extracted from the roughness curve in the direction of the center line, the center line of this extraction portion is the X axis, the direction of the vertical magnification is the Y axis, and the roughness curve is When expressed by y = f (x), it means a value obtained by the following formula expressed in micrometers (μm).

  In the image forming method used in the present invention, the toner carrier may be rotated in the same direction at the portion facing the photoconductor, or may be rotated in the opposite direction. When both rotations are in the same direction, it is preferable to set the peripheral speed of the toner carrier to be 1.05 to 3.0 times the peripheral speed of the photoreceptor.

When the peripheral speed of the toner carrier is less than 1.05 times the peripheral speed of the photoreceptor, the stirring effect received by the toner on the photoreceptor is insufficient, and good image quality cannot be expected. On the other hand, when the peripheral speed ratio exceeds 3.0, toner deterioration due to mechanical stress and toner adhesion to the toner carrier are generated and promoted, which is not preferable. As the photoreceptor, a photosensitive drum or a photosensitive belt having a photoconductive insulating material layer such as a-Se, CdS, ZnO ₂ , OPC, or a-Si is preferably used.

  The photosensitive layer in the OPC photoreceptor may be a single layer type containing a charge generation material and a material having charge transport performance in the same layer, or a function-separated type photosensitive layer having a charge transport layer and a charge generation layer as components. There may be. A laminated photosensitive layer having a structure in which a charge generation layer and then a charge transport layer are laminated in this order on a conductive substrate is one preferred example. In addition, the binder resin of the organic photosensitive layer is not particularly limited, but polycarbonate resin, polyester resin, and acrylic resin are particularly excellent in transferability, and the toner can be fused to the photosensitive member and external additives. It is preferable because filming is difficult to occur.

  Next, image formation using the toner of the present invention will be described below with reference to the accompanying drawings.

  In FIG. 2, 100 is a developing device, 109 is a photosensitive member, 105 is a transfer target such as paper, 106 is a transfer member, 107 is a fixing pressure roller, 108 is a fixing heating roller, and 110 is in contact with the photosensitive member 109. A primary charging member that performs direct charging is shown.

  A bias power source 115 is connected to the primary charging member 110 so as to uniformly charge the surface of the photoconductor 109.

  The developing device 100 contains toner 104 and includes a toner carrier 102 that rotates in the direction of an arrow in contact with an electrostatic latent image carrier (photoconductor) 109. Further, a developing blade 101 for regulating the amount of toner and applying a charge, and a coating roller that rotates in the direction of the arrow in order to attach the toner 104 to the toner carrier 102 and to apply a charge to the toner by friction with the toner carrier 102 103. A developing bias power source 117 is connected to the toner carrier 102. A bias power source (not shown) is also connected to the application roller 103, and when negatively charged toner is used, the voltage is more negative than the developing bias, and when positively charged toner is used, the voltage is more positive than the developing bias. Is set.

  A transfer bias power supply 116 having a polarity opposite to that of the photoconductor 109 is connected to the transfer member 106.

  Here, the length in the rotation direction, that is, the so-called development nip width at the contact portion between the photoconductor 109 and the toner carrier 102 is preferably 0.2 to 8.0 mm. If the thickness is less than 0.2 mm, the development amount is insufficient, and it is difficult to obtain a satisfactory image density, and the transfer residual toner tends to be insufficiently collected. If it exceeds 8.0 mm, the toner supply amount becomes excessive, fogging is likely to occur, and wear of the photoconductor tends to be remarkable.

  The toner coating amount is controlled by the developing blade 101, and the developing blade 101 is in contact with the toner carrier 102 through the toner layer. The contact pressure at this time is preferably in the range of 4.9 to 49 N / m (5 to 50 gf / cm). If it is less than 4.9 N / m, in addition to controlling the toner coating amount, uniform frictional charging becomes difficult, causing fogging. On the other hand, if it exceeds 49 N / m, the toner particles are subjected to an excessive load, so that the deformation of the particles and the fusion of the toner to the developing blade or the toner carrier are likely to occur.

  The free end portion of the regulating member may have any shape as long as it has a preferable NE length (the length from the contact portion of the developing blade to the toner carrying member to the free end). For example, the cross-sectional shape is linear. In addition to those, those having an L shape bent near the tip or those having a shape in which the tip is swelled in a spherical shape are preferably used.

  As the toner coat amount regulating member, a rigid metal blade or the like may be used in addition to the elastic blade for press-fitting toner.

  For the elastic regulating member, it is preferable to select a frictional charging material suitable for charging the toner to a desired polarity. A rubber elastic body such as silicone rubber, urethane rubber or NBR, or a synthetic resin such as polyethylene terephthalate. A metal elastic body such as an elastic body, stainless steel, steel, or phosphor bronze can be used. Moreover, those composites may be sufficient.

  Further, when durability is required for the elastic regulating member and the toner carrier, it is preferable that the metal elastic body is bonded or coated with a resin or rubber so as to contact the sleeve contact portion.

  Furthermore, an organic substance or an inorganic substance may be added to the elastic regulating member, and it may be melt-mixed or dispersed. For example, the chargeability of the toner can be controlled by adding a metal oxide, metal powder, ceramics, carbon allotrope, whisker, inorganic fiber, dye, pigment, surfactant or the like. In particular, when the elastic body is a molded body such as rubber or resin, fine metal oxide powders such as silica, alumina, titania, tin oxide, zirconia, and zinc oxide, carbon black, a charge control agent generally used for toners, etc. It is also preferable to contain.

  Furthermore, application of a DC electric field and / or an AC electric field to the regulating member also improves the uniform thin-layer coating property and uniform charging property due to the loosening action on the toner, achieving a sufficient image density and high quality. Images can be obtained. In particular, when a toner within the scope of the present invention is used, the unraveling action on the toner is effectively performed, so that the uniform thin layer coating property and the uniform charging property are further improved.

  As the charging member, there are a non-contact type corona charger and a contact type charging member using a roller or the like, and any of them is used. For efficient uniform charging, simplification, and low ozone generation, a contact type is preferably used.

  In FIG. 2, a contact-type charging member is used.

  The primary charging member 110 used in FIG. 2 is a charging roller that basically includes a central core metal 110b and a conductive elastic layer 110a that forms the outer periphery thereof. The charging roller 110 is brought into contact with the entire surface of the electrostatic latent image carrier with a pressing force, and is rotated following the rotation of the electrostatic latent image carrier 109.

  As a preferable process condition when the charging roller is used, the contact pressure of the roller is 4.9 to 490 N / m (5 to 500 gf / cm), and a DC voltage superimposed with an AC voltage is used as an applied voltage. Sometimes AC voltage = 0.5-5 kVpp, AC frequency = 50 Hz-5 kHz, DC voltage = ± 0.2- ± 1.5 kV, and when DC voltage is used, DC voltage = ± 0.2- ± 5 kV It is. In addition, since the amount of scraping of the drum can be suppressed, it is more preferable to use only a DC voltage as the applied voltage. Other contact charging means include a method using a charging blade and a method using a conductive brush. These contact charging means are superior to non-contact corona charging in that a high voltage is unnecessary and generation of ozone is reduced. The material of the charging roller and charging blade as the contact charging means is preferably conductive rubber, and a release coating may be provided on the surface thereof. As the releasable coating, nylon resin, PVDF (polyvinylidene fluoride), PVDC (polyvinylidene chloride), and the like are applicable.

  As the description of the image forming apparatus illustrated in FIG. 2, the contact charging unit has been described. However, in the case of using the contact charging unit in the image forming apparatus having other configurations, the same apparatus and conditions can be used. .

