JP4472387B2 - Image forming method - Google Patents

Description

  The present invention relates to an image forming apparatus that forms an image by an electrostatic copying process, such as a copying machine, a facsimile machine, and a printer, and a toner used in the image forming apparatus.

In an electrophotographic image forming apparatus, a charging step for applying a charge to the surface of a photoconductor as an image carrier, an exposure step for exposing the charged photoconductor surface to form an electrostatic latent image, and a photoconductor A toner image is formed on the photoreceptor through a developing process in which toner having a polarity opposite to that of the electrostatic latent image formed on the surface is supplied and developed. For this reason, the developing process is performed by a developing device provided in the image forming apparatus. To supplement toner consumption, toner is supplied from the toner container to the developing device.
Recently, high-precision reproducibility of images to be formed has been demanded. For this reason, a toner with a reduced particle size is used. However, the toner having a reduced particle size has low toner fluidity, and when toner is replenished with a screw or the like, a hollow is formed in a pillow shape and may not be replenished. In addition, the toner may clog by sticking to a screw or the like. Furthermore, the image forming apparatus tends to be reduced in size and speed. As the speed of the image forming apparatus increases, a large amount of toner for replenishment is required, so that the toner storage container is also increased, and stable replenishment is required. Further, the toner storage container may be disposed at a location away from the developing device due to the downsizing of the image forming apparatus. For this purpose, an agent transfer device using a powder pump is provided to smoothly and stably supply toner from a remote toner container to the developing device.

For this reason, for example, in Patent Document 1, the air supply path from the air outlet of the air pump to the air connection port that is the junction of the path 93 and the toner transfer tube in the toner supply path is the gravitational direction of the path and the toner transfer tube. An image forming apparatus is disclosed that is disposed so as to be at a height position higher than the lowest position.
In addition, for example, in Patent Document 2, a stator having a through hole and a rotor disposed in the through hole are provided. In the powder transfer pump for transferring the body, there is disclosed a powder transfer pump provided with stirring means for stirring the powder discharged from the outlet opening of the through hole.

JP 2004-037911 A JP 2002-087592

However, with the above disclosed technique, it is difficult to smoothly supply toner in a toner supply system using a toner having a reduced particle size and a powder pump.
Accordingly, the present invention has been made in view of the above circumstances, and an object thereof is to provide an image forming apparatus capable of smoothly replenishing toner with an agent transfer device using a powder pump, even for a small particle size toner. It is to be.

The features of the present invention, which is a means for solving the above problems, are listed below.
1. The image forming method of the present invention, using an image forming apparatus including a dosage transfer device transferring to the developing device using a powder pump a developer containing a toner or the toner having a volume average particle size. 2 to 5.88 [mu] m In the image forming method , the toner is produced after (1) a colorant, a release agent, a polymer or a polymerizable monomer is dispersed in an aqueous medium, and (2) a flow type particle. A circularity of 0.95 to 0.98 with an image analyzer, and (3) a penetration of the toner measured in accordance with JIS K2235 is 10 mm or more.
2. The image forming method of the present invention is further characterized in that the storage container storing the toner in the agent transfer device is a deformable storage bag.
3. Further, in the image forming method of the present invention, when the storage container is set in the main body of the image forming apparatus, the powder pump is drivingly connected to the drive unit of the main body of the image forming apparatus, and the developer or the toner is to contact a portion of the member which is movable by a drive coupling, the toner is you characterized by 0.7~2.0μm is 10% by number or less in the measurement of the flow-type particle size image analyzer.

4). Further, in the image forming method of the present invention, the powder pump is connected to a side surface of a transfer tube, and one end of the transfer tube is connected to the developing device, and the other end is connected to an air supply unit. The toner discharged from the storage container by the powder pump is transferred to the developing device by an air flow by the air supply means .
5. Further, in the image forming method of the present invention, the toner is a toner having a volume average particle diameter (Dv) to number average particle diameter (Dn) ratio Dv / Dn of 1.25 or less. .
6). The image forming apparatus of the present invention, further, the toner, characterized by the presence of fine particles having an average particle size of 30~300nm the toner surface.

7). The image forming method of the present invention is further characterized in that the toner has fine particles which are either or both of organic fine particles and / or inorganic fine particles present on the toner surface .
8). In the image forming apparatus of the present invention, the toner may further include a compound having an active hydrogen group, a polymer having a site capable of reacting with the compound having an active hydrogen group, a colorant, and a release agent in an organic solvent. Dissolving or dispersing the agent, dispersing the solution or dispersion in an aqueous medium, reacting the compound having an active hydrogen group and the polymer, or removing the organic solvent while reacting, It is characterized by being washed and dried.
9. The image forming method of the present invention is further characterized in that the image forming apparatus uses an amorphous silicon photoreceptor .
10. The image forming method of the present invention, further, charging device, characterized in that by contacting a charging member to the image bearing member.

11. Further, in the image forming method of the present invention, the image forming apparatus further includes a heating body having a heating element, a fixing film in contact with the heating body, and a pressure member in pressure contact with the heating body through the fixing film. And a fixing device that heats and fixes a recording member on which an unfixed image of toner is formed between the fixing film and the pressure member .
12 In the image forming apparatus of the present invention, the image forming apparatus further integrally supports an image carrier and at least one device selected from a charging device, a developing device, and a cleaning device. A process cartridge that is detachable is used .

In the toner of the present invention, even if the toner has low fluidity, it can be easily replenished by the means for solving the above problems, and toner clogging in the conveyance path can be prevented. Further, it is possible to toner remains in the toner conveying path can be prevented cheat the raw.
In the image forming apparatus of the present invention, the toner can be replenished smoothly, and the occurrence of a decrease in toner density and a decrease in image density can be prevented.

  As a result of intensive studies by the present inventors to solve such problems, a toner having a volume average particle diameter of 2 to 8 μm or a developer containing toner is transferred to a developing device using a powder pump. The toner is manufactured by dispersing (1) a colorant, a release agent, a polymer or a polymerizable monomer in an aqueous medium, and (2) a flow type particle image analyzer. In an agent transfer device using a powder pump, by using a toner having a circularity of 0.92 to 0.98 and (3) a toner characterized by a penetration of the toner of 10 mm or more, It has been found that even toner stored at high temperature can be conveyed to the developing device with good initial fluidity. In particular, the powder characteristics after long-term storage at high temperatures can be measured by the penetration, and if the penetration is 10 mm or more, the developing device has good initial fluidity even with toner stored at high temperatures. It was found that it can be transported.

  Further, preferably, in the agent transfer device 120 using the powder pump 140, the toner is stored in the deformable toner storage container 121, and the flow type particle image analyzer has a circularity of 0.92 to 0.98 and a heavy weight. The legal toner is easy to produce a toner having a small particle size and a narrow particle size distribution as compared with the pulverized toner. However, the polymerization toner has a shape closer to a sphere than the pulverized toner, but tends to have poor initial fluidity. Further, the deformable storage bag to be used with priority from the viewpoint of resource saving does not require a structure in which the entire toner storage container 121 is driven. Therefore, when the polymerization method toner is filled in a deformable storage bag and used, the state becomes close to closest packing. In order to release the toner, the entire toner storage container 121 cannot be driven, and furthermore, since it is a deformable storage bag, it is difficult to obtain a sufficient space for releasing the toner. As a result, even with a deformable storage bag, a sufficient degree of space between the particles for releasing the toner can be obtained by slightly deviating the circularity from the perfect sphere. The low fluidity can be improved.

Further, preferably, when the toner container 121 is set in the main body of the toner storage unit 114 of the image forming apparatus 100, the powder pump 140 is drivingly connected to the driving unit of the main body of the image forming apparatus 100, and the toner or developer. When the toner is used in an image forming apparatus that comes into contact with a part of a member that is moved by driving connection, the toner should be 0.7% to 2.0 μm and 10% by number or less as measured by a flow type particle image analyzer. Is desirable.
When the member moved by the drive connection and the toner or developer come into contact with each other, there is a possibility that fine powder in the toner enters between the movable parts. In particular, in the case of a system in which the drive unit is driven by setting the storage container 121 to the main body of the image forming apparatus 100, such as the powder pump 140, the reliability of the drive unit greatly affects toner conveyance. If the reliability of the drive unit is reduced, toner clogging, toner fusion, abnormal noise, etc. may occur. In order to ensure the reliability of the drive unit, at least the toner has a particle size of 0.7 to 2 μm as measured by a flow-type particle size analyzer and is 10% by number or less, preferably 5% by number or less, most preferably 3 % Or less is desirable.

The best mode for carrying out the present invention will be described below with reference to the drawings. FIG. 1 is a diagram showing a schematic configuration of an image forming apparatus of the present invention. FIG. 2 is a diagram showing a configuration of a process cartridge of the image forming apparatus shown in FIG.
A charging device 3, an exposure device 4, a developing device 5, a transfer device 6, a cleaning device 7, and a fixing device 8 are arranged around the photoreceptor 1 as an image carrier.

  The photoreceptor 1 is provided with a photosensitive layer on a belt-shaped or drum-shaped aluminum substrate. For the photosensitive layer, amorphous selenium, photoconductive perylene-based, phthalocyanine-based organic compound, or amorphous silicon is used. In particular, amorphous silicon is preferable. The conductive support is heated to 50 ° C. to 400 ° C., and a-Si is formed on the support by a film forming method such as a vacuum deposition method, a sputtering method, an ion plating method, a thermal CVD method, a photo CVD method, or a plasma CVD method. An amorphous silicon photoconductor (hereinafter referred to as “a-Si-based photoconductor”) having a photoconductive layer made of can be used. Among these, a plasma CVD method, that is, a method in which a source gas is decomposed by direct current, high frequency or microwave glow discharge to form an a-Si deposited film on a support is preferably used.

FIG. 3 is a schematic view schematically showing the structure of the amorphous silicon photosensitive member.
The photoconductor 1 shown in FIG. 1A is provided with a photoconductive layer 12 made of a-Si: H, X and having photoconductivity on a support 11. The photoconductor 1 shown in FIG. 2B includes a photoconductive layer 12 made of a-Si: H, X and having photoconductivity, and an amorphous silicon surface layer 13 on a support 11. The photoconductor 1 shown in (c) has a photoconductive layer 12 made of a-Si: H, X and having photoconductivity, an amorphous silicon surface layer 13 and an amorphous silicon charge injection on a support 11. And a blocking layer 14. The photoconductor 1 shown in (d) is provided with a photoconductive layer 12 on a support 11. The photoconductive layer 12 comprises a charge generation layer 15 and a charge transport layer 16 made of a-Si: H, X, and an amorphous silicon-based surface layer 13 is provided thereon. Amorphous silicon photoconductors have high surface hardness, high sensitivity to long-wavelength light such as LD laser light (770 to 800 nm), and almost no deterioration due to repeated use. It is used as the photoreceptor 1 of the image forming apparatus 100 such as a beam printer (LBP).