  Following the primary charging step, an electrostatic latent image corresponding to the information signal is formed on the photoconductor 109 by exposure 123 from the light emitting element, and the electrostatic latent image can be developed with toner at a position where it abuts the toner carrier 102. Visualize. Furthermore, in the image forming method of the present invention, particularly in combination with a developing system in which a digital latent image is formed on a photoreceptor, it becomes possible to develop the dot latent image faithfully without disturbing the latent image. . The visible image is transferred to the transfer target 105 by the transfer member 106 and passed between the heating roller 108 and the pressure roller 107 and fixed to obtain a fixed image. In addition to the heat roller system, which includes a heating roller incorporating a heating element such as a halogen heater and an elastic pressure roller pressed against the heating roller with a pressing force as a basic configuration, the heating and pressure fixing means may be provided via a film. A method of fixing by heating with a heater is also used.

  On the other hand, the untransferred toner remaining on the photoconductor 109 without being transferred is collected by a cleaner 138 having a cleaning blade in contact with the surface of the photoconductor 109, and the photoconductor 109 is cleaned.

  Next, an image forming method and an apparatus unit using the toner of the present invention will be described with reference to the drawings.

  3 and 4 are schematic views of an image forming apparatus that collectively transfers multiple toner images onto a recording material using an intermediate transfer member in the image forming method of the present invention.

  The surface of the electrostatic latent image carrier (photosensitive drum) 1 as a latent image carrier is brought into contact with the surface of the photosensitive drum 1 while rotating the charging roller 2 to which a charging bias voltage is applied, and then the surface of the photosensitive drum is primarily charged. Then, a first electrostatic latent image is formed on the photosensitive drum 1 by the laser light E emitted from the light source device L as the exposure means. The formed first electrostatic latent image is developed with the black toner in the black developing device 4Bk as a first developing device provided in the rotatable rotary unit 24 to form a black toner image. The black toner image formed on the photosensitive drum 1 is electrostatically primary transferred onto the intermediate transfer drum 5 by the action of the transfer bias voltage applied to the conductive support of the intermediate transfer drum. Next, a second electrostatic latent image is formed on the surface of the photosensitive drum 1 in the same manner as described above, and the rotary unit 24 is rotated so that the yellow toner in the yellow developing device 4Y as the second developing device is used. Development is performed to form a yellow toner image, and the yellow toner image is electrostatically primary transferred onto the intermediate transfer drum 5 on which the black toner image is primarily transferred. Similarly, a third electrostatic latent image is formed, and the rotary unit 24 is rotated to develop with the magenta toner in the magenta developer 4M as the third developer, and further, the fourth electrostatic latent image is developed. An image is formed, the rotary unit 24 is rotated, and primary transfer is sequentially performed with cyan toner in the cyan developing unit 4C as a fourth developing unit, and each color toner image is primary transferred onto the intermediate transfer drum 5. To do. The multiple toner image primarily transferred onto the intermediate transfer drum 5 is electrostatically applied onto the recording material P by the action of the transfer bias voltage from the second transfer device 8 positioned on the opposite side via the recording material P. Secondary transfer is performed at once. The multiple toner image secondarily transferred onto the recording material P is heated and fixed to the recording material P by a fixing device 9 having a heating roller 9a and a pressure roller 9b. The transfer residual toner remaining on the surface of the photosensitive drum 1 after the transfer is collected by a cleaner 6 having a cleaning blade in contact with the surface of the photosensitive drum 1, and the photosensitive drum 1 is cleaned.

  In the primary transfer from the photosensitive drum 1 to the intermediate transfer drum 5, the toner image is transferred by applying a transfer bias from a power source (not shown) to the conductive support of the intermediate transfer drum 5 as the first transfer device. Done.

  The intermediate transfer drum 5 includes a conductive support 5a that is a rigid body and an elastic layer 5b that covers the surface.

  As the conductive support 5a, a metal or an alloy such as aluminum, iron, copper, and stainless steel, and a conductive resin in which carbon or metal particles are dispersed can be used. The thing which penetrated the axis | shaft in the center, the thing which gave reinforcement to the inside of a cylinder, etc. are mentioned.

  The elastic layer 5b is not particularly limited, but styrene-butadiene rubber, high styrene rubber, butadiene rubber, isoprene rubber, ethylene-propylene copolymer, EPDM (terpolymer of ethylene propylene diene), Elastomer rubbers such as nitrile butadiene rubber (NBR), chloroprene rubber, butyl rubber, silicone rubber, fluorine rubber, nitrile rubber, urethane rubber, acrylic rubber, epichlorohydrin rubber and norbornene rubber are preferably used. A resin such as a polyolefin resin, a silicone resin, a fluorine resin, or a polycarbonate, and a copolymer or a mixture thereof may be used.

  Further, a surface layer in which lubricant powder having high lubricity and water repellency is dispersed in an arbitrary binder may be provided on the surface of the elastic layer.

  There are no particular limitations on the lubricant, but various fluororubbers, fluoroelastomers, fluorocarbons and polytetrafluoroethylenes, polytetrafluoroethylenes, polyvinylidene fluorides, ethylene-tetrafluoroethylene copolymers, and tetrafluoroethylene-perfluorocarbons with fluorine bonded to graphite or graphite. Fluorine compounds such as fluoroalkyl vinyl ether copolymers, silicone compounds such as silicone resins, silicone rubbers, and silicone elastomers, polyethylene, polypropylene, polystyrene, acrylic resins, polyamide resins, phenol resins, and epoxy resins are preferably used.

  In addition, a conductive agent may be added to the surface layer binder in order to control resistance. Examples of the conductive agent include various conductive inorganic particles and carbon black, an ionic conductive agent, a conductive resin, and a conductive particle-dispersed resin.

  The multiple toner images formed on the intermediate transfer drum 5 are secondarily transferred collectively onto the recording material P by the second transfer device 8, and the transfer means 8 is a non-contact electrostatic transfer such as a corona charger. Means or contact electrostatic transfer means such as transfer rollers and transfer belts can be used.

  When using a transfer roller, the voltage applied to the transfer roller can be reduced by setting the volume resistivity of the elastic layer of the transfer roller smaller than the volume resistivity of the elastic layer of the intermediate transfer drum. A good toner image can be formed and winding of the transfer material around the intermediate transfer member can be prevented. In particular, the volume specific resistance value of the elastic layer of the intermediate transfer member is particularly preferably 10 times or more than the volume specific resistance value of the elastic layer of the transfer roller.

  The hardness of the intermediate transfer drum and the transfer roller is measured according to JIS K-6301. The intermediate transfer drum used in the present invention is preferably composed of an elastic layer in the range of 10 to 40 degrees, while the hardness of the elastic layer of the transfer roller is harder than the hardness of the elastic layer of the intermediate transfer drum. Those having a value of ˜80 degrees are preferable for preventing the transfer material from being wound around the intermediate transfer drum. When the hardness of the intermediate transfer drum and that of the transfer roller are reversed, a recess is formed on the transfer roller side, and the transfer material is easily wound around the intermediate transfer drum.

  The fixing device 9 is replaced with a heat roller fixing device having a heating roller 9a and a pressure roller 9b, and the toner image on the recording material P is heated by heating a film in contact with the toner image on the recording material P. Also, a film heat fixing device that heat-fixes a multiple toner image on the recording material P can be used.

  Instead of the intermediate transfer drum as the intermediate transfer member used in the image forming apparatus shown in FIG. 3, it is also possible to batch transfer the multiple toner images onto the recording material using an intermediate transfer belt. The configuration of the intermediate transfer belt is shown in FIG.