The charging device 3 uniformly charges the surface of the photoreceptor 1. The charging device 3 in the present embodiment includes a charging roller 3a as a charging member that performs a charging process for charging to a negative polarity by a so-called contact / proximity charging method.
FIG. 4 is a graph showing the relationship between the applied voltage and the charging potential of the photoreceptor. In the injection charging mechanism by contact, the photosensitive member 1 can be charged simultaneously with the application of a voltage, and the applied voltage can be reduced to make the photosensitive member 1 have a constant charging potential Vd. Thereby, generation | occurrence | production of ozone can also be suppressed few. In the discharge charging mechanism, the threshold voltage Vth is required to destroy and discharge air according to Paschen's law, and therefore it is necessary to increase the potential applied to make the photoreceptor 1 have a constant potential Vd.

FIG. 5 is a schematic diagram showing a configuration of a charging device used in the image forming apparatus of the present invention.
The charging roller 3 a is preferably used in contact with the photoreceptor 1. As shown in FIG. 5, the charging roller 3a brought into contact with the photosensitive member 1 is basically composed of a core metal 3c and a conductive rubber layer 3d concentrically and integrally formed on the outer periphery of the core metal 3c. Both ends of the photosensitive drum are held freely rotating by a bearing member (not shown) and the photosensitive drum is pressed with a predetermined pressure by a pressing means (not shown). In the case of this figure, the charging roller 3a is photosensitive. It rotates following the rotational drive of the body 1. The charging roller 3a is formed to have a diameter of 16 mm by coating a medium resistance rubber layer of about 100,000 Ωcm on a core metal 3c having a diameter of 9 mm.
A cored bar 3c of the charging roller 3a and a power source 3g shown in the figure are electrically connected, and a predetermined bias is applied to the charging roller 3a by the power source 3g. As a result, the peripheral surface of the photoreceptor 1 is uniformly charged to a predetermined polarity and potential. Further, even when toner is slightly adhered, the surface of the charging roller 3a may be cleaned by the cleaning roller 3b in order to prevent charging failure such as charging unevenness by the charging roller 3a.

In addition to the roller, the charging member may take any form such as a magnetic brush or a fur brush, and can be selected according to the specifications and form of the image forming apparatus 100. When the magnetic brush is used, the magnetic brush is made up of various ferrite particles such as Zn-Cu ferrite as a charging member, a nonmagnetic conductive sleeve for supporting the ferrite member, and a magnet roll included in the nonmagnetic conductive sleeve. In addition, when using a fur brush, for example, as a material of the fur brush, a fur treated with carbon, copper sulfide, metal, and metal oxide is used, and this is wound around a metal or other conductive cored bar. By charging or pasting, the charging device 3 is obtained.
An electrostatic latent image corresponding to each color is formed on the surface of the photoreceptor 1 charged in this manner by exposure by the exposure device 4. The exposure device 4 writes an electrostatic latent image corresponding to each color on the photoreceptor 1 based on image information corresponding to each color. The exposure apparatus 4 of the present embodiment is a laser type exposure apparatus, but other types of exposure apparatuses such as an exposure apparatus including an LED array and an image forming unit may be employed.

  The exposure device 4 converts data read by the scanner in the reading device 20 and an image signal sent from the outside such as a PC (not shown), scans the laser beam 3a with a polygon motor, and converts the image signal read through the mirror. Based on this, an electrostatic latent image is formed on the photoreceptor 1.

The developing device 5 includes a developing sleeve 5 a that is a developer carrying member that carries a developer and supplies the developer 1 to the photoreceptor 1, a toner supply chamber, and the like. It has a cylindrical developer carrier 5a disposed at a minute distance from the photoreceptor 1, and a developer regulating member that regulates the amount of developer on the developer carrier 5a. The developer carrier 5a includes a hollow cylindrical developer carrier 5a that is rotatably supported, and a magnet roll fixed coaxially with the developer carrier 5a. The developer is magnetically attracted to the outer peripheral surface of the carrier 4a and conveyed. The developer carrier 4a is electrically conductive and is made of a nonmagnetic member, and is connected to a power source for applying a developing bias. A voltage is applied from the power source between the developer carrying member 4a and the photoreceptor 1, and an electric field is formed in the developing region.
Although the above has described a developing device using a two-component developer, the present invention is not limited to this, and a developing device using a one-component developer may be used.

  The transfer device 6 includes a transfer belt 6a, a transfer bias roller 6b, and a tension roller 6c. The transfer bias roller 6b is configured by providing an elastic layer on the surface of a core metal such as iron, aluminum, and stainless steel. The transfer bias roller 6 b is applied with a necessary pressure on the photosensitive member 1 side in order to bring the recording paper into close contact with the photosensitive member 1. The transfer belt 6a can obtain an effect by selecting various heat-resistant materials as a base material, and can be composed of, for example, a seamless polyimide film. A configuration in which a fluororesin layer is provided on the outside can be employed. Further, if necessary, a silicone rubber layer may be provided on the polyimide film, and a fluororesin layer may be provided thereon. Inside the transfer belt 6a, a tension roller 6c is provided to drive and stretch the transfer belt 6a.

  The fixing device 7 includes a fixing roller having a heater that is a heating unit such as a halogen lamp, and a pressure roller that is in pressure contact. In the fixing roller, an elastic layer such as silicone rubber is provided on the surface of the core metal to a thickness of 100 to 500 μm, preferably 400 μm, and for the purpose of preventing adhesion due to toner viscosity, a resin surface layer having good releasability such as fluororesin Is formed. The resin surface layer is composed of a PFA tube or the like, and its thickness is preferably about 10 to 50 μm in consideration of mechanical deterioration. A temperature detecting means is provided on the outer peripheral surface of the fixing roller, and the heater is controlled so as to keep the surface temperature of the fixing roller substantially constant within a range of about 160 to 200 ° C. In the pressure roller, the core metal surface is coated with an anti-offset layer such as tetrafluoroethylene-perfluoroalkyl vinyl ether (PFA) or polytetrafluoroethylene (PTFE). Similar to the fixing roller, an elastic layer such as silicone rubber may be provided on the surface of the core metal.

FIG. 6 is a schematic diagram showing the configuration of another type of fixing device used in the image forming apparatus of the present invention. Here, the fixing device 8 is a so-called surf fixing device 80 that rotates and fixes the fixing film 81 as shown in FIG. The fixing film 81 is an endless belt-like heat-resistant film, and is fixed and supported by a driving roller 82, a driven roller 83, which is a supporting rotating body of the film, and a flat substrate 86 provided below the rollers. It is stretched around the heating element 84 provided. The driven roller 83 also serves as a tension roller for the fixing film 81, and the fixing film 81 is rotationally driven in the clockwise direction by the rotational driving of the driving roller 82 in the clockwise direction. The rotational driving speed is adjusted to a speed at which the transfer material and the fixing film 81 are equal in the fixing nip region L where the pressure roller 88 and the fixing film 81 are in contact with each other.
Here, the pressure roller 88 is a roller having a rubber elastic layer having good releasability such as silicon rubber, and is in contact with the fixing nip region L with a total pressure of 4 to 10 kg while rotating counterclockwise. It is pressed with pressure.
The fixing film 81 preferably has excellent heat resistance, releasability, and durability, and a thin film having a total thickness of 100 μm or less, preferably 40 μm or less is used. For example, a single layer film of heat-resistant resin such as polyimide, polyetherimide, PES (polyether sulfide), PFA (tetrafluoroethylene bar fluoroalkyl vinyl ether copolymer resin), or a composite layer film, for example, a 20 micron thick film At least on the image contact surface side, a release coating layer in which a conductive material is added to fluororesin such as PTFE (tetrafluoroethylene resin) and PFA is applied to a thickness of 10 μm, and elasticity such as fluororubber and silicon rubber Layered.

In FIG. 6, the heating body 84 of the fixing device 80 includes a flat base 86 and a fixing heater 87, and the flat base 86 is made of a material having high thermal conductivity and high electrical resistivity such as alumina. On the surface in contact with the fixing film 81, a fixing heater 87 composed of a resistance heating element is installed in the longitudinal direction. The fixing heater 87 is formed by, for example, applying an electric resistance material such as Ag / Pd or Ta ₂ N in a linear or belt shape by screen printing or the like.
In addition, electrodes (not shown) are formed at both ends of the fixing heater 87, and the resistance heating element generates heat by energizing between the electrodes. Further, a fixing temperature sensor 85 constituted by a thermistor is provided on the surface opposite to the surface provided with the fixing heater 87 of the flat substrate 86. The substrate temperature information detected by the fixing temperature sensor 85 is sent to a control means (not shown), and the amount of electric power supplied to the fixing heater 87 is controlled by the control means, and the heating body 84 is controlled to a predetermined temperature.
With this surf fixing device 80, an image forming apparatus 100 using the fixing device 8 that is efficient and can shorten the rise time can be obtained.
As shown in FIG. 2, the cleaning device 8 includes a cleaning blade 8 a as a cleaning unit for toner remaining on the surface of the photoreceptor 1 after the transfer process. Further, a toner collection blade 8d for collecting the cleaned toner and a collection coil 8c for conveying the toner are provided. Further, a toner collection box (not shown) is provided. The cleaning blade 8a is made of a material such as metal, resin, rubber, etc., but rubber such as fluorine rubber, silicone rubber, butyl rubber, butadiene rubber, isoprene rubber, urethane rubber is preferably used, and among them, urethane rubber is particularly preferable.

In the image forming apparatus of the present invention, the developing device 5 further includes an agent transfer device 120 in which the toner in the toner storage container 121 is replenished via the transfer tube 115 by the pumping force of the powder pump 140.
FIG. 7 is a block diagram showing a schematic configuration of the agent transfer device.
The drive / control of the agent transfer device 120 is performed by driving / controlling the powder pump 140 and operating / controlling the air pump 130 by a power source and control circuit (not shown). The control of the agent transfer device 120 uses a mechanism that detects a change in the mixing ratio of the toner and the carrier based on a toner density sensor provided in a part of the developing device 5 and controls the toner replenishment amount. For example, a technique of detecting the reflection density of the toner image on the photosensitive member 1 and controlling the toner replenishment amount may be diverted. The agent transfer device 120 is controlled by a control device having an MPU (not shown). That is, the detection result of the toner density sensor is taken into the MPU, and an operation signal is transmitted from the MPU to the powder pump drive source or drive transmission means (clutch or the like) and the air pump 130 according to the detection result, whereby the developing device The toner replenishing operation is performed. The MPU has a timer function and can drive and control a drive motor, an air pump, and the like at an arbitrary timing.
When the toner supply signal is transmitted, the rotor 141 and the air pump 130 of the powder pump 140 are simultaneously operated for a predetermined time, and the fluidized toner is sent to the developing device 5 through the transfer tube 115 by the powder pump 140. The air pump 130 is stopped after a predetermined time of operation after the rotor 141 of the powder pump 140 is stopped. In this way, since the residual toner in the transfer tube 115 can be discharged only by air, toner clogging in the toner transfer tube 115 can be prevented.

FIG. 8 is a schematic view showing the configuration of the agent transfer device.
As shown in FIG. 8, as the transfer tube 115, it is very preferable to use a rubber material having an inner diameter of 4 to 10 mm, flexible and excellent in toner resistance, such as polyurethane, nitrile, EPDM, or silicon. It is effective for. The developer in the developing device 10 is circulated so as to be conveyed by the first stirring screw 12. During this circulation, the electrostatic latent image formed on the photoreceptor 1 is developed by the developer transferred to the developing sleeve 5a in the middle of the conveyance path. Further, an air filter is provided in the upper part of the developing device 5 to allow only air from the transferred toner and air to escape to the outside of the developing device 5 to prevent the toner from scattering from the connecting member and the developing device 5 when the toner is replenished. The toner storage container 121 has a bag shape with an opening at the lower center, and a base member 22 made of a resin such as polyethylene or nylon is fixed to the opening. As the toner storage container, a flexible and deformable bag is used as the toner storage container 121, and the bag portion 121 is formed of a flexible sheet material (about 80 to 125 μm thick) such as a polyester film or a polyethylene film with a single layer or multiple layers. Thus, a bag-like container shape is preferred. The toner storage container 121 is not limited to the bag shape, and may be a horizontal type as long as the toner is transported to the powder pump 140.
The base member 122 is formed in a sleeve shape, and the powder pump 140 is detachably mounted in the hollow portion thereof. The powder pump 140 is a discharge-type uniaxial eccentric screw pump, which is a rotor 141 made of a screw eccentric with a material having rigidity such as metal, and an elastic body such as rubber, and a twin screw inside. And a stator 142 that is fixed in shape and installed. In this case, the stator 142 is fitted into the base member 122 from below and is held at the fitted position by the receiving member 123. Since the receiving member 123 is detachably fixed to the base member 122 by screwing, engagement or the like, removing the receiving member 123 causes the stator 142 and the rotor 141 to move to the toner as shown in FIG. It can be detached from the storage container 121.

  The base member 122 is provided with a stopper 124 via an arm or the like, and this stopper 124 can prevent the rotor 141 from moving into the container by rotation. The stopper 124 may be provided with a bearing that rotatably supports the rotor 141. The set unit 150 in which the toner storage container 121 provided in the image forming apparatus main body is set is provided with a drive shaft 51 that is driven to rotate by a drive source (not shown) and extends in the vertical direction. The drive shaft 151 is a set unit. A joint 52 that can be engaged with the rotor 141 is fixed to the front end, that is, the upper end of the lower member 150a. Further, the drive shaft 151 is mounted so as to be movable up and down and is urged upward by a spring 154. Accordingly, the drive shaft 151 stands by at a position where the fixed plate 154a contacts the bearing 153, and when the toner storage container 121 is set, the joint 152 is lowered at a position lower than the standby position against the action of the spring 154. Since it engages with the rotor 141, the engagement is ensured by the spring force.

In the set unit 150, a portion from which the toner is discharged by the powder pump 140 is formed in a pipe shape extending in the left-right direction in the figure, and one end thereof is connected to the developing device 5 via the transfer tube 115. The other end is connected via an air pipe 131 and an air pump 130 as air supply means. Therefore, the toner discharged from the container by the powder pump 140 is transferred to the developing device 5 by the air flow by the air pump 130.
The single-shaft eccentric screw pump that is the powder pump 140 is known to be capable of continuous quantitative transfer of powder at a high solid-gas ratio and to obtain an accurate toner transfer amount proportional to the rotational speed of the rotor 141. ing. Therefore, the toner transfer amount that is the toner replenishment amount may be controlled by controlling the rotation speed and driving time of the powder pump 140. When the rotor 141 rotates, the powder pump 140 generates a discharge pressure in the downward direction and generates a suction pressure in the upward direction. The magnitude of the discharge pressure or the suction pressure depends on the shape of the rotor 141 and the stator 142 of the powder pump 140 and the rotational speed of the rotor 141. Further, the transfer path of the transfer tube 115 is free and can be freely transferred in a high position or in any direction of up, down, left and right. Further, the supply amount of air may be very small, such as a maximum flow rate (no load) of 1 to 2 liters / minute, and air can be easily evacuated in the developing device 5 and the occurrence of toner scattering can be easily prevented.

The powder pump provided in the toner storage container 121 serves as a self-closing valve that is completely sealed when stopped, and the opening of the toner storage container 121 is sealed so that the toner does not scatter to the outside. Therefore, it is possible to reliably prevent toner scattering and contamination at the time of replacement.
Furthermore, since the powder pump 140 can be detached from the toner storage container 121, the pump portion can be regenerated and reused. Note that the powder pump 140 has a life when the rubber stator 142 is worn, but in this case as well, the rotor 141 can be used any number of times if only the stator 142 is replaced. Since the lower part of the toner container 121 has a funnel shape toward the toner discharge hole, the toner in the container is discharged without remaining in the container by gravity and the suction force on the upstream side of the powder pump. The

Next, another embodiment of the present invention will be described. FIG. 9 is a schematic view showing the configuration of the agent transfer device of another embodiment. In FIG. 9, in the image forming apparatus 100, the electrostatic latent image formed on the photoreceptor 1 is developed as a toner image by the developing device 5. The toner replenishing mechanism includes a developing device 5, a powder pump 140, an air pump 130, and a flow path opening / closing member.
The developing device 5 is replenished with toner from a toner container 121 containing toner as a developer container through a powder pump 140 and a transfer tube 115 as suction means. The developing device 5 is provided with a developing sleeve 5a disposed opposite to the photoreceptor 1, a stirring screw 5b, and a supply screw 5d. Reference numeral 5c denotes a doctor blade for making the developer layer thickness uniform.

As shown in FIG. 9, the powder pump 140 uses a suction type uniaxial eccentric screw pump provided in the vicinity of the developing device 5. The configuration of the powder pump 140 includes a rotor 141 formed in a screw shape eccentric with a rigid material such as metal, and a stator 142 formed in an elastic body such as rubber and formed in a double thread shape. have. The rotor 141 has a drive shaft 143 coupled by a pin joint and is coupled to a drive motor 144.
The powder pump 140 is connected to a toner discharge path 156 provided in the nozzle 155 by a toner transfer tube 115.
The single-shaft eccentric screw pump that is the powder pump 140 is known to be capable of continuous quantitative transfer at a high solid-gas ratio, and to obtain an accurate toner transfer amount proportional to the rotational speed of the rotor 141. Yes. Therefore, when a toner replenishment command is issued by image density detection or the like, the powder pump 140 is operated, and the requested amount of toner can be smoothly replenished to the developing device 5.

In addition, a toner having a volume average particle diameter in the range of 2 to 8 μm used for the agent transfer device 120, after dispersing a colorant, a release agent, a polymer or a polymerizable monomer in an aqueous medium. It is manufactured and has a circularity of 0.92 to 0.98 by a flow type particle image analyzer, and the penetration of toner is 10 mm or more.
The toner has a volume average particle diameter Dv of 2 to 8 μm. The smaller the volume average particle diameter Dv of the toner, the better the fine line reproducibility. For this reason, at most 8 μm or less is preferable for high thin line reproducibility. However, since the cleaning property decreases when the particle size is small, at least 2 μm is preferable.
In the present invention, toner having an average circularity in the range of 0.93 to 0.98 is used. This circularity is defined by the circularity SR = (peripheral length of a circle having the same area as the particle projection area / perimeter length of the particle projection image), and becomes closer to 1.00 as the toner is closer to a true sphere. Since toner having a circularity in the range of 0.93 to 0.98 is easy to roll, it can be easily transferred by the agent transfer device. Further, it is easily affected by the lines of electric force on the developing sleeve in the image forming apparatus, and is faithfully developed along the electric lines of force of the electrostatic latent image. When reproducing minute latent image dots, fine line reproducibility is enhanced because it is easy to obtain a dense and uniform toner arrangement. In addition, a toner with a high degree of circularity has a smooth surface and a suitable fluidity, so it is easily affected by the lines of electric force and easily transfers faithfully along the lines of electric force. A quality image can be obtained. However, when the average circularity of the toner is less than 0.93, the toner has an irregular shape, a dead space is formed by the agent transfer device, and in other words, the developing device may not be replenished. Further, if it exceeds 0.98, it becomes close to a true sphere, easily rolls, leaks from the cap of the toner storage container, and leaks from the replenishing port of the developing device with a momentum on the air flow. . In addition to being in the range of average circularity, the proportion of toner having a circularity of less than 0.93 is preferably 30% or less. In a toner with a large variation in circularity such that this ratio exceeds 30%, the amount of toner leaking from the gap increases.
The average circularity was measured using a flow type particle image analyzer (FPIA-2000; manufactured by Sysmex Corporation). In a predetermined container, 100 to 150 mL of water from which impure solids had been removed in advance was added, 0.1 to 0.5 mL of a surfactant was added as a dispersant, and about 0.1 to 9.5 g of a measurement sample was further added. . The suspension in which the sample was dispersed was subjected to dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the dispersion concentration was set to 3,000 to 10,000 / μL, and the shape and distribution of the toner were measured.