  The toner image formed and supported on the electrostatic latent image carrier (photosensitive drum) 1 is applied from the primary transfer roller 312 to the intermediate transfer belt 310 in the process of passing through the nip portion between the photosensitive drum 1 and the intermediate transfer belt 310. The primary transfer is sequentially performed on the outer peripheral surface of the intermediate transfer belt 310 by the electric field formed by the primary transfer bias. Reference numeral 311 denotes a roller around which the intermediate transfer belt 310 is stretched.

  A primary transfer bias for sequentially superimposing and transferring toner images of the first to fourth colors from the photosensitive drum 1 to the intermediate transfer belt 310 is applied from a bias power source 314 with a polarity opposite to that of the toner.

  In the primary transfer process of the first to third color toner images from the photosensitive drum 1 to the intermediate transfer belt 310, the secondary transfer roller 13 b and the cleaning charging member 309 can be separated from the intermediate transfer belt 10.

  Reference numeral 313b denotes a secondary transfer roller, which is supported in parallel with the secondary transfer counter roller 313a so as to be separated from the lower surface portion of the intermediate transfer belt 310.

  When the multi-color toner image transferred onto the intermediate transfer belt 310 is transferred to the transfer material P, the secondary transfer roller 313b is brought into contact with the intermediate transfer belt 310, and the intermediate transfer belt 310 and the secondary transfer roller 313b. The transfer material P is fed to the contact nip with a predetermined timing, and a secondary transfer bias is applied from the bias power source 316 to the secondary transfer roller 313b. The multi-color toner image is secondarily transferred from the intermediate transfer belt 310 to the transfer material P by the secondary transfer bias.

  After the image transfer to the transfer material P is completed, a cleaning charging member 309 is brought into contact with the intermediate transfer belt 310, and a bias having a polarity opposite to that of the photosensitive drum 1 is applied from the bias power source 315, thereby transferring the image to the transfer material P. Instead, a charge having a polarity opposite to that of the photosensitive drum 1 is applied to the toner (transfer residual toner) remaining on the intermediate transfer belt 310.

  The transfer residual toner is electrostatically transferred to the photosensitive drum 1 at and near the nip portion with the photosensitive drum 1 to clean the intermediate transfer member.

  The intermediate transfer belt includes a belt-shaped base layer and a surface treatment layer provided on the base layer. The surface treatment layer may be composed of a plurality of layers. Rubber, elastomer, or resin can be used for the base layer and the surface treatment layer.

  For example, as rubber and elastomer, natural rubber, isoprene rubber, styrene-butadiene rubber, butadiene rubber, butyl rubber, ethylene-propylene rubber, ethylene-propylene terpolymer, chloroprene rubber, chlorosulfonated polyethylene, chlorinated polyethylene, acrylonitrile butadiene rubber, Urethane rubber, syndiotactic 1,2-polybutadiene, epichlorohydrin rubber, acrylic rubber, silicone rubber, fluorine rubber, polysulfurized rubber, polynorbornene rubber, hydrogenated nitrile rubber and thermoplastic elastomer (for example, polystyrene, polyolefin, 1 type or 2 types or more selected from the group consisting of polyvinyl chloride, polyurethane, polyamide, polyester, fluororesin, etc. can be used.However, it is not limited to the said material.

  As the resin, a resin such as a polyolefin resin, a silicone resin, a fluorine resin, or a polycarbonate can be used. A copolymer or a mixture of these resins may be used.

  As the base layer, one obtained by coating, dipping, or spraying the above-described rubber, elastomer, or resin on one side or both sides of a core layer having a woven fabric shape, a nonwoven fabric shape, a thread shape, or a film shape may be used.

  The material constituting the core layer is not particularly limited. For example, natural fibers such as cotton, silk, hemp and wool; regenerated fibers such as chitin fiber, alginic acid fiber and regenerated cellulose fiber; and half fibers such as acetate fiber Synthetic fiber: polyester fiber, nylon fiber, acrylic fiber, polyolefin fiber, polyvinyl alcohol fiber, polyvinyl chloride fiber, polyvinylidene chloride fiber, polyurethane fiber, polyalkyl paraoxybenzoate fiber, polyacetal fiber, aramid fiber, polyfluoroethylene fiber and phenol Synthetic fibers such as fibers; inorganic fibers such as carbon fibers, glass fibers, and boron fibers; one or more selected from the group consisting of metal fibers such as iron fibers and copper fibers can be used.

  Further, a conductive agent may be added to the base layer and the surface treatment layer in order to adjust the resistance value of the intermediate transfer belt. Although it does not specifically limit as a electrically conductive agent, For example, metal powder, such as carbon, aluminum, and nickel, metal oxides, such as a titanium oxide, and quaternary ammonium salt containing polymethyl methacrylate, polyvinyl aniline, polyvinyl pyrrole, One kind or two or more kinds selected from the group consisting of polydiacetylene, polyethyleneimine, boron-containing polymer compounds, conductive polymer compounds such as polypyrrole, and the like can be used.

  Further, a lubricant may be added as necessary in order to increase the slipperiness of the intermediate transfer belt surface and improve the transferability. As the lubricant, the same lubricant as that used for the elastic layer of the intermediate transfer drum can be used.

  Next, an image forming method will be described with reference to FIG. 5 in which toner images of respective colors are formed by a plurality of image forming units and transferred onto the same transfer material in sequence.

  In the image forming apparatus shown in FIG. 5, first, second, third and fourth image forming units 29a, 29b, 29c and 29d are arranged in parallel, and each image forming unit has its own electrostatic capacity. A latent image carrier, so-called photosensitive drums 19a, 19b, 19c and 19d are provided.

  On the outer peripheral side of the photosensitive drums 19a to 19d, charging means 30a, 30b, 30c and 30d, latent image forming means 23a, 23b, 23c and 23d, developing means 17a, 17b, 17c and 17d, transfer means (transfer discharge means) ) 24a, 24b, 24c and 24d and cleaning means 18a, 18b, 18c and 18d are arranged.

  With such a configuration, first, the photosensitive drum 19a of the first image forming unit 29a is charged by the charging unit 30a, and a latent image of, for example, a yellow component color in the original image is formed by the latent image forming unit 23a. The latent image is converted into a visible image by the developer having yellow toner of the developing unit 17a, and transferred to the recording material S as a transfer material by the transfer unit 24a.

  As described above, while the yellow image is transferred to the transfer material S, the second image forming unit 29b forms a magenta component color latent image on the photosensitive drum 19b, and subsequently has the magenta toner of the developing unit 17b. A visible image is formed with the developer. This visible image (magenta toner image) is transferred to a predetermined position of the transfer material S when the transfer material S, which has been transferred by the first image forming unit 29a, is transferred to the transfer unit 24b. The

  Thereafter, cyan and black images are formed by the third and fourth image forming portions 29c and 29d in the same manner as described above, and the cyan and black colors are transferred onto the same transfer material S. To do. After such an image forming process is completed, the transfer material S is conveyed to the fixing unit 22 and the image on the transfer material S is fixed. As a result, a multicolor image is obtained on the transfer material S. The photosensitive drums 19a, 19b, 19c, and 19d that have completed the transfer have the residual toner removed by the cleaning units 18a, 18b, 18c, and 18d, and then a series of image forming processes are repeated.

  In the image forming apparatus, a conveyance belt 25 is used for conveying the recording material S as a transfer material.

  In this image forming apparatus, a transport belt using a mesh of Tetron (registered trademark) fiber as a transport means for transporting a transfer material and a polyethylene terephthalate resin, a polyimide resin, and a urethane resin from the viewpoint of durability. A conveyance belt using such a thin dielectric sheet is preferably used.