Also, penetration was measured according to JIS K2235 is Ru der least 10 mm. By this, it is possible to evaluate the resistance to thermal or mechanical impact of the toner. Therefore, when the penetration is 10 mm or more, the resistance to thermal or mechanical impact is low, and in the case of conveyance by a normal conveyance screw, the molten toner adheres to the conveyance screw. Further, even when the air flow is conveyed by the powder pump, the toner clogs by being stuck to the conveying tube and blocking the conveying path. However, it becomes easy to roll by increasing the circularity, and mechanical impact due to the shape is applied, so even if the toner has a penetration of 10 mm or more, it can be fixed to the tube with an agent transfer device using a powder pump. Therefore, toner can be replenished.

  More preferably, when the toner container 121 is set in the main body of the toner storage unit 114 of the image forming apparatus 100, the powder pump 140 is drivingly connected to the driving unit of the main body of the image forming apparatus 100, and the toner is driven and connected. It is desirable that the toner is in contact with a part of the movable member, and the toner has a number of 0.7 to 2.0 μm of 10% by number or less as measured by a flow type particle size analyzer. When the member moved by the drive connection and the developer or toner come into contact with each other, there is a possibility that fine powder in the toner may enter between the movable parts. In particular, in the case of a system in which the drive unit is driven by setting the storage container to the image forming apparatus main body, such as a powder pump, the reliability of the drive unit greatly affects toner conveyance. If the reliability of the drive unit is reduced, toner clogging, toner fusion, abnormal noise, etc. may occur. In order to ensure the reliability of the drive unit, at least the toner has a particle size of 0.7 to 2 μm as measured by a flow-type particle size analyzer, which is 10% or less, preferably 5% or less, and most preferably 3 It is desirable that the number is not more than%.

  Further, the toner preferably has a ratio (Dv / Dn) of 1.25 or less between the volume average particle diameter (Dv) and the number average particle diameter (Dn). Preferably, by setting Dv / Dn to be 1.25 or less, even when the air flow is transported in the powder pump, the toner having a small particle diameter is reduced, and the toner hits the transport tube and is fixed. By clogging the path, toner clogging can be reduced.

Further, this toner causes fine particles having an average particle diameter of 30 to 300 nm to be present on the toner surface. As the fine particles, inorganic fine particles and / or organic fine particles are used. If the average particle size is less than 30 nm, the particle size is weak against thermal or mechanical shock and is fixed to the drive connecting portion of the powder pump 140. On the other hand, if it exceeds 300 nm, the toner surface is prevented from coming into contact with other members, so that the fixing property is lowered and the fluidity of the toner is significantly lowered. Transport becomes difficult. Therefore, the primary particle diameter of the fine particles as an external additive is preferably 30 to 300 nm, particularly preferably 80 nm to 200 nm.
Specific examples of the inorganic fine particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, silica sand, clay, mica, silica, and the like. Examples include apatite, diatomaceous earth, chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride. The use ratio of the inorganic fine particles is preferably 0.1 to 10 wt% of the toner, and particularly preferably 1 to 5 wt%.
Also, organic fine particles, such as polystyrene obtained by soap-free emulsion polymerization, suspension polymerization, and dispersion polymerization, methacrylic acid ester and acrylic acid ester copolymer, polycondensation systems such as silicone, benzoguanamine, and nylon, and heavy polymers by thermosetting resin. Examples include coalesced particles.
Such external additives can be surface treated to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity. For example, silane coupling agents, silylating agents, silane coupling agents having an alkyl fluoride group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils and the like are preferable surface treatment agents. . In particular, it is preferable to use hydrophobic silica and hydrophobic titanium oxide obtained by subjecting silica and titanium oxide to the above surface treatment.

  The toner suitably used in the image forming apparatus 100 of the present invention is produced by a polymerization method (suspension polymerization, emulsion polymerization dispersion polymerization, emulsion aggregation, emulsion association, etc.), but is not limited to these production methods. . A toner composition comprising at least a compound having a site that reacts with an active hydrogen group as a polymer, in particular, a polyester prepolymer having a functional group containing a nitrogen atom, a polyester, a colorant, and a release agent. It is preferable to use a toner produced by a production method in which crosslinking and / or elongation reaction is performed in the presence of resin fine particles in an aqueous medium. By producing in such an aqueous medium, a toner having excellent dispersion of the colorant and the release agent and high fluidity can be obtained, and transferred to the developing device without forming a dead space in the agent transfer device. be able to. Hereinafter, the constituent material of the toner and the manufacturing method thereof will be described.

(Modified polyester)
The toner according to the present invention contains a modified polyester (i) as a binder resin. The modified polyester (i) refers to a state in which a bonding group other than an ester bond is present in the polyester resin, or resin components having different configurations are bonded to the polyester resin by a covalent bond, an ionic bond, or the like. Specifically, the polyester terminal is modified by introducing a functional group such as a carboxylic acid group or an isocyanate group that reacts with a hydroxyl group into the polyester terminal and further reacting with an active hydrogen-containing compound.

  Examples of the modified polyester (i) include urea-modified polyester obtained by a reaction between a polyester prepolymer (A) having an isocyanate group and amines (B). As the polyester prepolymer (A) having an isocyanate group, a polyester having a polycondensate of a polyhydric alcohol (PO) and a polyvalent carboxylic acid (PC) and having an active hydrogen group is further added to a polyvalent isocyanate compound (PIC). And those reacted with. Examples of the active hydrogen group possessed by the polyester include a hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group), an amino group, a carboxyl group, a mercapto group, and the like. Among these, an alcoholic hydroxyl group is preferable.

The urea-modified polyester is produced as follows.
Examples of the polyhydric alcohol compound (PO) include dihydric alcohol (DIO) and trihydric or higher polyhydric alcohol (TO). (DIO) alone or a mixture of (DIO) and a small amount of (TO) preferable. Examples of the dihydric alcohol (DIO) include alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.); alkylene ether glycol (diethylene glycol) , Triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); bisphenols (bisphenol A, bisphenol) F, bisphenol S, etc.); alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of the above alicyclic diol; Alkylene oxide bisphenol (ethylene oxide, propylene oxide, butylene oxide, etc.), etc. adducts. Among them, preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols, and particularly preferred are alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. It is a combined use. As trihydric or higher polyhydric alcohol (TO), 3 to 8 or higher polyhydric aliphatic alcohol (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); trihydric or higher phenols (Trisphenol PA, phenol novolak, cresol novolak, etc.); and alkylene oxide adducts of the above trivalent or higher polyphenols.

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

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

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

  The ratio of the polyvalent isocyanate compound (PIC) is usually 5/1 to 1/1, preferably as an equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] and the hydroxyl group [OH] of the polyester having a hydroxyl group. 4/1 to 1.2 / 1, more preferably 2.5 / 1 to 1.5 / 1. When [NCO] / [OH] exceeds 5, low-temperature fixability deteriorates. When the molar ratio of [NCO] is less than 1, when a urea-modified polyester is used, the urea content in the ester is lowered and hot offset resistance is deteriorated.

The content of the polyvalent isocyanate compound (PIC) component in the polyester prepolymer (A) having an isocyanate group is usually 0.5 to 40 wt%, preferably 1 to 30 wt%, more preferably 2 to 20 wt%. . If it is less than 0.5 wt%, the hot offset resistance deteriorates, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. On the other hand, if it exceeds 40 wt%, the low-temperature fixability deteriorates.
The number of isocyanate groups contained per molecule in the polyester prepolymer (A) having an isocyanate group is usually 1 or more, preferably 1.5 to 3 on average, more preferably 1.8 to 2 on average. Five. If it is less than 1 per molecule, the molecular weight of the urea-modified polyester will be low, and the hot offset resistance will deteriorate.

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

The ratio of amines (B) is equivalent to the equivalent ratio [NCO] / [NHx] of isocyanate groups [NCO] in the polyester prepolymer (A) having isocyanate groups and amino groups [NHx] in amines (B). Is usually 1/2 to 2/1, preferably 1.5 / 1 to 1 / 1.5, more preferably 1.2 / 1 to 1 / 1.2. When [NCO] / [NHx] is more than 2 or less than 1/2, the molecular weight of the urea-modified polyester is lowered, and the hot offset resistance is deteriorated.
The urea-modified polyester may contain a urethane bond together with a urea bond. The molar ratio of the urea bond content to the urethane bond content is usually 100/0 to 10/90, preferably 80/20 to 20/80, and more preferably 60/40 to 30/70. When the molar ratio of the urea bond is less than 10%, the hot offset resistance is deteriorated.

The modified polyester (i) used in the present invention is produced by a one-shot method or a prepolymer method. The weight average molecular weight of the modified polyester (i) is usually 10,000 or more, preferably 20,000 to 10,000,000, more preferably 30,000 to 1,000,000. The peak molecular weight at this time is preferably 1000 to 10,000, and if it is less than 1,000, the elongation reaction hardly occurs and the elasticity of the toner is small, and as a result, the resistance to hot offset deteriorates. On the other hand, if it exceeds 10,000, the problem in production becomes high in the case of a decrease in fixability, particle formation or pulverization. The number average molecular weight of the modified polyester (i) is not particularly limited when the unmodified polyester (ii) described later is used, and may be a number average molecular weight that can be easily obtained to obtain the weight average molecular weight. (I) When used alone, the number average molecular weight is usually 20000 or less, preferably 1000 to 10000, and more preferably 2000 to 8000. When it exceeds 20000, the low-temperature fixability and the glossiness when used in a full-color device are deteriorated.
In the crosslinking and / or extension reaction between the polyester prepolymer (A) and the amines (B) to obtain the modified polyester (i), a reaction terminator is used as necessary to adjust the molecular weight of the resulting urea-modified polyester. be able to. Examples of the reaction terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), and those obtained by blocking them (ketimine compounds).

(Unmodified polyester)
In the present invention, not only the modified polyester (i) is used alone, but also the unmodified polyester (ii) can be contained as a binder resin component together with the (i). By using (ii) in combination, the low-temperature fixability and the gloss when used in a full-color device are improved, which is preferable to single use. Examples of (ii) include polycondensates of polyhydric alcohol (PO) and polyvalent carboxylic acid (PC) similar to the polyester component of (i), and preferred ones are also the same as (i). . (Ii) is not limited to unmodified polyester, but may be modified with a chemical bond other than a urea bond, and may be modified with a urethane bond, for example. It is preferable that (i) and (ii) are at least partially compatible in terms of low-temperature fixability and hot offset resistance. Accordingly, the polyester component (i) and (ii) preferably have similar compositions. When (ii) is contained, the weight ratio of (i) to (ii) is usually 5/95 to 80/20, preferably 5/95 to 30/70, more preferably 5/95 to 25/75, Particularly preferred is 7/93 to 20/80. When the weight ratio of (i) is less than 5%, the hot offset resistance is deteriorated, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability.

  The peak molecular weight of (ii) is usually 1000 to 10,000, preferably 2000 to 8000, and more preferably 2000 to 5000. If it is less than 1000, heat-resistant storage stability will deteriorate, and if it exceeds 10,000, low-temperature fixability will deteriorate. The hydroxyl value of (ii) is preferably 5 or more, more preferably 10 to 120, and particularly preferably 20 to 80. If it is less than 5, it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. The acid value of (ii) is preferably 1 to 5, more preferably 2 to 4. Since a high acid value wax is used as the wax, the low acid value binder leads to electrification and high volume resistance, so that it is easy to match the toner used for the two-component developer.

  The glass transition point (Tg) of the binder resin is usually 35 to 70 ° C, preferably 55 to 65 ° C. If the temperature is lower than 35 ° C., the heat-resistant storage stability of the toner deteriorates, and if it exceeds 70 ° C., the low-temperature fixability becomes insufficient. Since the urea-modified polyester is likely to be present on the surface of the obtained toner base particles, the toner of the present invention tends to have good heat storage stability even when the glass transition point is low, as compared with known polyester-based toners. Show.

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

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

(Charge control agent)
Known charge control agents can be used, such as nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (fluorine-modified 4 Secondary ammonium salts or compounds, tungsten simple substances or compounds, fluorine activators, salicylic acid metal salts, and metal salts of salicylic acid derivatives. Specifically, Bontron 03 of a nigrosine dye, Bontron P-51 of a quaternary ammonium salt, Bontron S-34 of a metal-containing azo dye, E-82 of an oxynaphthoic acid metal complex, E-84 of a salicylic acid metal complex , Phenolic condensate E-89 (above, Orient Chemical Industries, Ltd.), quaternary ammonium salt molybdenum complex TP-302, TP-415 (above, Hodogaya Chemical Co., Ltd.), quaternary ammonium salt copy Charge PSY VP2038, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, LR-147 which is a boron complex (Nippon Carlit) Manufactured), copper phthalocyanine, perylene, quinacridone, azo series Fee, a sulfonic acid group, a carboxyl group, and polymer compounds having a functional group such as quaternary ammonium salts. Of these, substances that control the negative polarity of the toner are particularly preferably used.
The amount of the charge control agent used is determined by the type of binder resin, the presence or absence of additives used as necessary, and the toner production method including the dispersion method, and is not uniquely limited. Preferably, it is used in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the binder resin. The range of 0.2 to 5 parts by weight is preferable. When the amount exceeds 10 parts by weight, the chargeability of the toner is too high, the effect of the charge control agent is reduced, the electrostatic attraction with the developing roller is increased, the flowability of the developer is lowered, and the image density is lowered. Invite.

(Release agent)
As a release agent, a low melting point wax having a melting point of 50 to 120 ° C. works more effectively as a release agent in the dispersion with the binder resin between the fixing roller and the toner interface. The effect on high temperature offset is exhibited without applying a release agent such as oil. Examples of such a wax component include the following. Examples of waxes and waxes include plant waxes such as carnauba wax, cotton wax, wood wax, rice wax, animal waxes such as beeswax and lanolin, mineral waxes such as ozokerite and cercin, and paraffin, microcrystalline, And petroleum waxes such as petrolatum. In addition to these natural waxes, synthetic hydrocarbon waxes such as Fischer-Tropsch wax and polyethylene wax, and synthetic waxes such as esters, ketones, and ethers can be used. Furthermore, fatty acid amides such as 12-hydroxystearic acid amide, stearic acid amide, phthalic anhydride imide, chlorinated hydrocarbon, and low molecular weight crystalline polymer resin, poly-n-stearyl methacrylate, poly-n- A crystalline polymer having a long alkyl group in the side chain such as a homopolymer or copolymer of polyacrylate such as lauryl methacrylate (for example, a copolymer of n-stearyl acrylate-ethyl methacrylate, etc.) can also be used. .
The charge control agent and the release agent can be melt-kneaded together with the master batch and the binder resin, and of course, they may be added when dissolved and dispersed in the organic solvent.

(External additive)
Inorganic fine particles are preferably used as an external additive for assisting the fluidity, developability and chargeability of the toner. The primary particle diameter of the inorganic fine particles is preferably 5 × ¹⁰ -3 ~2μm, it is particularly preferably 5 × ¹⁰ -3 ~0.5μm. Moreover, it is preferable that the specific surface area by BET method is 20-500 m < ² > / g. The use ratio of the inorganic fine particles is preferably 0.01 to 5 wt% of the toner, and particularly preferably 0.01 to 2.0 wt%.
Specific examples of the inorganic fine particles include, for example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, quartz sand, clay, mica, wollastonite, diatomaceous earth. Examples include soil, chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride. Among these, as the fluidity-imparting agent, it is preferable to use hydrophobic silica fine particles and hydrophobic titanium oxide fine particles in combination. In particular, when stirring and mixing are performed using particles having an average particle diameter of 5 × 10 ⁻² μm or less, the electrostatic force and van der Waals force with the toner are remarkably improved. Even when stirring and mixing inside the developing device is performed to obtain a good image quality that does not cause the release of the fluidity imparting agent from the toner and does not generate firefly, etc., and further reduces the residual toner. It is done.
Titanium oxide fine particles are excellent in environmental stability and image density stability, but have a tendency to deteriorate the charge rising characteristics. It can be considered large. However, when the added amount of the hydrophobic silica fine particles and the hydrophobic titanium oxide fine particles is in the range of 0.3 to 1.5 wt%, the charge rising characteristics are not greatly impaired, and the desired charge rising characteristics can be obtained, that is, repeated copying. Stable image quality can be obtained even if

Next, a toner manufacturing method will be described. Here, although a preferable manufacturing method is shown, it is not limited to this.
(Toner production method)
1) A toner material solution is prepared by dispersing a colorant, unmodified polyester, a polyester prepolymer having an isocyanate group, and a release agent in an organic solvent.
The organic solvent is preferably volatile with a boiling point of less than 100 ° C. from the viewpoint of easy removal after toner base particle formation. Specifically, toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, methyl ethyl ketone, Methyl isobutyl ketone and the like can be used alone or in combination of two or more. In particular, aromatic solvents such as toluene and xylene and halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, chloroform, and carbon tetrachloride are preferable. The usage-amount of an organic solvent is 0-300 weight part normally with respect to 100 weight part of polyester prepolymers, Preferably it is 0-100 weight part, More preferably, it is 25-70 weight part.

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

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

Further, by using a surfactant having a fluoroalkyl group, the effect can be obtained in a very small amount. Preferred anionic surfactants having a fluoroalkyl group include fluoroalkyl carboxylic acids having 2 to 10 carbon atoms and metal salts thereof, disodium perfluorooctanesulfonyl glutamate, 3- [ω-fluoroalkyl (C6-C11 ) Oxy] -1-alkyl (C3-C4) sodium sulfonate, 3- [ω-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (C11-C20) carvone Acids and metal salts, perfluoroalkylcarboxylic acids (C7 to C13) and metal salts thereof, perfluoroalkyl (C4 to C12) sulfonic acids and metal salts thereof, perfluorooctanesulfonic acid diethanolamide, N-propyl-N- ( 2-Hydroxyethyl) Perful Olooctanesulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate, etc. Can be mentioned.
Product names include Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.), Florard FC-93, FC-95, FC-98, FC-129 (Sumitomo 3M Co., Ltd.), Unidyne DS-101. DS-102 (manufactured by Daikin Industries, Ltd.), Megafac F-110, F-120, F-113, F-191, F-812, F-833 (manufactured by Dainippon Ink, Inc.), Xtop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products), and Fgentent F-100, F150 (manufactured by Neos).

  Moreover, as the cationic surfactant, aliphatic quaternary ammonium such as aliphatic primary, secondary or secondary amic acid, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt which has a right fluoroalkyl group is used. Salts, benzalkonium salts, benzethonium chloride, pyridinium salts, imidazolinium salts, trade names include Surflon S-121 (Asahi Glass Co., Ltd.), Florard FC-135 (Sumitomo 3M Co., Ltd.), Unidyne DS-202 (Daikin Industries) Smoke), Megafac F-150, F-824 (Dainippon Ink Co., Ltd.), Xtop EF-132 (Tochem Products), Footage F-300 (Neos), and the like.

The resin fine particles are added to stabilize the toner base particles formed in the aqueous medium. For this reason, it is preferable to add so that the coverage existing on the surface of the toner base particles is in the range of 10 to 90%. For example, polymethyl methacrylate fine particles 1 μm and 3 μm, polystyrene fine particles 0.5 and 2 μm, poly (styrene-acrylonitrile) fine particles 1 μm, trade names are PB-200H (manufactured by Kao Corporation), SGP (manufactured by Soken Co., Ltd.), Techno Examples include polymer SB (manufactured by Sekisui Chemical Co., Ltd.), SGP-3G (manufactured by Sokensha), and micropearl (manufactured by Sekisui Fine Chemical Co., Ltd.).
In addition, inorganic compound dispersants such as tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, and hydroxyapatite can also be used.