  In general, such a conveyance belt has a high volume resistance, and the charge amount of the conveyance belt increases in the process of repeating several times of transfer in color image formation. Therefore, in order to maintain uniform transfer, each transfer is required. However, since the toner of the present invention has excellent transferability, even if the charge of the conveying means increases each time the transfer is repeated, the transfer property of the toner in each transfer can be increased with the same transfer current. It can be made uniform and a high-quality image with good quality can be obtained.

  When the transfer material S passes through the fourth image forming portion 29d, an AC voltage is applied to the static eliminator 20, the transfer material S is neutralized and separated from the belt 25, and then enters the fixing device 22 where the image is fixed and discharged. It is discharged from the outlet 26.

  FIG. 6 shows an image formation using a transfer belt as a secondary transfer means when a color toner image of four colors transferred onto the intermediate transfer drum using the intermediate transfer drum is secondarily transferred collectively to a recording material. It is explanatory drawing of an apparatus.

In the apparatus system shown in FIG. 6, each of the developing devices 244-1, 244-2, 244-3, and 244-4 includes a developer having cyan toner, a developer having magenta toner, a developer having yellow toner, and A developer having black toner has been introduced. The photosensitive member 241 is charged by charging means, and further exposed to light 243 to form an electrostatic latent image. The electrostatic image is developed using the developing devices 244-1 to 244-4, and each color toner image is electrostatically charged. They are sequentially formed on a latent image carrier (photoconductor) 241. The photosensitive member 241 is a photosensitive drum or a photosensitive belt having a photoconductive insulating material layer such as a-Se, Cds, ZnO ₂ , OPC, or a-Si. The photoreceptor 241 is rotated in the direction of the arrow by a driving device (not shown).

  In the charging step, a charging roller 242 having a basic configuration of a central cored bar 242b and a conductive elastic layer 242a that forms the outer periphery thereof is used. The charging roller 242 is pressed against the surface of the photoconductor 241 with a pressing force, and is driven to rotate as the photoconductor 241 rotates.

  The toner image on the photoreceptor is transferred to an intermediate transfer drum 245 to which a voltage (for example, ± 0.1 to ± 5 kV) is applied. The surface of the photoreceptor after the transfer is cleaned by a cleaning unit 249 having a cleaning blade 248.

  As the intermediate transfer drum 245, the same intermediate transfer drum as described above can be used. 245b is a rigid conductive support, and 245a is an elastic layer covering the surface.

  The intermediate transfer drum 245 is disposed in parallel with the photoconductor 241 and is in contact with the lower surface of the photoconductor 241, and rotates in the counterclockwise direction indicated by an arrow at the same peripheral speed as the photoconductor 241.

  The first color toner image formed and supported on the surface of the photosensitive member 241 passes through the transfer nip where the photosensitive member 241 and the intermediate transfer drum 245 are in contact with each other, and is applied to the transfer nip region by the transfer bias applied to the intermediate transfer drum 245. The intermediate transfer is sequentially performed on the outer surface of the intermediate transfer drum 245 by the formed electric field.

  If necessary, the surface of the intermediate transfer drum 245 is cleaned by a removable cleaning unit 280 after the toner image is transferred onto the transfer material. When there is a toner image on the intermediate transfer drum, the cleaning means 280 is separated from the surface of the intermediate transfer member so as not to disturb the toner image.

  In FIG. 6, a transfer belt 247 is disposed below the intermediate transfer drum 245. The transfer belt 247 is stretched between two rollers arranged in parallel to the axis of the intermediate transfer drum 245, that is, a bias roller 247a and a tension roller 247c, and is driven by a driving unit (not shown). Since the transfer belt 247 is configured such that the bias roller 247a side can move in the arrow direction around the tension roller 247c side, the transfer belt 247 can contact and separate from the intermediate transfer drum 245 in the arrow direction from below. A desired secondary transfer bias is applied to the bias roller 247a by a secondary transfer bias source 247d, while the tension roller 247c is grounded.

Next, as for the transfer belt 247, in this embodiment, a thermosetting urethane elastomer layer in which carbon is dispersed (thickness: about 300 μm, volume resistivity: 10 ⁸ to 10 ¹² Ω · cm (when 1 kV is applied)) A rubber belt was used in which a fluororubber layer (thickness 20 μm, volume resistivity 10 ¹⁵ Ω · cm (when 1 kV was applied)) was stacked thereon. The outer diameter is a tube shape with a circumference of 80 × width of 300 mm.

  The transfer belt 247 described above may be applied with a tension that extends about 5% by the bias roller 247a and the tension roller 247c.

  The transfer belt 247 is rotated at a constant speed or a peripheral speed with respect to the intermediate transfer drum 245. The transfer material 246 is conveyed between the intermediate transfer drum 245 and the transfer belt 247, and at the same time, a bias having a polarity opposite to the frictional charge of the toner is applied to the transfer belt 247 from the secondary transfer bias source 247d. The toner image on the transfer drum 245 is transferred to the surface side of the transfer material 246.

  As the material of the bias roller, the same material as that of the charging roller can be used. As preferable transfer process conditions, the contact pressure of the roller is 4.9 to 490 N / m (5 to 500 gf / cm), and the direct current is DC. The voltage is ± 0.2 to ± 10 kV.

For example, the conductive elastic layer 247a1 of the bias roller 247a has a volume resistance of about 10 ⁶ to 10 ¹⁰ Ωcm such as polyurethane, ethylene-propylene-diene terpolymer (EPDM) in which a conductive material such as carbon is dispersed. Made with body. A bias is applied to the cored bar 247a2 by a constant voltage power source. The bias condition is preferably ± 0.2 to ± 10 kV.

  Next, the transfer material 246 is conveyed to a fixing device 281 which basically includes a heating roller incorporating a heating element such as a halogen heater and an elastic pressure roller pressed against it with a pressing force. By passing between the pressure rollers, the toner image is fixed to the transfer material by heating and pressing. A method of fixing with a heater through a film may be used.

  The present invention will be described below with reference to examples, but the present invention is not limited to the examples. In addition, all the parts used in an Example show a mass part.

<Example 1>
In a four-necked vessel, 450 parts by mass of ion exchange water and 6 parts by mass of Na ₃ PO ₄ were added, and the mixture was maintained at 60 ° C. while stirring at 12,000 rpm using a high-speed stirring device TK type-homomixer. 4 parts by mass of CaCl ₂ was gradually added thereto to prepare an aqueous dispersion medium containing a fine hardly water-soluble dispersion stabilizer Ca ₃ (PO ₄ ) ₂ .

Styrene monomer 80 parts by mass n-butyl acrylate 20 parts by mass Copper phthalocyanine pigment 5 parts by mass Styrene-acrylic acid 2-ethylhexyl 2-acrylamido-2-methylpropanesulfonic acid copolymer (Mw = 28000) 1 part by mass Polystyrene (Mw = 2800) 25 parts by mass Negative charge control agent (aluminum compound of 3,5-jettery butylsalicylic acid)
1 part by weight Fischer-Tropsch wax (mp = 75 ° C.) 10 parts by weight Polyester resin comprising ethylene oxide / propylene oxide adduct of bisphenol A and terephthalic acid (Mw = 10000, acid value = 10) 6 parts by weight The monomer mixture was dispersed for 5 hours using an attritor to obtain a polymerizable monomer composition. A polymerizable monomer composition is charged into the aqueous dispersion medium, and 8.0 parts by mass of 2,2′-azobis-isobutyrovaleronitrile as a polymerization initiator is added thereto, and the stirrer is rotated. Granulation was carried out for 10 minutes while maintaining the number at 12,000 rpm. Thereafter, the high-speed stirrer was transferred to a propeller-type stirrer, the internal temperature was raised to 70 ° C., and the reaction was allowed to proceed for 5 hours with slow stirring. Next, the inside of the container was heated to 85 ° C. and maintained for 5 hours. Steam was poured directly into the contents in the container, the temperature was raised to 100 ° C., and maintained for 3 hours. Then it was cooled. Dilute hydrochloric acid was added to the container to adjust the pH to 1.4, and the dispersion stabilizer was dissolved. Further, after filtration and washing, the particles were vacuum dried at 40 ° C., and the particle diameter was adjusted by classification to obtain cyan toner particles.