As a dispersant that can be used in combination with the above resin fine particles and inorganic compound dispersant, the dispersed droplets may be stabilized by a polymer protective colloid. For example, acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride and other (meth) acrylic monomers containing hydroxyl groups Bodies such as acrylic acid-β-hydroxyethyl, methacrylic acid-β-hydroxyethyl, acrylic acid-β-hydroxypropyl, methacrylic acid-β-hydroxypropyl, acrylic acid-γ-hydroxypropyl, methacrylic acid-γ-hydroxy Propyl, acrylic acid-3-chloro-2-hydroxypropyl, methacrylic acid-3-chloro-2-hydroxypropyl, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate Luric acid esters, N-methylol acrylamide, N-methylol methacrylamide, etc., vinyl alcohol or ethers with vinyl alcohol, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, or compounds containing vinyl alcohol and a carboxyl group Esters such as vinyl acetate, vinyl propionate, vinyl butyrate, acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds, acid chlorides such as acrylic acid chloride, methacrylic acid chloride, vinyl pyridine, vinyl pyrrolidone, vinyl Nitrogen compounds such as imidazole and ethyleneimine, or homopolymers or copolymers such as those having a heterocyclic ring thereof, polyoxyethylene, poly Xoxypropylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxy Polyoxyethylenes such as ethylene nonylphenyl ester, celluloses such as methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose can be used.
The dispersion method is not particularly limited, and known equipment such as a low-speed shear method, a high-speed shear method, a friction method, a high-pressure jet method, and an ultrasonic wave can be applied. Among these, the high-speed shearing method is preferable in order to make the particle size of the dispersion 2 to 20 μm. When a high-speed shearing disperser is used, the rotational speed is not particularly limited, but is usually 1000 to 30000 rpm, preferably 5000 to 20000 rpm. The dispersion time is not particularly limited, but in the case of a batch method, it is usually 0.1 to 5 minutes. The temperature during dispersion is usually 0 to 150 ° C. (under pressure), preferably 40 to 98 ° C.

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

4) After completion of the reaction, the organic solvent is removed from the emulsified dispersion (reactant), washed and dried to obtain toner base particles.
In order to remove the organic solvent, the temperature of the entire system is gradually raised in a laminar stirring state, and after giving strong stirring in a certain temperature range, the solvent base is removed to produce spindle-shaped toner base particles. . Further, when an acid such as calcium phosphate salt or an alkali-soluble material is used as the dispersion stabilizer, the calcium phosphate salt is dissolved from the toner base particles by a method such as dissolving the calcium phosphate salt with an acid such as hydrochloric acid and washing with water. Remove. It can also be removed by operations such as enzymatic degradation.

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

Further, the toner according to the present invention has a substantially spherical shape and can be represented by the following shape rule.
FIG. 10 is a diagram schematically showing the shape of the toner according to the present invention. In FIG. 10, when a substantially spherical toner is defined by a major axis r1, a minor axis r2, and a thickness r3 (where r1 ≧ r2 ≧ r3), the toner of the present invention has a major axis and a minor axis. Ratio (r2 / r1) (see (b)) is 0.5 to 1.0, and ratio of thickness to minor axis (r3 / r2) (see (c)) is 0.7 to 1.0. It is preferable to be in the range. However, r3 / r1 is 0.98 or less. When the ratio of the major axis to the minor axis (r2 / r1) is less than 0.5, the dot reproducibility and transfer efficiency are inferior because of being away from the true spherical shape, and high-quality image quality cannot be obtained. On the other hand, if the ratio of thickness to minor axis (r3 / r2) is less than 0.7, the shape is close to a flat shape, and a high transfer rate like a spherical toner cannot be obtained. In particular, when the ratio of the thickness to the minor axis (r3 / r2) is 1.0, the rotating body has a major axis as a rotation axis, and the fluidity of the toner can be improved. However, it is not preferable that r3 / r1 is 0.99 or more because toner may leak from the toner cap or the developing device replenishing port because it has a substantially spherical shape. Note that r1, r2, and r3 were measured with a scanning electron microscope (SEM) while changing the angle of field of view and taking pictures.

The toner produced as described above can also be used as a one-component magnetic toner that does not use a magnetic carrier or a non-magnetic toner.
When used in a two-component developer, it may be used by mixing with a magnetic carrier, and the magnetic carrier is a ferrite containing a divalent metal such as iron, magnetite, Mn, Zn, Cu, The weight average particle diameter D ₄ is preferably 20 to 100 μm. If the average particle size is less than 20 μm, carrier adhesion is likely to occur on the photoreceptor 1 during development, and if it exceeds 100 μm, the miscibility with the toner is low and the charge amount of the toner is insufficient, resulting in poor charging during continuous use. Cheap. In addition, Cu ferrite containing Zn is preferable because of high saturation magnetization, but can be appropriately selected according to the process of the image forming apparatus. The resin for coating the magnetic carrier is not particularly limited, and examples thereof include silicone resin, styrene-acrylic resin, fluorine-containing resin, and olefin resin. In the manufacturing method, the coating resin may be dissolved in a solvent, sprayed into a fluidized bed and coated on the core, or the resin particles are electrostatically attached to the core particles and then thermally melted for coating. It may be a thing. The resin to be coated has a thickness of 0.05 to 10 μm, preferably 0.3 to 4 μm.

  The image forming apparatus 100 according to the present invention includes a photosensitive member 1 and one or more devices selected from a coating device 21, a charging device 3, a developing device 5, and a cleaning device 7, which are integrally supported to be attached and detached. A possible process cartridge 2 is provided. Accordingly, the developer and the developing device 5 can be easily replaced, and the main body of the image forming apparatus 100 can be used for a long time.

Hereinafter, the present invention will be specifically described based on examples.
(Production Example 1)
Styrene monomer: 185 parts butyl acrylate: 15 parts carnauba wax: 10 parts carbon black: 8 parts phthalocyanine blue: 1 part divinylbenzene: 2 parts azobisisobutyronitrile: 8 parts Heating the above materials to 70 ° C Then, the mixture was further mixed for about 5 minutes while heating at about 60 ° C. in a container equipped with a TK homomixer to obtain [Polymerizable mixture 1] having the above composition.

on the other hand,
Ion-exchanged water 1000 parts Colloidal silica (Aerol # 200) 4 parts The above materials are dispersed and heated to 60 ° C. to prepare [Aqueous Phase 1]. 1] was added and stirred at 4000 rpm for 60 minutes. This mixed system was stirred with a paddle blade stirring blade in a three-one motor to complete the polymerization. Thereafter, the dispersant is removed, washed thoroughly with water, the obtained cake is blown off, dried at 45 ° C. for 48 hours in a circulating dryer, and then air-sieved with a sieve having a mesh opening of 75 μm. 1] was obtained.

Example 1
(Mixing / Surface treatment ⇒ Toner)
[Toner base 1] To 200 parts of the toner, the following inorganic fine particles were added, followed by stirring at 45 m / s for 2 minutes with a Henschel mixer (manufactured by Mitsui Miike Chemical Co., Ltd.).
○ Inorganic fine particle A (BET200m2 / g) obtained by treating the surface with 9 parts of hexamethylene disilazane on 100 parts of silica fine particles: 0.3 part ○ The surface is treated with 8 parts of silicone oil on 100 parts of silica fine particles Inorganic fine particles B (BET50m2 / g) obtained by 7 parts This mixed toner was treated with a hybridization system (manufactured by Nara Machinery Co., Ltd.) at 50 m / s for 3 minutes. The maximum temperature in the system was 29 ° C.
Furthermore, the following inorganic fine particles were added to 100 parts of the obtained toner, and the mixture was stirred for 3 minutes at 45 m / s with a Henschel mixer (manufactured by Mitsui Miike Chemical Co., Ltd.).
○ Inorganic fine particles A (BET200m2 / g) obtained by treating the surface with 9 parts of hexamethylene disilazane to 100 parts of silica fine particles: 1.0 part ○ 100 parts of anatase-type titanium fine particles and 12 parts of isobutyltrimethoxysilane Inorganic fine particles C obtained by treating the surface with (BET 115 m 2 / g): 0.5 part The obtained toner was air sieved with a sieve having a mesh opening of 75 μm to obtain [Toner 1], which was evaluated. .

(Example 2)
(Mixing / Surface treatment ⇒ Toner)
[Toner base 1] To 200 parts of the toner, the following inorganic fine particles were added, followed by stirring at 45 m / s for 2 minutes with a Henschel mixer (manufactured by Mitsui Miike Chemical Co., Ltd.).
○ Inorganic fine particles A (BET200m2 / g) obtained by treating the surface with 9 parts of hexamethylene disilazane to 100 parts of silica fine particles: 0.3 parts ○ Resin fine particles produced by soap-free polymerization from styrene-methyl methacrylate B (volume average particle diameter 0.08 μm): 2.4 parts This mixed toner was treated with a hybridization system (manufactured by Nara Machinery Co., Ltd.) at 40 m / s for 5 minutes. The maximum temperature in the system was 31 ° C.
Furthermore, the following inorganic fine particles were added to 100 parts of the obtained toner, and the mixture was stirred for 3 minutes at 45 m / s with a Henschel mixer (manufactured by Mitsui Miike Chemical Co., Ltd.).
○ Inorganic fine particle A (BET200m2 / g) obtained by treating the surface with 9 parts of hexamethylene disilazane to 100 parts of silica fine particles: 1.0 part ○ 100 parts of anatase-type titanium fine particles and 12 parts of isobutyltrimethoxysilane Inorganic fine particles C obtained by treating the surface with (BET 115 m 2 / g): 0.5 part The obtained toner was air sieved with a sieve having a mesh opening of 75 μm to obtain [Toner 2], which was evaluated. .

(Comparative Example 1)
[Toner base 1] To 200 parts of the toner, the following inorganic fine particles were added, followed by stirring at 45 m / s for 3 minutes with a Henschel mixer (manufactured by Mitsui Miike Chemical Co., Ltd.).
○ Inorganic fine particles A (BET200m2 / g) obtained by treating the surface with 100 parts of silica fine particles and 9 parts of hexamethylene disilazane: 1.2 parts ○ 100 parts of anatase titanium fine particles and 12 parts of isobutyltrimethoxysilane Inorganic fine particles C obtained by treating the surface with (BET 115 m 2 / g): 0.5 part The obtained toner was air sieved with a sieve having a mesh opening of 75 μm to obtain [Toner 3], which was evaluated. .

(Comparative Example 2)
[Toner base 1] To 200 parts of the toner, the following inorganic fine particles were added, followed by stirring at 45 m / s for 3 minutes with a Henschel mixer (manufactured by Mitsui Miike Chemical Co., Ltd.).
○ Inorganic fine particles A (BET200m2 / g) obtained by treating the surface with 9 parts of hexamethylene disilazane on 100 parts of silica fine particles: 1.2 parts ○ The surface is treated with 8 parts of silicone oil on 100 parts of silica fine particles Inorganic fine particles B (BET 50 m2 / g) obtained in this manner: 0.85 parts of the obtained toner were air sieved with a sieve having a mesh size of 75 μm to obtain [Toner 4], which was evaluated.

~ Synthesis of low molecular weight polyester ~
(Production Example 2)
In a reaction vessel equipped with a condenser, stirrer and nitrogen inlet tube, 319 parts bisphenol A propylene oxide 2-mole adduct, 449 parts bisphenol A ethylene oxide 2-mole adduct, 243 parts terephthalic acid, 53 parts adipic acid and dibutyl Add 2 parts of tin oxide, react for 8 hours at 230 ° C. under normal pressure, and further react for 5 hours under reduced pressure of 10-15 mmHg, then add 7 parts of trimellitic anhydride to the reaction vessel at 180 ° C. under normal pressure. The mixture was reacted for 2 hours to obtain [Low molecular weight polyester]. [Low molecular weight polyester] had a number average molecular weight of 2000, a weight average molecular weight of 6600, Tg of 46 ° C., and an acid value of 1.3.

~ Creation of master batch ~
(Production Example 3-1)
1200 parts of water, 800 parts of carbon black and 1200 parts of [low molecular weight polyester] were mixed with a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). Grinding to obtain [Masterbatch 1].

(Production Example 3-2)
1200 parts of water, 800 parts of Cu-phthalocyanine 15: 3, and 1200 parts of [low molecular weight polyester] were mixed with a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.), the mixture was kneaded at 150 ° C. for 30 minutes using two rolls, and then rolled. The mixture was cooled and pulverized with a pulverizer to obtain [Masterbatch 2].

(Production Example 3-3)
1200 parts of water, C.I. I. 800 parts of Pigment yellow 155 and 1200 parts of [low molecular weight polyester] were mixed with a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.), the mixture was kneaded at 150 ° C. for 30 minutes using two rolls, rolled and cooled, and pulverized with a pulverizer. A master batch 3] was obtained.

(Production Example 3-4)
1200 parts of water, C.I. I. 800 parts of Pigment red 184 and 1200 parts of [low molecular weight polyester] were mixed with a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.), kneaded at 150 ° C. for 30 minutes using two rolls, rolled and cooled, and pulverized with a pulverizer. A master batch 4] was obtained.

~ Synthesis of organic fine particle emulsion ~
(Production Example 4)
In a reaction vessel in which a stir bar and a thermometer were set, 680 parts of water, 11 parts of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30: manufactured by Sanyo Chemical Industries), 69 parts of styrene, 110 parts of methacrylic acid, When 69 parts of butyl acrylate and 1 part of ammonium persulfate were charged and stirred at 400 rpm for 15 minutes, a white emulsion was obtained. The system was heated to raise the temperature in the system to 75 ° C. and reacted for 5 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours, and an aqueous dispersion of a vinyl resin (a copolymer of styrene-methacrylic acid-methacrylic acid ethylene oxide adduct sulfate sodium salt) [fine particles Dispersion] was obtained. The volume average particle diameter of the [fine particle dispersion] measured by LA-920 was 0.11 μm. A part of the [fine particle dispersion] was dried to isolate the resin component. The resin content Tg was 150 ° C.

-Adjustment of aqueous phase-
(Production Example 5)
240 parts of water, 13 parts of [fine particle dispersion], 50 parts of 50% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7): Sanyo Kasei Kogyo Co., Ltd., and 25 parts of ethyl acetate were mixed and stirred. A liquid was obtained. This is referred to as [aqueous phase].

~ Synthesis of intermediate polyester and prepolymer ~
(Production Example 6)
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen introduction pipe, 682 parts of bisphenol A ethylene oxide 2-mole adduct, 81 parts of bisphenol A propylene oxide 2-mole adduct, 283 parts of terephthalic acid, 22 parts of trimellitic anhydride And 2 parts of dibutyltin oxide were added, reacted at 230 ° C. under normal pressure for 8 hours, and further reacted for 5 hours at a reduced pressure of 10 to 15 mmHg to obtain an [intermediate polyester]. The [intermediate polyester] had a number average molecular weight of 2100, a weight average molecular weight of 9600, Tg of 55 ° C., an acid value of 0.5, and a hydroxyl value of 51.
Next, 410 parts of [Intermediate Polyester 1], 89 parts of isophorone diisocyanate and 500 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours. Polymer] was obtained. [Prepolymer] had a free isocyanate weight% of 1.60%. The solid content concentration of [Prepolymer] (calculated from the weight after standing at 150 ° C. for 45 minutes) was 50%.

~ Synthesis of ketimine ~
(Production Example 7)
In a reaction vessel equipped with a stirrer and a thermometer, 170 parts of isophoronediamine and 75 parts of methyl ethyl ketone were charged and reacted at 50 ° C. for 5 hours to obtain [ketimine compound]. The amine value of [ketimine compound] was 423.

~ Creation of oil phase ~
(Production Example 8-1)
In a container in which a stir bar and a thermometer are set, 50 parts of synthetic ester wax WAX, 30 parts of CCA (salicylic acid metal complex E-84: Orient Chemical Industry), 330 parts of ethyl acetate are charged and heated to 80 ° C. with stirring. After maintaining at 80 ° C. for 5 hours, it was cooled to 30 ° C. over 1 hour. Next, 250 parts of [Masterbatch 1] were mixed in the container for 1 hour to obtain [Raw material solution 1].
[Raw material solution 1] 132 parts were transferred to a container, and using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), a liquid feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 0.5 mm zirconia beads were 80% by volume. The pigment and WAX were dispersed under conditions of filling and 6 to 24 passes. Next, 200 parts of a 70 wt% ethyl acetate solution of [low molecular weight polyester] and 80 parts of ethyl acetate were added, followed by one pass with a bead mill under the above conditions to obtain [Pigment / WAX Dispersion 1]. The solid content concentration of [Pigment / WAX Dispersion 1] (calculated from the weight after standing at 150 ° C. for 45 minutes) was 50%.

(Production Example 9-1)
~ Toner granulation ⇒ Tonerization ~
[Pigment / WAX Dispersion 1] 206 parts, [Prepolymer] 30 parts, 20 wt% MEK-ST 10 parts, [Ketimine compound] 2.8 parts are put in a container, and TK homomixer (manufactured by Tokushu Kika) 5 After mixing at 000 rpm for 1 minute, 360 parts of [aqueous phase] was added to the vessel and mixed with a TK homomixer at 13,000 rpm for 20 minutes to obtain [Emulsion slurry 1]. [Emulsion slurry 1] was put into a container equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 8 hours, aging was carried out at 50 ° C. for 8 hours to obtain [Dispersion slurry 1].
[Dispersion Slurry 1] 100 parts of the resulting mixture were filtered under reduced pressure, washed thoroughly with water, the obtained cake was blown off, dried at 45 ° C. for 48 hours in a circulating drier, and then sieved with a sieve having a mesh opening of 75 μm. [Toner base 2] was obtained.

(Example 3)
[Toner base 2] To 100 parts of the toner base, the following inorganic fine particles were added, followed by stirring at 45 m / s for 3 minutes with a Henschel mixer (manufactured by Mitsui Miike Chemical Co., Ltd.).
○ Inorganic fine particle A (BET200m2 / g) obtained by treating the surface with 9 parts of hexamethylene disilazane to 100 parts of silica fine particles: 1.0 part ○ 100 parts of anatase type titanium fine particles and 12 parts of isobutyltrimethoxysilane Inorganic fine particles C obtained by treating the surface with (BET 115 m 2 / g): 0.5 part The obtained toner was air sieved with a 75 μm mesh sieve to obtain [Toner 5], which was evaluated. .

(Production Example 8-2)
[Pigment / WAX dispersion 2] was prepared in the same manner as in Production Example 8-1, except that [Master batch 1] in Production example 8-1 was changed to [Master batch 2].

(Production Example 8-3)
[Pigment / WAX dispersion 3] was prepared in the same manner as in Production Example 8-1, except that [Master batch 1] in Production example 8-1 was changed to [Master batch 3].

(Production Example 8-4)
[Pigment / WAX dispersion 4] was prepared in the same manner as in Production Example 8-1, except that [Master batch 1] in Production example 8-1 was changed to [Master batch 4].

(Production Example 9-2)
[Toner Base 3] was prepared in the same manner as in Production Example 9-1 except that [Pigment / WAX Dispersion 1] in Production Example 9-1 was changed to [Pigment / WAX Dispersion 2].

(Production Example 9-3)
[Toner Base 4] was prepared in the same manner as in Production Example 9-1 except that [Pigment / WAX Dispersion 1] in Production Example 9-1 was changed to [Pigment / WAX Dispersion 3].

(Production Example 9-4)
[Toner Base 5] was prepared in the same manner as in Production Example 9-1 except that [Pigment / WAX Dispersion 1] in Production Example 9-1 was changed to [Pigment / WAX Dispersion 4].

Example 4
[Toner 6] was obtained and evaluated in the same manner as in Example 3 except that [Toner Base 2] in Example 3 was changed to [Toner Base 3].

(Example 5)
[Toner 7] was obtained and evaluated in the same manner as in Example 3 except that [Toner Base 2] in Example 3 was changed to [Toner Base 4].

(Example 6)
[Toner 8] was obtained and evaluated in the same manner as in Example 3 except that [Toner Base 2] in Example 3 was changed to [Toner Base 5].

(Example 7)
[Toner base 2] To 100 parts of the toner base, the following inorganic fine particles were added, followed by stirring at 45 m / s for 3 minutes with a Henschel mixer (manufactured by Mitsui Miike Chemical Co., Ltd.).
○ Inorganic fine particle A (BET200m2 / g) obtained by treating the surface with 9 parts of hexamethylene disilazane on 100 parts of silica fine particles: 1.0 part ○ The surface with 8 parts of hexamethylene disilazane on 100 parts of silica fine particles Inorganic fine particles D (BET 50 m2 / g) obtained by treating No. 8: 0.85 parts of the obtained toner was air sieved with a sieve having a mesh size of 75 μm to obtain [Toner 9], which was evaluated.