To 100 parts by mass of the toner particles obtained, 2.0 parts by mass of hydrophobic silica having a specific surface area of 200 m ² / g by BET method (10 parts by mass treated with silicone oil for 100 parts by mass of silica) Mg / Al = 3 hydrotalcite compound particles (hydrotalcite (treated with 10 parts by mass of zinc stearate with respect to 100 parts by mass)) 0.1 part by mass of inorganic fine powder consisting of Mg and Al, Henschel mixer (FM10B) was externally added by stirring at 3500 rpm for 10 minutes to obtain toner No. 1.

  Toner No. 1 is a non-magnetic one-component developer no. The image was evaluated using an image forming apparatus as shown in FIG. The image forming apparatus will be described below.

  FIG. 7 is a schematic view of a modified 1200 dpi laser beam printer (manufactured by Canon: LBP-840) using a non-magnetic one-component contact development type electrophotographic process. In this example, an apparatus in which the following parts (a) to (g) were modified was used.

  (A) The charging method of the apparatus was direct charging performed by contacting a rubber roller, and the applied voltage was a direct current component (-1200 V).

(B) The toner carrier was changed to a medium resistance rubber roller (diameter 16 mm, hardness ASKER-C 45 degrees, resistance 10 ⁵ Ω · cm) made of silicone rubber dispersed with carbon black, and contacted with the photoreceptor.

  (C) The toner carrying member was driven so that the rotational peripheral speed of the toner carrying member was in the same direction at the contact portion with the photosensitive member, and was 150% of the photosensitive member rotational peripheral speed.

  (D) The photoconductor was changed to the following.

The photoreceptor used here was an Al cylinder as a substrate, and layers having the following constitution were sequentially laminated by dip coating to produce a photoreceptor.
Conductive coating layer: Mainly composed of a powder of tin oxide and titanium oxide dispersed in a phenol resin. Film thickness 15 μm.
-Undercoat layer: Mainly composed of modified nylon and copolymer nylon. Film thickness 0.6 μm.
Charge generation layer: Mainly composed of a titanyl phthalocyanine pigment having absorption in a long wavelength region dispersed in a butyral resin. Film thickness 0.6 μm.
Charge transport layer: Mainly composed of a hole-transporting triphenylamine compound dissolved in a polycarbonate resin (molecular weight 20,000 by Ostwald viscosity method) at a mass ratio of 8:10. Film thickness 20 μm.

  (E) As a means for applying the toner to the toner carrier, an application roller made of foamed urethane rubber was provided in the developing unit and brought into contact with the toner carrier. A DC component (−600 V) voltage was applied to the coating roller.

  (F) In order to control the coat layer of the toner on the toner carrier, an untreated stainless steel blade was used, and a DC component (−600 V) voltage was applied to the blade.

  (G) Only the DC component (-450 V) was applied during development.

  A commercially available paint is applied very thinly on the surface of a rubber roller having the same diameter, the same hardness, and the same resistance as the toner carrier used in the image forming apparatus, and after temporarily assembling the image forming apparatus, the rubber roller is removed, and an optical microscope The surface of the stainless steel blade was observed and the NE length was measured. The NE length was 1.05 mm.

  The electrophotographic apparatus was remodeled and process conditions were set as follows in order to conform to the remodeling of these process cartridges.

  The modified device uses a roller charger (applying only DC) to charge the image carrier. Subsequent to charging, an image portion is exposed with a laser beam to form an electrostatic latent image, and a visible image is formed with toner, and then the toner image is transferred to a transfer material by a roller to which a voltage of +700 V is applied. As for the photosensitive member charging potential, the dark portion potential was set to -600V and the bright portion potential was set to -150V.

  Further, the fixing device was modified so that the heating temperature can be controlled to 170 ° C. ± 20 ° C. using the apparatus shown in FIG.

  The process speed was modified to 150 (mm / sec).

  Under the above conditions, two images of a printing ratio of 2% are intermittently generated in a high-temperature and high-humidity environment (30 ° C., 80% RH) (that is, the developer is stopped for 10 seconds every time two images are printed out) After the image is printed at a constant speed of 90 sheets in a preliminary operation at the time of restarting, the image is printed at a constant speed of 90 sheets. The image was printed at a speed of (second speed), up to 8000 sheets were printed, and the following items were evaluated at the initial time and every 8000 hours. The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2.

(1) Image Density Using a normal copying machine plain paper (75 g / m ² ) transfer material, a solid image was output at the end of the endurance evaluation in an image output test, and the density was measured for evaluation. The image density was measured by using a “Macbeth reflection densitometer RD918” (manufactured by Macbeth Co., Ltd.) to measure the relative density with respect to an image of a white background portion having a document density of 0.00.
A: Very good 1.40 or more B: Good 1.35 or more, less than 1.40 C: No problem in practical use 1.00 or more, less than 1.35 D: Somewhat difficult Less than 1.00

(2) Glossiness The solid image output in (1) was measured using a gloss meter PG-3D (manufactured by Nippon Denshoku Industries Co., Ltd.).
A: Very good 20 (target value) within ± 1.
B: Good 20 (target value) within ± 2.
C: No problem in practical use Within 20 (target value) ± 5.
D: Somewhat difficult 20 (target value) exceeds ± 5.

(3) Image fog In gloss paper mode (1/2 speed), print out an image with a printing ratio of 30% on glossy paper, and measure the print using “REFECTRECTER MODEL TC-6DS” (manufactured by Tokyo Denshoku). The fog density (%) was calculated from the difference between the whiteness of the white background portion of the printout image and the whiteness of the transfer paper, and the image fogging at the end of the durability evaluation was evaluated. The filter used was amber light for cyan, blue for yellow, and green for magenta and black.
A: Very good Less than 0.5% B: Good 0.5% or more and less than 1.0% C: No practical problem 1.0% or more and less than 1.5% D: Somewhat difficult 1.5% or more

(4) Roughness of halftone image In order to evaluate the balance between the fluidity and chargeability of the toner, it was judged by the uniformity of the halftone image output after three solid images were printed.
A: Very good Image uniformity is very excellent and extremely clear image B: Good Image uniformity is excellent and good image C: No problem in practical use Image quality D: no problem in practical use Image uniformity is poor and is not practically desirable

(5) Contamination in main body / cartridge due to scattering of toner To evaluate the balance between chargeability and fluidity of toner, the degree of contamination by toner around the cartridge after printing 7000 sheets and the cartridge in the main body was observed.
A: Very good No contamination due to toner around the cartridge and cartridge in the main body is observed at all B: Good Contamination due to a small amount of toner is observed on the cartridge C: No problem in practical use Observed, but does not affect the attachment / detachment of the image / cartridge D: Somewhat difficult The toner around the cartridge and the cartridge in the main unit is extremely dirty with toner, and the attachment / detachment of the image / cartridge is also adversely affected

(6) Charging Rise Evaluation The toner charge rise is determined after the CRG is set and before the initial images (1) to (3) are output, the solid patch images from the first to the 20th print are printed. Judgment was made according to the following criteria by density change (measured with a Macbeth reflection densitometer).
Rank A: Very good The number of sheets up to density 1.4 is 5 or less Rank B: Good The number of sheets up to density 1.4 is 6 to 10 Rank C: No problem in practical use The density reaches 1.4 Number of sheets up to 11 to 20 Rank D: Somewhat difficult Number of sheets up to density 1.4 is 21 or more

(7) Storage Stability Test 10 g of the initial developer was taken out from the developing unit, the toner was put in a 100 ml glass bottle, and allowed to stand at 50 ° C. for 10 days.
Rank A: Very good No change Rank B: Good Aggregates, but immediately loosen Rank C: No problem in practical use Difficult to loosen Rank D: Slightly difficult Rank E: No problem Clear caking

<Example 2>
In Example 1, as an inorganic fine powder to be processed to 100 parts by mass of toner particles, hydrophobic silica having a specific surface area of 200 m ² / g by BET method (10 parts by mass with silicone oil for 100 parts by mass of silica) Except for adding only 3.0 parts by mass, the same procedure as in Example 1 was performed for cyan toner no. 2 (non-magnetic one-component developer No. 2) was obtained. The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2.

<Example 3>
In Example 1, as an inorganic fine powder to be processed to 100 parts by mass of toner particles, hydrophobic silica having a specific surface area of 90 m ² / g by BET method (10 parts by mass with silicone oil for 100 parts by mass of silica) Except for changing to 0.3 part by mass of 2.5 parts by mass and hydrophobic titanium oxide having a specific surface area by BET method of 10 m ² / g (10 parts by mass with silicone oil for 100 parts by mass of silica). In the same manner as in No. 1, cyan toner no. 3 (nonmagnetic one-component developer No. 3) was obtained. The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2.

<Example 4>
In Example 1, as an inorganic fine powder to be processed to 100 parts by mass of toner particles, hydrophobic silica having a specific surface area of 50 m ² / g by BET method (10 parts by mass with silicone oil for 100 parts by mass of silica) It consists of 2.0 parts by mass, Mg and Al, and Mg / Al = 3 hydrotalcite compound particles (hydrotalcite (20 parts by mass with zinc stearate for 100 parts by mass)) Except for the change, cyan toner No. 4 (non-magnetic one-component developer No. 4) was obtained in the same manner as in Example 1. Table 1 shows the toner physical properties and Table 2 shows the evaluation results.

<Example 5>
In Example 1, in preparing an aqueous dispersion medium containing the fine hardly water-soluble dispersion stabilizer Ca ₃ (PO ₄ ) ₂ , Na ₃ PO ₄ is added to ion exchange water to 5 parts by mass, and thereafter In the same manner as in Example 1, except that CaCl ₂ added to 3 parts by mass is changed to cyan toner No. 5 (Non-magnetic one-component developer No. 5) was obtained. The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2.

<Example 6>
In Example 1, when preparing an aqueous dispersion medium containing the fine hardly water-soluble dispersion stabilizer Ca ₃ (PO ₄ ) ₂ , Na ₃ PO ₄ is added to ion exchange water to 8 parts by mass, and thereafter In the same manner as in Example 1 except that the CaCl ₂ added to the toner is changed to 5 parts by mass, 6 (Non-magnetic one-component developer No. 6) was obtained. The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2.

<Example 7>
In Example 1, cyan toner No. 1 was prepared in the same manner as in Example 1 while stirring at 7000 rpm. 7 (Non-magnetic one-component developer No. 7) was obtained. The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2.

<Example 8>
In Example 7, except that the classification conditions were adjusted, the cyan toner No. 8 (nonmagnetic one-component developer No. 8) was obtained. The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2.

<Example 9>
In Example 1, the cyan toner No. 1 was changed in the same manner as in Example 1 except that the physical properties of the polyester resin were changed to 2.5 parts by mass of polyester having Mw = 30000 and acid value = 10. 9 (non-magnetic one-component developer No. 9) was obtained. The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2.

<Example 10>
In Example 9, cyan toner No. 1 was used in the same manner as in Example 9 except that after the classification, the spheronization process was performed using a thermal spheronizer. 10 (nonmagnetic one-component developer No. 10) was obtained. The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2.

<Example 11>
In Example 1, cyan toner No. 1 was changed in the same manner as in Example 1 except that the amount of negative charge control agent (aluminum compound of 3,5-jettery butylsalicylic acid) was changed to 3 parts by mass. 11 (Non-magnetic one-component developer No. 11) was obtained. The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2.

<Example 12>
In Example 1, cyan toner No. 1 was changed in the same manner as in Example 1 except that the amount of negative charge control agent (aluminum compound of 3,5-jettery butylsalicylic acid) was changed to 2 parts by mass. 12 (nonmagnetic one-component developer No. 12) was obtained. The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2.

<Example 13>
In Example 1, without adding polystyrene, the amount of 2,2′-azobis-isobutyrovaleronitrile added is 8.5 parts by mass, and the internal temperature for raising the temperature to 70 ° C. is changed to 75 ° C. Except for the case of cyan toner no. 13 (Non-magnetic one-component developer No. 13) was obtained. The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2.

<Example 14>
In Example 1, except that the type of polystyrene was changed to polypropylene (Mw = 3500), the same procedure as in Example 1 was carried out for cyan toner No. 14 (Non-magnetic one-component developer No. 14) was obtained. The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2.

<Example 15>
(Prepolymer production example)
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 630 parts by mass of bisphenol A ethylene oxide 2-mole adduct, 165 parts by mass of adduct, 200 parts by mass of isophthalic acid, 65 parts by mass of terephthalic acid, and 2 parts by mass of dibutyltin oxide was added, and a condensation reaction was performed at 205 ° C. for 8 hours under a normal pressure nitrogen stream. Next, the reaction was continued for 5 hours while dehydrating under reduced pressure of 10 to 15 mmHg, then cooled to 80 ° C., reacted with 150 parts by mass of isophorone diisocyanate in ethyl acetate for 2 hours, and prepolymer a (Mw = 3500) was obtained. Obtained.

(Production example of ketimine compound)
In a reaction vessel equipped with a stir bar and a thermometer, 30 parts by mass of isophorodiamine and 70 parts of methyl ethyl ketone were charged and reacted at 50 ° C. for 5 hours to obtain a ketimine compound (b).

(Example of toner production)
In a beaker, 14.3 parts by mass of prepolymer (a), 55 parts by mass of polyester (Mw = 8000, acid value = 10) and 78.6 parts by mass of ethyl acetate consisting of bisphenol A-terephthalic acid were stirred and dissolved. Separately, 10 parts by mass of rice wax as a release agent, 4 parts of copper phthalocyanine blue pigment, and ethyl acetate were placed in a 100 parts by mass bead mill and dispersed for 30 minutes. The two liquids were mixed and stirred for 5 minutes at a rotational speed of 12,000 rpm using a TK homomixer, and then dispersed in a bead mill for 10 minutes. This is designated as toner material oil dispersion (c).

  In a four-necked vessel, 306 parts by mass of ion-exchanged water, 265 parts by mass of a 10% tricalcium phosphate suspension, and 0.2 parts by mass of sodium dodecylbenzenesulfonate are added and stirred at 12,000 rpm with a TK homomixer. Then, 2.7 parts by mass of the toner material oil dispersion (c) and the ketimine compound (b) were added to the aqueous dispersion, and the reaction was continued for 30 minutes while stirring. Further, steam was directly poured into the contents in the container, the temperature was raised to 100 ° C., and the state was maintained for 3 hours. Thereafter, filtration, washing, drying, and air classification were performed to obtain a spherical toner base.