(Example 8)
[Toner base 2] To 200 parts of the toner, the following inorganic fine particles were added, followed by stirring at 45 m / s for 2 minutes with a Henschel mixer (manufactured by Mitsui Miike Chemical Co., Ltd.).
○ Inorganic fine particles A (BET200m2 / g) obtained by treating the surface with 9 parts of hexamethylene disilazane on 100 parts of silica fine particles: 0.3 part ○ The surface with 8 parts of hexamethylene disilazane on 100 parts of silica fine particles Inorganic fine particles D (BET50m2 / g) obtained by treating with: 7 parts This mixed toner was treated with a hybridization system (manufactured by Nara Machinery Co., Ltd.) at 50 m / s for 3 minutes. The maximum temperature in the system was 33 ° C.
Furthermore, the following inorganic fine particles were added to 100 parts of the obtained toner, and the mixture was stirred for 3 minutes at 45 m / s with a Henschel mixer (manufactured by Mitsui Miike Chemical Co., Ltd.).
○ Inorganic fine particle A (BET200m2 / g) obtained by treating the surface with 9 parts of hexamethylene disilazane to 100 parts of silica fine particles: 1.0 part ○ 100 parts of anatase-type titanium fine particles and 12 parts of isobutyltrimethoxysilane Inorganic fine particles C obtained by treating the surface with (BET 115 m 2 / g): 0.5 part of the obtained toner was air sieved with a sieve having a mesh opening of 75 μm to obtain [Toner 10], which was evaluated. .

Example 9
[Toner Base 2] was finely classified with Elbow Jet (manufactured by Matsubo Co., Ltd.) to obtain [Toner Base 3].
[Toner base 3] To 100 parts of the toner base, the following inorganic fine particles were added, followed by stirring at 45 m / s for 3 minutes with a Henschel mixer (manufactured by Mitsui Miike Chemical Co., Ltd.).
○ Inorganic fine particles A (BET200m2 / g) obtained by treating the surface with 9 parts of hexamethylene disilazane to 100 parts of silica fine particles: 1.0 part ○ The surface with 100 parts of silica fine particles and 8 parts of hexamethylene disilazane Inorganic fine particles D (BET 50 m2 / g) obtained by treating No. 1: 0.85 parts of the obtained toner was air sieved with a sieve having a mesh size of 75 μm to obtain [Toner 11], which was evaluated.

(Evaluation item)
(1) Particle Size The particle size of the toner was measured with a particle size measuring device “Coulter Counter TAII” manufactured by Coulter Electronics Co., Ltd., with an aperture diameter of 100 μm. The volume average particle diameter and the number average particle diameter were determined by the particle size measuring instrument.
(2) Circularity and fine powder amount The average circularity was measured by a flow type particle image analyzer FPIA-1000 (manufactured by Toa Medical Electronics Co., Ltd.). A surfactant, preferably alkylbenzene sulfonate, is added in an amount of 0.1 to 0.5 mL as a dispersant in 100 to 150 mL of water from which impure solids have been removed in advance, and a measurement sample is further added in an amount of 0.1 to 0. Add about 5g. The suspension in which the sample was dispersed was subjected to dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the shape and distribution of the toner were measured with the above apparatus at a dispersion concentration of 3000 to 10,000 / μL.
(3) Penetration Degree of penetration of this toner stored at 50 ° C. for 24 hours was measured according to JIS K2235 (25 ° C.). A penetration meter VR-5610 (manufactured by Ueshima Seisakusho Co., Ltd.) was used as the penetration meter.
(4) Charge amount 6 g of developer was weighed and stirred until the charge was saturated. The stirred developer was charged into a metal cylinder that can be sealed and blown to determine the charge amount. The toner concentration was adjusted to 4.5 to 5.5 wt%.
(5) Fixability Using a remodeled imgio Neo 325 machine manufactured by Ricoh, a solid image of 1.0 ± 0.00% on plain paper and cardboard transfer paper (type 6200 made by Ricoh and copy printing paper <135> made by NBS Ricoh). Adjustment was performed so that 1 mg / cm 2 of toner was developed, and the temperature of the fixing belt was adjusted to be variable, and the temperature at which no offset occurred on plain paper and the lower limit of fixing temperature on thick paper were measured. The lower limit fixing temperature was defined as the fixing lower limit temperature at which the remaining ratio of the image density after rubbing the obtained fixed image with a pad was 75% or more.
(6) Powder pump transportability Using a remodeled imgio Neo 325 manufactured by Ricoh, a solid image and a thick paper transfer paper (type 6200 made by Ricoh and copy printing paper <135> made by NBS Ricoh) with a solid image of 1.0 The toner was adjusted so that a toner of ± 0.1 mg / cm 2 was developed, and continuously used in the range of the fixing lower limit temperature to the fixing lower limit temperature + 20 ° C. The number of printed sheets and the transportability at this time were evaluated.

Here, Table 1 shows the result of each evaluation item.

In Table 1, in the powder pump characteristics, “No image” means that the toner conveying portion has become clogged with toner, and the image cannot be output, so the evaluation has to be stopped. “Scratch” means that toner clogging occurred in the toner conveying section, and the toner supply amount decreased, but the evaluation was continued.
As shown in Examples 1 to 9, even when 10k continuous image formation was performed using a powder pump by setting the circularity to 0.92 to 0.98 and the penetration to 10 mm or more, there is a problem. There is no problem and there is no practical problem.
In Comparative Examples 1 and 2, 10k continuous image formation was performed using a powder pump by deviating from the range of circularity of 0.92 to 0.98 and penetration of 10 mm or more. However, toner clogging occurred. It occurs and no image is produced, which is problematic in practice.

1 is a diagram illustrating a schematic configuration of an image forming apparatus of the present invention. FIG. 2 is a diagram illustrating a configuration of a process cartridge of the image forming apparatus illustrated in FIG. 1. It is the schematic which showed the structure of the amorphous silicon photoconductor typically. 6 is a graph showing a relationship between an applied voltage and a charging potential of a photoreceptor. 1 is a schematic diagram illustrating a configuration of a charging device used in an image forming apparatus of the present invention. FIG. 6 is a schematic view illustrating a configuration of another type of fixing device used in the image forming apparatus of the present invention. It is a block diagram which shows schematic structure of an agent transfer apparatus. It is the schematic which shows the structure of an agent transfer apparatus. It is the schematic which shows the structure of the agent transfer apparatus of other embodiment. FIG. 3 is a diagram schematically illustrating the shape of a toner according to the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Photoconductor 11 Support body 12 Photoconductive layer 13 Surface layer 14 Charge injection blocking layer 15 Charge generation layer 16 Charge transport layer 2 Image forming unit 20 Process cartridge 3 Charging device 3a Charging roller 3b Cleaning roller 3c Core metal 3d Conductive rubber layer 3g Power supply 4 Exposure device 5 Developing device 5a Developing roller 5b Agitating and conveying screw 5c Doctor blade 5d Supply roller 5e Thin layer forming member 5f Power source 6 Transfer device 6a Intermediate transfer belt 6b, 6c, 6d Support roller 6e Primary transfer roller 6g Secondary transfer roller 7 Cleaning device 7a Cleaning blade 7b Support member 7c Recovery screw 7d Pressure spring 8 Fixing device 8a Heating roller 8b Pressure roller 80 Surf fixing device 81 Fixing film 82 Drive roller 83 Follower roller 84 Heating body 85 Fixing Temperature sensor 86 Flat substrate 87 Fixing heater 88 Pressure roller 100 Image forming apparatus 109 Paper feed unit 110 Pickup roller 111 Registration roller 112 Paper discharge roller 114 Toner storage 115 Transfer tube 120 Agent transfer device 121 Toner storage container 122 Base 130 Air pump 140 Powder pump

Claims (12)

The volume average particle size. 2 to 5.88 [mu] m of the toner or developer containing the toner, an image forming method using an image forming apparatus having a dosage transfer device transferring to the developing device using a powder pump,
The toner is
(1) manufactured after dispersing a colorant, a release agent, a polymer or a polymerizable monomer in an aqueous medium, and (2) circularity of 0.95 with a flow type particle image analyzer. (3) An image forming method , wherein the penetration of the toner measured in accordance with JIS K2235 is 10 mm or more. The image forming method according to claim 1,
The image forming method according to claim 1, wherein the storage container storing the toner in the agent transfer device is a deformable storage bag. The image forming method according to claim 1 or 2,
When the storage container is set in the main body of the image forming apparatus, the powder pump is drivingly connected to the driving unit of the main body of the image forming apparatus, and the developer or the toner is a part of a member that is moved by the driving connection. An image forming method , wherein the toner has a ratio of 0.7 to 2.0 μm of 10% by number or less as measured by a flow particle image analyzer. The image forming method according to any one of claims 1 to 3,
The powder pump is connected to a side surface of a transfer tube, and the transfer tube has one end connected to the developing device and the other end connected to an air supply unit.
Toner discharged from the container by the powder pump, an image forming method characterized in that it is transferred to the developing device by the air flow by the air supply means. The image forming method according to any one of claims 1 to 4,
The image forming method , wherein the toner has a volume average particle diameter (Dv) to number average particle diameter (Dn) ratio Dv / Dn of 1.25 or less . The image forming method according to any one of claims 1 to 5,
The image forming method , wherein the toner contains fine particles having an average particle size of 30 to 300 nm on the toner surface . The image forming method according to any one of claims 1 to 5,
An image forming method , wherein the toner has fine particles which are either or both of organic fine particles and / or inorganic fine particles present on the toner surface . The image forming method according to claim 1,
The toner is obtained by dissolving or dispersing a compound having an active hydrogen group, a polymer having a site capable of reacting with the compound having an active hydrogen group, a colorant, and a release agent in an organic solvent. was dispersed in an aqueous medium, after reacting the polymer with a compound having an active hydrogen group, or while the reaction, the organic solvent is removed, washed, image forming method characterized by drying . The image forming method according to any one of claims 1 to 8,
Wherein the image forming apparatus, image forming method, which comprises using an amorphous silicon photosensitive member. The image forming method according to any one of claims 1 to 9,
The image forming method , wherein the charging device has a charging member in contact with an image carrier. The image forming method according to claim 1,
The image forming apparatus includes a heating body provided with a heating element, a fixing film in contact with the heating body, and a pressure member in pressure contact with the heating body through the fixing film, and between the fixing film and the pressure member. An image forming method comprising: a fixing device that heats and fixes a recording member on which an unfixed image is formed with toner . The image forming method according to any one of claims 1 to 11,
The image forming apparatus uses a process cartridge that integrally supports an image carrier and at least one device selected from a charging device, a developing device, and a cleaning device, and is detachable from the main body of the image forming device. image forming method characterized in that there.

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