To 100 parts by mass of the toner particles obtained, 2.0 parts by mass of hydrophobic silica having a specific surface area of 200 m ² / g by BET method (10 parts by mass treated with silicone oil for 100 parts by mass of silica) Mg / Al = 3 hydrotalcite compound particles (hydrotalcite (treated with 10 parts by mass of zinc stearate with respect to 100 parts by mass)) 0.1 part by mass of inorganic fine powder consisting of Mg and Al, Henschel mixer Cyan toner No. 15 (nonmagnetic one-component developer No. 15) was obtained by externally adding (FM10B) with stirring at 3500 rpm for 10 minutes.

<Example 16>
(Preparation of release agent fine particle dispersion 1)
78.33 parts by mass of demineralized water, 20 parts by mass of an ester compound mainly composed of behenyl behenate (Unistar M-2222SL, manufactured by NOF Corporation) and 1.7 parts by mass of sodium dodecylbenzenesulfonate were mixed, and the pressure was increased at 90 ° C. The mixture was emulsified by shearing to obtain a release agent fine particle dispersion 1. The average particle size was 340 nm.

(Preparation of resin fine particle dispersion 1)
In a reactor (with a high-shear stirring device, volume 1 liter flask), 150 parts by mass of ion-exchanged water, 1.5 parts by mass of nonionic surfactant (manufactured by Sanyo Chemical Co., Ltd .: Nonipol 400) and anionic surfactant 3.5 parts by mass of an agent (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) was added.

Next, 71 parts by mass of styrene, 29 parts by mass of n-butyl acrylate, 3 parts by mass of acrylic acid, 0.35 parts by mass of octanethiol, 0.7 parts by mass of carbon tetrabromide, and dissolved, are added to the reactor. While adding and slowly mixing, 10 parts by mass of ion-exchanged water having 5 parts by mass of ammonium persulfate dissolved therein was added dropwise over 10 minutes. Ten minutes later, the contents were heated in an oil bath while stirring the contents until the temperature reached 75 ° C., and after 1 hour, the temperature was further raised to 70 ° C. and emulsion polymerization was continued for 4 hours under a nitrogen atmosphere. After a predetermined time, cooling was performed until the temperature reached room temperature at a rate of 2 ° C. per minute. Thus, a resin particle dispersion 1 in which resin particles having an average particle diameter of 0.07 μm were dispersed was prepared.

(Preparation of colorant fine particle dispersion 1)
・ C. I. Pigment Blue 15: 3 25 parts by mass, anionic surfactant 2 parts by mass (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC)
-Ion exchange water 78 mass parts The above was mixed and it disperse | distributed using the sand grinder mill. When the particle size distribution in the colorant particle dispersion 1 was measured using a particle size measuring device (LA-920, manufactured by Horiba, Ltd.), the average particle size of the contained colorant particles was 0.2 μm and 1 μm. No coarse particles exceeding were observed.

(Preparation of charge control fine particle dispersion 1)
-15 parts by mass of a metal compound of di-alkyl-salicylic acid (charge control agent, Bontron E-84, manufactured by Orient Chemical Industries)
・ Anionic surfactant 2 parts by mass (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC)
-Ion exchange water 78 mass parts The above was mixed and it disperse | distributed using the sand grinder mill. When the particle size distribution in the charge control fine particle dispersion 1 was measured using a particle size measurement device (LA-920, manufactured by Horiba, Ltd.), the average particle size of the charge control particles contained was 0.2 μm and 1 μm. No coarse particles exceeding were observed.

(Example of toner production)
-Resin fine particle dispersion 1 360 parts by mass-Colorant fine particle dispersion 1 40 parts by mass-Release agent fine particle dispersion 1 70 parts by mass-Charge control particle dispersion 1 7 parts by mass-Anionic surfactant 2 parts by mass ( Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC)
Using each of the above components, a toner was produced by the following procedure. The resin fine particle dispersion 1 and the anionic surfactant were charged into a reactor (a 1 liter flask having a baffle and an anchor blade with a baffle) and mixed uniformly, and then the colorant fine particle dispersion was added and mixed uniformly. While stirring the obtained mixed dispersion, 0.6 part by mass of an aqueous aluminum sulfate solution as a solid content was dropped (aggregation step).

  After completion of the dropwise addition, the system was replaced with nitrogen, and the system was maintained at 50 ° C. for 1 hour and further at 55 ° C. for 1 hour.

  After completion of the predetermined time, the charge control fine particle dispersion, the release agent fine particle dispersion 1, and the aluminum sulfate aqueous solution (0.6 parts by mass as a solid content) were added, and then 1 hour at 60 ° C., 30 minutes at 90 ° C. Retained (thermal fusion process). Finally, the temperature was raised to 100 ° C. and held for 1 hour. The reaction at this time was performed in a nitrogen atmosphere.

After completion of the predetermined time, after further filtering, washing and drying, the particle diameter was adjusted by classification to obtain cyan toner particles. To 100 parts by mass of the toner particles obtained, 2.0 parts by mass of hydrophobic silica having a specific surface area of 200 m ² / g by BET method (10 parts by mass treated with silicone oil for 100 parts by mass of silica) Mg / Al = 3 hydrotalcite compound particles (hydrotalcite (treated with 10 parts by mass of zinc stearate with respect to 100 parts by mass)) 0.1 part by mass of inorganic fine powder consisting of Mg and Al, Henschel mixer (FM10B) was added externally by stirring at 3500 rpm for 10 minutes, and cyan toner No. 16 (non-magnetic one-component developer No. 16)

<Comparative Example 1>
In a four-necked vessel, 450 parts by mass of ion exchange water and 4 parts by mass of Na ₃ PO ₄ were added, and the mixture was kept at 60 ° C. while stirring at 12,000 rpm using a high-speed stirring device TK type-homomixer. Here, ₂ parts by mass of CaCl ₂ was gradually added to prepare an aqueous dispersion medium containing a fine hardly water-soluble dispersion stabilizer Ca ₃ (PO ₄ ) ₂ .

Styrene monomer 70 parts by weight n-butyl acrylate 30 parts by weight Copper phthalocyanine pigment 5 parts by weight Negative charge control agent (aluminum compound of salicylic acid) 1 part by weight Paraffin wax (mp = 66 ° C.) 15 parts by weight The above monomer The mixture was dispersed using an attritor for 5 hours to obtain a polymerizable monomer composition. Into the aqueous dispersion medium, a polymerizable monomer composition is added, and 8 parts by mass of 2,2′-azobis-isobutyrovaleronitrile as a polymerization initiator is added thereto, and the rotation speed of the stirrer is increased. The mixture was granulated for 10 minutes while maintaining 12,000 rpm. Thereafter, the high-speed stirrer was transferred to a propeller-type stirrer, the internal temperature was raised to 75 ° C., and the reaction was allowed to proceed for 5 hours with slow stirring. Next, the inside of the container was heated to 85 ° C. and maintained for 5 hours. Then it was cooled. Dilute hydrochloric acid was added to the container to adjust the pH to 1.4, and the dispersion stabilizer was dissolved. Further, after filtration and washing, the particles were vacuum dried at 40 ° C., and the particle diameter was adjusted by classification to obtain cyan toner particles.

To 100 parts by mass of the toner particles obtained, 2.0 parts by mass of hydrophobic silica having a specific surface area of 200 m ² / g by the BET method (10 parts by mass treated with silicone oil for 100 parts by mass of silica) The inorganic fine powder was externally added by stirring for 10 minutes at 3500 rpm with a Henschel mixer (FM10B). 17 (Non-magnetic one-component developer No. 17) was obtained. Thereafter, the same evaluation as in Example 1 was performed. The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2.

<Comparative example 2>
In Comparative Example 1, as an inorganic fine powder to be processed to 100 parts by mass of toner particles, hydrophobic silica having a specific surface area of 90 m ² / g by BET method (10 parts by mass with silicone oil for 100 parts by mass of silica) Comparative example except that 0.7 parts by mass and hydrophobic titanium oxide having a specific surface area by BET method of 150 m ² / g (10 parts by mass treated with silicone oil for 100 parts by mass of silica) are changed to 0.7 parts by mass In the same manner as in No. 1, cyan toner no. 18 (nonmagnetic one-component developer No. 18) was obtained. The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2.

<Comparative Example 3>
In Comparative Example 1, the inorganic fine powder is changed to 84 parts by mass of styrene monomer and 16 parts by mass of n-butyl acrylate, and processed to 100 parts by mass of toner particles. The hydrophobicity is 200 m ² / g in specific surface area by BET method. It consists of 2.0 parts by mass of silica (10 parts by mass of silicone oil with respect to 100 parts by mass of silica), Mg and Al, and Mg / Al = 3 hydrotalcite compound particles (hydrotalcite (100 parts by mass). Cyan toner No. 19 (non-magnetic one-component developer No. 19), except that it was changed to 0.1 part by mass of inorganic fine powder. Table 1 shows the toner physical properties and Table 2 shows the evaluation results.

<Comparative example 4>
In Comparative Example 1, the same procedure as in Comparative Example 1 was conducted except that the internal temperature for raising the temperature to 75 ° C. was changed to 80 ° C., with the change to 9 parts by mass of 2,2′-azobis-isobutyrovaleronitrile. Cyan toner no. 20 (nonmagnetic one-component developer 20) was obtained. The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2.

It is explanatory drawing of the external appearance (a) of the propeller-type blade of a powder fluidity | liquidity analyzer, and the twist angle (b) of a blade outermost edge part. 1 is a schematic diagram illustrating an example of an image forming apparatus to which the toner of the present invention can be applied. 1 is a schematic diagram illustrating an example of an image forming apparatus using an intermediate transfer drum. FIG. 6 is an explanatory diagram illustrating an example of a configuration of an intermediate transfer belt. FIG. 5 is a schematic diagram illustrating an example of an image forming method in which toner images of respective colors are formed in a plurality of image forming units, and the toner images are sequentially superimposed and transferred onto the same transfer material. FIG. 2 is a schematic diagram illustrating an example of an image forming apparatus in which toner images of respective colors are formed in a plurality of image forming units and are sequentially transferred onto the same transfer material. 1 is a schematic diagram illustrating an example of an image forming apparatus used in an embodiment. It is a schematic cross-sectional side view of a heating device (film type fixing device).

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Photosensitive drum 2 Charging roller 4Y Yellow developing device 4M Magenta developing device 4C Cyan developing device 4Bk Black developing device 5 Intermediate transfer drum 5a Conductive support 5b Elastic layer 6 Cleaner 8 Transfer device 9 Fixing device 9a Heating roller 9b Pressure roller 24 Rotary units 17a, 17b, 17c, 17d Developing means 18a, 18b, 18c, 18d Cleaning means 19a, 19b, 19c, 19d Photosensitive drum 20 Charger 22 Fixing devices 23a, 23b, 23c, 23d Latent image forming means 24a, 24b, 24c, 24d transfer means 25 belt 26 discharge ports 29a, 29b, 29c, 29d image forming units 30a, 30b, 30c, 30d charging means 100 developing device 101 developing blade 102 toner carrier 103 coating roller 104 toner 105 transferred object 1 6 Transfer member 107 Fixing pressure roller 108 Fixing heating roller 109 Photoconductor 110 Primary charging member 123 Exposure 138 Cleaner 241 Photoconductor 242 Charging roller 242a Conductive elastic layer 242b Core metal 243 Exposure 244-1, 244-2, 244 -3, 244-4 Developer 245 Intermediate transfer drum 245a Elastic layer 245b Conductive support 246 Transfer material 247 Transfer belt 247a Bias roller 247a1 Conductive elastic layer 247a2 Core metal 247c Tension roller 247d Secondary power source bias source 248 Cleaning blade 249 Cleaning unit 280 Cleaning unit 281 Fixing device 309 Cleaning charging member 310 Intermediate transfer belt 311 Tension roller 312 Transfer roller 313a Secondary transfer counter roller 313b Secondary Transfer roller 314, 315, 316 Bias power supply 10 Fixing belt 16a, 16b Film (belt) guide members 17a, 17b, 17c Magnetic core 18 Excitation coil 19 Insulating member (excitation coil holding member)
22 Pressurized rigid stay 26 Temperature sensor
30 Pressure roller (elastic)
30a Metal core 30b Elastic material layer 40 Good heat conducting member 50 Thermo switch N Fixing nip P Transfer material (recording material)

Claims (9)

A non-magnetic toner having toner particles containing at least a resin, a colorant, a release agent and an inorganic fine powder,
100 ° C viscosity (Pa · s) by flow tester
15000 ≦ 100 ° C. viscosity (Pa · s) ≦ 45000
A nonmagnetic toner characterized by satisfying the following relational expressions (1) and (2):
0 ≦ Et100 (mJ) ≦ 500 (1)
1.00 ≦ Et10 / Et100 ≦ 1.60 (2)
[However, Et100 (mJ) is allowed to vertically enter the toner powder layer in the container while rotating the peripheral speed of the outermost edge of the propeller blade at 100 mm / sec, and 100 mm from the bottom surface of the powder layer. This represents the sum of the rotational torque and the vertical load obtained when starting measurement from the position and entering the position 10 mm from the bottom, and Et10 (mJ) represents the rotational torque when rotated at 10 mm / sec. Represents the total vertical load. ] The nonmagnetic toner according to claim 1, wherein the toner satisfies the following relational expressions (3) and (4).
150 ≦ Et100 (mJ) ≦ 470 (3)
1.20 ≦ Et10 / Et100 ≦ 1.60 (4) The toner has an average particle diameter and an average circularity of particles having an equivalent circle diameter of 2 μm or more and a circularity of 0.70 or more in a number-based equivalent circle diameter-circularity scattergram measured by a flow type particle image measuring device. It meets the following range,
4.00 ≦ average particle size (μm) ≦ 6.30
0.950 ≦ average circularity ≦ 0.990
The nonmagnetic toner according to claim 1, wherein the 10% particle diameter and the 90% particle diameter satisfy the following relational expression (5).
1.20 ≦ 90% particle size / 10% particle size ≦ 2.00 (5) The toner is a toner having a circle equivalent diameter of 0.60 μm or more and less than 1.00 μm with respect to the total number of particles having a circularity of 0.70 or more in a scattergram based on the number of circles measured by a flow type particle image measuring apparatus. The nonmagnetic toner according to any one of claims 1 to 3, wherein the abundance A (number%) of the particles satisfies the following range.
0.10 ≦ A (%) ≦ 8.00 5. The non-magnetic toner according to claim 1, wherein the A (number%) satisfies the following range.
0.10 ≦ A (%) ≦ 5.00 The toner is non-magnetic according to any one of claims 1 to 5, characterized in that it contains a single polymer or copolymer obtained by polymerizing at least a styrene or a styrene derivative as a low molecular weight polymer toner. The toner is non-magnetic toner according to any one of claims 1 to 6, characterized in that said toner particles are toner particles produced in an aqueous medium. The toner is non-magnetic toner according to any one of claims 1 to 7, characterized in that said toner particles are toner particles produced by suspension polymerization. The toner is non-magnetic toner according to any one of claims 1 to 8, characterized in that a one-component developer.

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